-
International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
G.A. Razuvaev Institute of Organometallic Chemistry of RAS,
Chemistry and Material Science Division of RAS
Scientific Council on Organic and Elementoorganic Chemistry of
RAS Russian Foundation for Basic Research
N.I. Lobachevsky Nizhny Novgorod State University Nizhny
Novgorod Science Center of RAS
INTERNATIONAL CONFERENCE «TOPICAL PROBLEMS OF ORGANOMETALLIC
AND COORDINATION CHEMISTRY» V RAZUVAEV LECTURES
Book of Abstracts
The conference is supported by
Bruker Ltd. (ООО «Брукер»)
September 3-9, 2010
Volga and Kama rivers Nizhny Novgorod – Elabuga – Ulyanovsk -
Nizhny Novgorod, Russia
-
International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
Organizing committee:
Gleb A. Abakumov (Chairman), Sergey M. Aldoshin, Mikhail Yu.
Antipin, Irina P. Beletskaya, Mikhail N. Bochkarev, Vladimir I.
Bregadze, Yury N. Bubnov, Anatoly L.
Buchachenko, Vadim Yu. Kukushkin, Vladimir K. Cherkasov (Vice
Chairman), Oleg N. Chupahin, Viktor A. Dodonov, Georgy A.
Domrachev, Dmitry F.Grishin, Mikhail P. Egorov,
Igor L. Eremenko, Alexandr I. Konovalov, Ilya I. Moiseev, Aziz
M. Muzafarov, Oleg M. Nefedov, Elena S. Shubina, Klara G. Shalnova
(Scientific Secretary), Oleg G. Sinyashin.
Program committee:
Gleb.A. Abakumov (chairman), Irina P. Beletskaya, Mikhail N.
Bochkarev, Vladimir I.
Bregadze, Yury N. Bubnov, Vladimir K. Cherkasov, Dmitry F.
Grishin, Mikhail P. Egorov, Elena S. Shubina, Oleg G. Sinyashin
Travel itinerary:
-
International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
Plenary lectures
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
PL1
NANOSIZED CATALYTIC SYSTEMS IN ORGANOMETALLIC AND ORGANIC
CATALYSIS
I.P. Beletskaya
Moscow State University, 119991, Leninskie Gory, Moscow,
RUSSIA
In the lecture two topics will be considered:
1. the problem of leaching and recycling of organometallic and
organic catalysts; 2. cross-coupling reactions for
carbon-heteroatom (C-P, C-S, C-Se, C-N) bond
formation. e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
PL2
NOVEL TRANSITION METAL-CATALYZED METHODS FOR SYNTHESIS AND
FUNCTIONALIZATION OF ARENES AND HETEROARENES
V. Gevorgyana
aDepartment of Chemistry, University of Illinois at Chicago,
Chicago, Illinois USA
A set of novel efficient transition metal-catalyzed
methodologies for synthesis of multisubstituted carbo- and
heterocycles has been developed [1-7]. Commonly, regioselective
synthesis of carbo- and heterocycles possessing various functional
groups is not a trivial task. We have shown, however, that
incorporation of migrating step(s) in the cyclization cascade often
helps solving this problem. Thus, it was found that in the presence
of Cu-, Ag-, and Au catalysts, a number of groups, such as Hal-,
RS-, AcO-, TsO-, Ar-, and SiR3 could undergo 1,2- or 1,3-migration,
or in some cases even double migration, which allows for
expeditious synthesis of densely-functionalized carbo- and
heterocycles, which are not easily accessible via existing
techniques. We have also explored a direct Pd-catalyzed C-H
functionalization approach toward synthesis of multisubstituted
aromatic and heteroaromatic molecules [8-11]. Thus, a novel
silicon-tether approach for the Pd-catalyzed C-H arylation of
phenols has been developed. Next development involved employment of
the PyDipSi-, a Si-tethered directing group in the Pd-catalyzed C-H
acyloxylation and halogenation reactions. The PyDipSi group is
traceless or can easily be converted into a variety of useful
functionalities. The scope of these transformations will be
demonstrated and the mechanisms will be discussed. [1] J. T. Kim,
A. V. Kel'in, V. Gevorgyan, Angew. Chem., Int. Ed. 2003, 42,
98-101. [2] A. W. Sromek, A. V. Kel’in, V. Gevorgyan, Angew. Chem.,
Int. Ed. 2004, 43, 2280-2282. [3] A. W. Sromek, M. Rubina, V.
Gevorgyan, J. Am. Chem. Soc. 2005, 127, 10500-10501. [4] A. S.
Dudnik, V. Gevorgyan, Angew. Chem., Int. Ed. 2007, 46, 5195-5197.
[5] T. Schwier, A. W. Sromek, D. L. M. Yap, D. Chernyak, V.
Gevorgyan, J. Am. Chem. Soc. 2007, 129, 9868-
9878. [6] A. S. Dudnik, A. W. Sromek, M. Rubina, J. T. Kim, A.
V. Kel'in, V. Gevorgyan, J. Am. Chem. Soc. 2008,
130, 1440-1452. [7] A. S. Dudnik, Y. Xia, Y. Li, V. Gevorgyan,
V. J. Am. Chem. Soc. 2010, 132, 7645-7655. [8] I. V. Seregin, V.
Ryabova, V. Gevorgyan, J. Am. Chem. Soc. 2007, 129, 7742-7743. [9]
C. Huang, V. Gevorgyan, J. Am. Chem. Soc. 2009, 131, 10844-10845.
[10] A. S. Dudnik, V. Gevorgyan, Angew. Chem., Int. Ed. 2010, 49,
2096-2098. [11] N. Chernyak, A. S. Dudnik, C. Huang, V. Gevorgyan,
J. Am. Chem. Soc. 2010, 132, 8270-8272.
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
PL3
STUDIES OF BIOMIMETIC METALLOPORPHYRIN MODELS
Roger Guilard
Université de Bourgogne, ICMUB (UMR 5260), 9 avenue Alain
Savary, BP 47870, 21078 Dijon Cedex, FRANCE.
Our research effort in the field of bioinspired chemistry has
spanned over three decades, with much of our effort being devoted
to the synthesis and characterization of metalloporphyrin model
compounds which can perform or mimic different biochemical,
enzymatic and photochemical functions, the exact nature of which
will vary with the properties of the specific tetrapyrrolic
macrocycle being investigated. Several high points of our previous
work as well as a discussion of our most recent investigations in
the area will be given in the current talk which is divided into
three main sections: I. Porphyrins with metal-carbon bonds which
can lead to a better understanding of the
evolution of P 450 cytochrome derivatives; II. Pacman porphyrins
which can selectively reduce dioxygen by a four electron
mechanism
mimicking the cytochrome c oxydase, and III. Compounds which
mimic the energy and electron transfer modules of Photosystems I
and
II, our current interest. The above three topics have led to
major collaborations over a number of years with Karl Kadish, James
P. Collman and Pierre Harvey on the above topics I, II and III,
respectively. Our advances in these areas were also made possible
by the continuous support from numerous other collaborators as well
as the important involvement of my own coworkers over the years,
most notably Drs. Panayotis Cocolios, Alain Tabard, Jean-Michel
Barbe, Claude Gros and Christine Stern. [1] Guilard, R.; Kadish, K.
M., Chem. Rev. 1988, 88, 1121. [2] Collman, J. P.; Hutchison, J.
E.; Lopez, M. A.; Tabard, A.; Guilard, R.; Seok, W. K.; Ibers, J.
A.; L'Her, M.,
J. Am. Chem. Soc. 1992, 114, 9869. [3] Harvey, P. ; Stern, C. ;
Guilard, R. ; « Bio-Inspired Molecular Devices of the Antennas in
Photosynthetic
Bacteria », Handbook of Porphyrin Science, World Scientific,
2010, Vol. 11, in press. e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
PL4
SOME PROGRESS IN METAL-METAL BONDING
Rhett Kempe
Anorganische Chemie II, Universität Bayreuth, 95440 Bayreuth,
Germany. Chemical bonding and in particular the nature of a
chemical bond, the electronic structure and its reactivity, is of
fundamental interest. Metal-metal bonding has received a lot of
attention recently. In the talk it is focussed on two topics: polar
metal-metal bonds and quintuple bonding. First, recent progress in
synthesising polar metal-metal bonds namely unsupported bonds
between rare earths (RE) and transition metals (TM) is discussed
[1] with a special focus on using such bond formation methodologies
to generate highly reactive albeit in solution and in the solid
state stable RE-TM core-shell compounds [2]. Secondly, recent
progress in quintuple bonding is discussed [3] with a special focus
on synthesising compounds with ultra-short metal-metal bonds [4]
and understanding quintuple bonds by their reactivity [4]. [1] M.
V. Butovskii, O. L. Tok, F. R. Wagner and R. Kempe, Angew. Chem.,
Int. Ed., 2008, 47, 6469-6472. [2] M. V. Butovskii, Ch. Döring, V.
Bezugly, F. R. Wagner, Y. Grin and R. Kempe, Nature Chem., 2010, 2,
July
issue. [3] F. R. Wagner, A. Noor and R. Kempe, Nature Chem.,
2009, 1, 529-536. [4] Noor, F. R. Wagner and R. Kempe, Angew. Chem.
Int. Ed., 2008, 47, 7246-7249. [5] A. Noor, G. Glatz, R. Müller, M.
Kaupp, S. Demeshko and R. Kempe, Nature Chem., 2009, 1, 322-325.
e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
PL5
SYNCHRONIZED COOPERATION OF PD AND BRØNSTED ACID IN ADDITION OF
SECONDARY PHOSPHINE OXIDES WITH ALKYNES
M. Tanaka
Chemical Resources Laboratory, Tokyo Institute of Technology
4259-R1-13 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
Some ten years ago an interesting regiochemical reversal induced
by Ph2P(O)OH in Pd-catalyzed addition of Ph2P(O)H with terminal
acetylenes was disclosed and [Ph2P(O)-Pd-OP(O)Ph2] species was
proposed as key intermediate.1 During the course of
addition-carbocyclization of α,ω-diynes with HP(O)Ph2,2 however, we
have come across unexpected result that suggests the real active
species is a zwitterionic palladium complex formed though hydrogen
bonding with ligated P(O)Ph2 moiety with a Ph2P(O)OH (Scheme 1).
Detailed study has shown (1) HP(O)Ph2 is activated by palladium
center through oxidative addition, (2) resulting species interacts
with Ph2P(O)OH through hydrogen bonding, forming an intermediate
having PPh2(O-H-OP(O)Ph2), which is a sort of phosphine ligand and
prone to dissociate to generate a vacant coordination site, and (3)
then an alkyne occupies the site to undergo insertion. Thus, the
whole process is carried by duo of palladium and Ph2P(O)OH. This
type dual activation facilitates the catalysis more efficiently as
compared with the regime without Ph2P(O)OH or other Brønsted acids
and has been found to successfully work in addition of
dialkylphosphine oxide to alkynes (Table 1). Brief summary of H-P
bond addition reactions and recent progress are presented.
HOP
HP
HOP
R
P
RPd
L
PPh2
L
OPO HR
PdL
PPh2H
L
OP
O HI-1
PdL L
Markovnikov addition
P = P(O)Ph2
C6 H P(O)nBu2
C6
P
Pd(dba)2 (5 mol %)
+ toluene-d80.500 mmol0.500 mmol
yield (%)
15
H-P conv (%)
2680100
< 124
859
110 єC, 3 h
HOP(O)Ph2 (5%)
yes
no
yes
yes
ligand (P/Pd = 2)
dppben
dppben
PPh3PMePh2
86100dppeyes
Table 1. Addition of Bu2P(O)H with 1-octyneScheme 1
[1] L.-B. Han, R. Hua, M. Tanaka, Angew. Chem., Int. Ed. Engl.
1998, 37, 94. [2] J. Kanada, K.-i. Yamashita, S. K. Nune, M.
Tanaka, M. Tetrahedron Lett. 2009, 50, 6196. Acknowledgements -
e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
Section Lectures
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S1
OXO- AND IMIDO-ALKOXIDE VANADIUM COMPLEXES AS PRECATALYTS FOR
THE GUANYLATION OF AMINES
Antonio Antiñolo,a Fernando Carrillo-Hermosilla,a Javier
Romero-Fernández,a Carlos
Alonso-Moreno,a Ana M. Rodríguez,a Isabel López-Solera,a and
Antonio Oteroa
a Área de Química Inorgánica Facultad de Ciencias Químicas.
Universidad de Castilla-La Mancha
Campus Universitario de Ciudad Real, 13071-CIUDAD REAL,
SPAIN
The catalytic production of organic molecules of interest is one
of the most important applications of the Inorganic Chemistry. In
fact, the compounds containing nitrogen, such as amines, enamines,
imines and derivatives are interesting compounds as bulk chemicals,
or fine chemicals. At the present, there have been intensified the
studies related to the synthesis and behaviour of transition metal
complexes that contain in his structure one or more terminal imido
ligands. These ligands could be implied in different catalytic
processes or acting as stabilizer ligands of the active centre. In
this communication, we present the synthesis and characterization
of a family of oxoalkoxide derivatives of Vanadium (V),
[VCl3-x(O)(OR)x] (x = 1, 2; R = Me, Et, Pr), as precursors of
imidoalkoxide complexes, {VCl3-x[N(2,6-iPr2C6H3)](OR)x}2 (x = 1, 2;
R = Me, Et, Pr). These complexes are very efficient catalysts in a
guanylation process of aromatic amines, to the obtaining the
corresponding N,N',N”-guanydines.
NH2
+ iPrN=C=NPriN
NH
NH
Acknowledgements - We gratefully acknowledge financial support
from the MICINN of Spain (Grants No. CTQ2009-09214 and ORFEO
PROJECT-CONSOLIDER INGENIO No. CSD2007-00006), and the Junta de
Comunidades de Castilla-La Mancha (Grant No. PCI08-0032-0957).
e-mail: [email protected]; [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S2
WHAT INTERATOMIC DISTANCES WE MAY CONSIDER AS A CHEMICAL BOND
?
M.Yu. Antipin
A.N. Nesmeyanov Institute of Organoelement Compounds of the
Russian Academy of
Sciences, 119991, Vavilov Str. 28, B-334, Moscow, RUSSIA.
Traditionally, a chemical bond between two atoms or groups of
atoms is considered to exist in those cases when the distance
between “bonded” atoms is close to the sum of their covalent radii.
Quite many systems of these empirical values were described in
literature, and for the same atom the covalent radius sometimes may
differ by 0.01Å in different systems. More complicated situation
about declaration the presence/absence of chemical bond arises when
interatomic distance is larger than the sum of covalent radii, but
is less than the sum of their van-der-Waals radii. This is the
interval, where interatomic interactions are considered to be
attractive and correspond to “additional” interactions, weak
interactions, hydrogen bonds, “specific” interactions, etc. But in
different systems of van-der-Waals radii (at least 8 such systems
exists) the difference in radius for the same atom may be as large
as 0.2 Å or even more. Therefore, it is very difficult sometimes to
declare the presence or absence of chemical bond (attractive
interaction) between two atoms on the basis of interatomic
distances only, because result may depend, especially in case of
weak interactions, on the choice of the system of van-der-Waals
radii. In these cases the final conclusion will depend on chemical
intuition and sense. So, interatomic distances in some cases (e.g.
weak bonds) may not be considered as the only criteria of chemical
bond, and other approaches must be developed. At present,
physically most valid criteria of a chemical bond were suggested by
R. Bader et al. in the frame of his theory “Atoms in Molecules”
(AIM), and based on analysis of the topology of the full electron
density distribution (ED) function, which may be obtained from
accurate X-ray diffraction data or calculated from quantum
chemistry. According to AIM, chemical bond (interatomic
interaction) exists between two atoms, if there is a “bond path”
and critical point (3,-1) between them in the relief of ED, and the
density of the potential energy at critical point is negative.
Note, that there is no interatomic distances in this definition,
and all named values may be obtained from the accurate X-ray
diffraction experiment. In the lecture, some examples of different
molecular systems with large set of long and short interatomic
distances, corresponding bonding/non-bonding situation, will be
analysed in the frame of AIM theory. The systems studied include
transition metal complexes and clusters, hypervalent derivatives of
Si, Ge, Sn, cabroranes and metallocarboranes, strained organic
molecules, molecular donor-acceptor complexes, and others.
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S3
NEW MATERIALS FOR ORGANIC LIGHT EMITTING DIODES
Mikhail N. Bochkarev and Marina A. Katkova
G. A. Razuvaev Institute of Organometallic Chemistry of Russian
Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod,
RUSSIA.
During 10 years in IOMC active search and investigation of new
effective materials for OLEDs are currying out. Main efforts were
concentrated on rare earth metals and their derivatives because low
work function of these metals and same advantages which these
metals have as emitters. In presentations achievements in the area
of cathode materials and emitters are quoted. It was found that
heterobimetallic composite Tm:Yb used as cathode in simple OLED of
configuration ITO/TPD/Alq3/M (ITO- anode, TPD – hole-transport
layer, Alq3 – emitting layer, M – cathode) provides best
characteristics of a device as compared with tradition cathodes –
Al, Ca:Al, Mg:Al. Four groups of rare earth complexes were
synthesized and studied as emitters: (i) 8-oxyquinolates Lnq3 and
their derivatives containing in 2-position of a ligand Me, CN and
NH2 groups; (ii) imidodiphosphinate complexes Ln(pip)3; (iii)
2-mercaptobenzothiazolate complexes Ln(mbt)3 and (iv) phenolates
containing in 2-position of the ligand 2-benzoimidazol-2-yl
(Ln(non)3), 2-benzoxyazol-2-yl (Ln(oon)3) and 2-benzothiazol-2-yl
(Ln(son)3) substituents. Highest efficiency and brightness were
obtained for scandium complex Sc(oon)3. Most of the complexes were
structurally characterized. For Lnq3, Ln(non)3, Ln(oon)3 and
Ln(son)3 DFT calculation were performed. Some of these data have
been confirmed by UPS measurements (Dr. S.E. Alexandrov, Dr. A.L.
Shakhmin, St. Petersburg State Polytechnic University) which gave a
chance to determine the energy level of HOMO and LUMO of the used
compounds. The found value of HOMO and LUMO turned out in good
agreement with electroluminesecent characteristics of the materials
tested in modeling OLED devices of configuration ITO/TPD/Ln
complex/Bath/Yb (Bath – electron-transporting layer). Design of
effective electroluminescent complexes of rare earth metals are
discussing. Acknowledgements - The work was supported in part by
the Russian Foundation of Basic Research (Grants, 10-03-00190,
09-03-97016p). e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S4
METALLOCOMPLEXES WITH CARBORANECHALCOGENOLATE LIGANDS
Vladimir I. Bregadze,a Sergey A. Glazun, a Olga B. Zhidkova, a
Zoya A. Starikova, a Nisha P. Kushwah, b Manoj K. Pal, b Amey P.
Wadawale, b Vimal K. Jain b,
Yuguang Lic, Qibai Jiangc, Yizhi Lic, Hong Yanc
a A.N.Nesmeyanov Institute of Organoelement Compounds, RAS, 28
Vavilov Str. 119991 Moscow, Russia, b Chemistry Divison, Bhabha
Atomic Research Center, Mumbai, India,
cState Key Laboratory of Coordination Chemistry, School of
Chemistry and Chemical Engineering, Nanjing University, Jiangsu
210093, China
The reactions of [M2Cl2(µ-Cl)2(PMe2Ph)2] with
mercapto-o-carboranes in the presence of pyridine afforded
mono-nuclear complexes 1-3. The treatment of [PdCl2(PEt3)2] with
Ph-o-CB10H10CSH yielded trans-derivative 4 [1]. A variety of
palladium and platinum complexes (5-7) have been isolated by the
reactions of Ph-o-CB10H10CSeNa with [M2Cl2(µ-Cl)2(PR3)2] and
[MCl2(PR3)2] [2].
PdPEt3S
Ph
Et3P
Ph
S
4
Se
Pd Pd
Cl
Se
Et3P
PEt3
Cl
Ph
Ph
5PR3=PMe2Ph 6 PMePh2 7
PtSe
Se
R3P
R3P
Ph
Ph
M=Pd, Pt; R=H, Ph
1 - 3
R
Me2PhPM
PyCl
S
CBH
A series of new compounds based on cobalt complex containing
o-carborane thiolate ligand, CpCoS2C2B10H10, was prepared, such as
CpCo(S2C2B10H9)(CH=CH-C(O)R) (8),
[(CpCoS2C2B10H10)(CpCoSC2B10H11)(SC4H9)] (9),
[(CpCo)2S2(S2C2B10H10)(SC2B10H10) (SC4H9)] (10),
[(CpCo)2Co(SC4H9)6]+[Co(S2C2B10H10)2]- (11), [(CpCo)2Co(SC2B10H11)
(SC4H9)5]+[Co(S2C2B10H10)2]- (12) [3-5]. [1] N.P. Kushwah, V.K.
Jain, A. Wadawale, O.B. Zhidkova, Z.A. Starikova, V.I. Bregadze, J.
Organomet. Chem., 2009, 694, 4146-4151. [2] M.K. Pal, V.K .Jain,
N.P. Kushwah, A. Wadawale, S.A. Glazun, Z.A. Starikova, V.I
.Bregadze, J. Organomet. Chem., 2010, in press. [3] Y. Li, Q.
.Jiang, Y. Li, H. Yan, V.I. Bregadze, Inorg. Chem., 2010, 49, 4-6.
[4] Y. Li, Q. Jiang, X. Zhang, Y. Li, H. Yan, V.I. Bregadze, Inorg.
Chem., 2010, 49, 3911-3917. [5] Y. Li, Q. Jiang, X. Shen, Y. Li, H.
Yan, V.I. Bregadze, Inorg. Chem., 2010, 49, DOI: 10.1021/ic100497h.
Acknowledgements Authors are grateful to the Russian Foundation for
Basic Researches (RFBR), Russian Academy of Sciences (RAS),
National Science Foundation of China (NSFC) and Department of
Science and Technology (DST), New Delhi, for financial support
under ILTP project of RAS-DST No. B-5.22, RFBR-NSFC joint grant
(09-03-92216 and 20911-20057) and RFBR-DST grant (10-03-92657-IND
and RUSP-1005). e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S5
SCADIUM TERMINAL IMIDO COMPLEXES: SYNTHESIS, STRUCTURES AND
REACTIVITIES
Y. Chen, E. Lu and J. Chu
State Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry,
Chinese Academy of Sciences,354 Fenglin Road, Shanghai 200032,
P.R.C. The terminal imido complexes of early-transition-metal,
which containing the M=N double bond, have attracted intensive
interesting in last two decades, due to their applications in the
group transfer and catalysis procedures, as well as the unique
structural properties [1]. Many examples of group 4 and 5 metal
terminal imido complexes as well as the actinide ones have been
reported. On the other hand, the synthesis of terminal imido
complexes of rare-earth-metal (Sc, Y and lanthanide) is difficult
[2]. The rare-earth-metal terminal imido species once formed easily
assemble as the more stable bimetallics µ2-bridged imido complexes
or multi-metallic imido clusters, or undergo reactions with
solvents via C-H bond activation [3]. The increased Lewis acidity
of the rare-earth-metal ion and high active Ln=NR double bond
should led to interesting reactivities. The understanding of the
nature of Ln=NR double bond is also of fundamental concern. Herein
we present the use of multidentate nitrogen ligands to isolate and
structurally characterize of the scadium terminal imido complexes
as well as the reactivities of these complexes.
LSc=NR
L: multidentate nitrogen monanionic ligands
Reference: [1] (a) A. P. Duncan and R. G. Bergman, The Chemical
Record., 2002, 2, 431; (b) L. H. Gade and P. Mountford, Coord.
Chem. Rev., 2001, 216 – 217, 65; (c) D. J. Mindiola, Acc. Chem.
Res., 2006, 39, 813. [2] G. R. Giesbrecht and J. C. Gordon, Dalton
Trans., 2004, 2387. [3] (a) A. A. Trifonov, M. N. Bochkarev, H.
Schumann and J. Loebel, Angew. Chem. Int. Ed. Engl., 1991, 30,
1149; (b) Z. W. Xie, S. W. Wang, Q. C. Yang and T. C. W. Mak,
Organometallics, 1999, 18, 1578; (c) S. W. Wang, Q. C. Yang, T. C.
W. Mak and Z. W. Xie, Organometallics, 1999, 18, 5511; (d) H. S.
Chan, H. W. Li and Z. W. Xie, Chem. Commun., 2002, 652; (e) J. C.
Gordon, G. R. Giesbrecht, D. L. Clark, P. J. Hay, D. W. Keogh, R.
Poli, B. L. Scott and J. G. Watkin, Organometallics, 2002, 21,
4726; (f) D. J. Beetstra, A. Meetsma, B. Hessen and J. H. Teuben,
Organometallics, 2003, 22, 4372; (g) A. G. Avent, P. B. Hitchcock,
A. V. Khvostov, M. F. Lappert and A. V. Protchenko, Dalton Trans.,
2004, 2272; (h) D. M. Cui, M. Nishiura and Z. M. Hou, Angew. Chem.
Int. Ed., 2005, 44, 959; (i) C. L. Pan, W. Chen, S. Y. Song, H. J.
Zhang and X. W. Li, Inorg. Chem., 2009, 48, 6344. Acknowledgements:
This work was supported by the National Natural Science Foundation
of China and Chinese Academy of Sciences. e-mail:
[email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S6
LIVING CATALYZED-CHAIN-GROWTH POLYMERIZATION AND BLOCK
COPOLYMERIZATION OF ISOPRENE BY RARE-EARTH METAL ALLYL
PRECURSORS BEARING CGC LIGAND
D. Cuia, and Z. Jiana
aState Key Laboratory of Polymer Physics and Chemistry,
Changchun Institute of Applied Chemistry, Chinese Academy of
Sciences, 130022, Renmin str, 5625, Changchun, CHINA.
Chain transfer polymerization has gathered an upsurge in
research interests in the past decade, as which presents various
advantages over single component catalyst polymerization such as
atom economy, molecular weight control, and especially terminal
functionlization of nonpolar polymers [1,2]. However, chain
transfer is a dominant chain-termination pathway, giving oligomeric
or low molecular weight polymers owing to the potential catalyst
poisoning and deactivation. Therefore a process in which the
transmetallation between the growing metal centers and the chain
transfer agents majorly metal alkyl compounds, possessing a rapid
and reversible character without termination reactions, sounds
promising. This is the so called catalyzed-chain-growth (CCG) [3].
Herein we report the novel aminophenyl functionalized
mono-cyclopentadienyl constrained-geometry-conformation lanthanide
bis(allyl) precursors (C5Me4-C6H4-o-NMe2)Ln(η3-C3H5)2 (Ln = Y (1),
Nd (2), Gd (3), Dy (4)). Complexes 1–4 with the activation of
AliBu3 and [PhMe2NH][B(C6F5)4] displayed high cis-1,4 selectivity
(98%) and excellent livingness for isoprene polymerization.
Remarkably, in the presence of an excess amount of AliBu3, the
unprecedented living CCG, a rapid and reversible transmetalation
without termination, was achieved, indicating that each catalytic
metal center produced more than one polymer chain with high
molecular weight. [1] S. B. Amin and T. J. Marks, Angew. Chem.,
Int. Ed., 2008, 47, 2006-2025. [2] R. Kempe, Chem.–Eur. J., 2007,
13, 2764-2773. [3] A. Valente, P. Zinck, A. Mortreux and M.
Visseaux, Macromol. Rapid Commun., 2009, 30, 528-531.
Acknowledgements - This work is supported by The National Natural
Science Foundation of China for project No. 20934006. The Ministry
of Science and Technology of China for projects Nos. 2005CB623802;
2009AA03Z501. e-mail: [email protected], [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S7
POLYPHOSPHORYLPORPHYRINS – NEW BUILDING BLOCKS FOR
SUPRAMOLECULAR NETWORKS FORMATION
Yu.G. Gorbunovaa,b, Yu. Yu. Enakievaa,b, E.V. Vinogradovaa, A.
Bessmertnykhc, C. Sternc,
S.E. Nefedovb, Y. Rousselinc, A.Yu. Tsivadzea,b and R.
Guilardc
aA.N. Frumkin Institute of General & Inorganic Chemistry of
RAS, bN.S. Kurnakov Institute of General & Inorganic Chemistry
of RAS, Leninskiy p.31, Moscow, 119991 RUSSIA, cUniversité de
Bourgogne - ICMUB UMR CNRS 5260, 9 avenue Alain Savary - BP 47870,
21078 Dijon, FRANCE Metalloporphyrins are remarkable precursors in
supramolecular chemistry and the rapid development of this
chemistry led to many self-assembled networks1. The specific design
of networks provides solid-state materials with unique electronic,
optical, mechanical and catalytic properties.
Polyphosphorylporphyrins represent a novel group of promising
precursors with attractive binding properties, where P=O groups
play a key role in the self-assembling process. Recently we have
synthesized porphyrins possessing phosphoryl groups2 at the
periphery of the macrocycle. Pd-catalysed coupling has been used to
prepare meso-polyphosphorylporphyrins. The features of the networks
formation using the synthesized
meso-poly(diethoxyphosphoryl)porphyrins have been investigated in
detail by means of X-ray crystallography, NMR, ESR and UV-Vis
spectroscopy. It was shown that depending from the structure of
porphyrin, the nature of transition metal and anion during complex
formation as the ratio of reagents and solvent, 1D or 2D
coordination polymers can be synthesized.
2D network We have been also involved in the synthesis of
β-diethoxyphosphoryl substituted derivatives. These compounds are
also promising precursors for molecular materials since
β-functionalized porphyrins play a key role in the naturally
occurring porphyrin self-assembling. It should be noted that
β-phosphoryl porphyrins were unknown. Our first attempts have
revealed that the transition metal-catalyzed phosphorylation of
β-monobromo-substituted porphyrins is also a suitable method for
the synthesis of such derivatives. [1] I. Beletskaya, V.S. Tyurin,
A.Yu.Tsivadze, R.Guilard, C.Stern //Chem. Rev., 2009, 109, 1659.
[2] Yu.Yu. Enakieva, A.G. Bessmertnykh, Yu.G. Gorbunova, C. Stern,
Y. Rousselin, A.Yu. Tsivadze, and R. Guilard // Org. Lett., 2009,
11, 3842. Acknowledgements - This work was supported by ARCUS 2007
Burgundy-Russia project, Russian Foundation for Basic Research
(grant#07-03-92212), the CNRS and Russian Academy of Sciences.
e-mails: [email protected], [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S8
COMPLEXES WITH "SUPERPODAL LIGANDS" – REACTIVITY ENHANCEMENT,
SURFACE MODIFICATION, AND
INFORMATION STORAGE
Andreas Grohmann
Technische Universität Berlin, Institut für Chemie, Straße des
17. Juni 135,
10623 Berlin, Germany; e-mail: [email protected]
Our work delineates some unusual reactivity patterns in iron
complexes of highly
symmetrical polyamines/polyimines L and pyridine-derived
polyphosphanes L’. The
complexes have a “labile” sixth coordination site, thereby
creating a platform for reactivity
studies of small monodentate ligands.[1]
The modification of the ligands with respect to variations in
the donor set and—in the
case of FeN6 complexes—spin state switching will also be
discussed. With a view to creating
spin-switchable units on surfaces, we are investigating the
self-assembly of iron(II)
complexes containing pairs of planar terdentate nitrogen ligands
on highly oriented pyrolytic
graphite (HOPG).[2]
[1] A. Grohmann, Dalton Trans. 2010, 39, 1432 – 1440.
[2] M. S.Alam, M. Stocker, K. Gieb, P. Müller, M. Haryono, K.
Student, A. Grohmann, Angew. Chem.
2010, 122, 1178 – 1182; Angew. Chem. Int. Ed. 2010, 49, 1159 –
1163.
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S9
CHEMISTRY OF PYRIDINE-2-SELENOLATE AND -TELLUROLATE COMPLEXES OF
PLATINUM GROUP METALS AND MAIN GROUP
ELEMENTS
Vimal K. Jaina, G. Kedarnath, Rohit Singh Chauhan, Amey P.
Wadawale and Rakesh K. Sharma
aChemistry Division, Bhabha Atomic Research Centre, Mumbai-400
085, INDIA
.
Pyridine-2-chalcogenolate ligands (I) represents an interesting
family of hemilabile ligands. The chemistry of 2-oxo and 2-thio
pyridine ligands has been extensively explored, while the
coordination chemistry of 2-selenopyidines has been investigated
only recently by others and us. In contrast, chemistry of
2-telluropyridines is still in infancy.
This presentation aims to discuss our results on
pyridine-2-selenolate and-tellurolate
complexes of platinum group metals and main group elements1-3.
Reactions of [Pt(PPh3)4] with dipyridylditellurides yield, in
addition to simple oxidative addition product, [Pt(Tepy)2(PPh3)2],
a serendipitous complex, [Pt(Te)(Tepy)2)(PPh3)] containing
tellurium(0) as a ligand. Reactions of metal halides of main group
elements with the NaEpy (E = Se or Te) afforded several selenolate
and tellurolate complexes including [Cd(Tepy)2(tmeda)],
[Hg(Tepy)2], [M(Sepy)3] (M = Sb or Bi), [In(Sepy)3], [Cu(Epy)]4 (E
= Se and Te). The main group metal complexes have been used as
molecular precursors for the preparation of metal chalcogenide
nanostructures and deposition of thin films.
[1] G. Kedarnath, V.K. Jain, A. Wadawale and G. K. Dey, Dalton
Trans., 2009, 8378 [2] R. S. Chauhan, G. Kedarnath, A. Wadawale, A.
Muñoz-Castro, R. Arratia-Perez, V. K. Jain and W. Kaim,
Inorg. Chem., 2010, 49, 4175 [3] R. K. Sharma, G. Kedarnath, V.
K. Jain, A. Wadawale, M. Nalliath, C. G. S. Pillai and B.
Vishwanadh,
(unpublished results) e-mail: [email protected];
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S10
LANTHANOID AND GROUP 2 COMPLEXES INVOLVING ARYLOXIDE LIGANDS OF
MODERATE STERIC BULK
Glen B. Deacon, a Peter C. Junk,a Graeme J. Moxeya and Josh P.
Townleya
aSchool of Chemistry, Monash University, Clayton, Victoria,
3800, AUSTRALIA
Traditionally, ligands of large steric bulk have been used to
stabilize and isolate metal complexes and to control the
coordination environment of the metal, while inhibiting
polymerization of the compounds, in metal-organic chemistry.
Phenolate ligands with sterically demanding groups on the
2,6-positions (e.g. tBu, Ph) have been used in this regard to
synthesise lanthanoid aryloxides with low coordination numbers and
compounds of high structural novelty.1 Recently we have been
interested in phenolate ligands of modest steric2 bulk to moderate
the degree of de-aggregation in attempts to form polynuclear
lanthanoid and group 2 cage complexes. To do this, we have used the
2,6-dimethylphenolate, 2,4,6-trimethylphenolate and
2,4-di-tert-butyl phenolate in metal based reactions (equation 1)
to study these systems. In this presentation, the results obtained
from this chemistry will be discussed.
M + Hg(C6F5)2 + 2LH -------> ML2 + 2C6F5H + Hg↓ (1a) (M =
Group 2 or lanthanoid metal)
2Ln + 3Hg(C6F5)2 + 6LH -------> 2LnL3 + 6C6F5H + 3Hg↓
(1b)
2Ln + 6LH --------> 2LnL3 + 3H2 (1c)
Figure 1: Structure of [Ba5(Omes)5(OMe)5(dme)4]·dme
Reference 1. Deacon,G.B.; Forsyth, C.M.; Junk, P.C.; Skelton,
B.W.; White, A.H. Chem. Euro. J., 1999, 5, 1452-59; Deacon, G.B.;
Junk, P.C.; GJ Moxey, G.J.; K Ruhlandt-Senge, 2. K.; C. St. Prix,
C.; FelisaZuniga, M. Chem. Eur. J. 2009, 15, 5503-5519; Deacon,
G.B.; Junk, P.C.; Moxey, G.J.; Guino-o, M.; Ruhlandt-Senge, K.
Dalton Trans., 2009, 4878-4887; Deacon, G.B.; Junk, P.C.; Moxey,
G.J. Chem. Asian J., 2009, 4, 1717-1728; Deacon, G.B.; Junk, P.C.;
Moxey, G.J. Dalton Trans.., 2010, submitted; Clark, L.; Deacon,
G.B.; Forsyth, C.M.; Junk, P.C.; Mountford, P.; Townley, J.P.
Dalton Trans., 2010, submitted. e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S11
COMPOSITION, STRUCTURE AND NUCLEARITY OF 3d METALS HOMO- AND
HETEROLIGAND CARBOXYLATES AS FACTORS OF DIOXYGEN AND
HYDROPEROXIDES ACTIVATION
G.L. Kamalov
A.V. Bogatsky Physico-Chemical Institute of National Academy of
Sciences of Ukraine, Department of Catalysis; 65080, Lustdorfskaya
Doroga, 86, Odessa, UKRAINE.
On the examples of dibenzyl ether (DBE, the waste product of
some makings) and cyclohexene (CH) liquid-phase oxidation by air
oxygen (1 and 2) and by hydrogen peroxide (3 and 4, respectively),
decomposition of hydroperoxides НР (5), СННР (6) and Н2О2 (7) in
the presence
PhCH2OCH2Ph PhCH(OOH)OCH2PhO2
O22 PhCHO 2 PhCOOH- H2O
DBE HP
BAld BAc
PhCOOCH2PhO2
O2
BAldPhCHO
BB
(1)
OOH OH O
OO2 -H2O
CH-ol CH-on CHE
+ +
CH CHHP
CH(2)
of homo- and heterometallic (Cr, Fe, Mn, Сo, Ni, Cu, VO, Pd)
polynuclear carboxylates (pivalates, benzoates, acetates – more
than 100 complexes in total, with nuclearity from 2 to 12), the
influence of the metals’ nature and their oxidation level, the
character of bridging and terminal ligands and also the nuclearity
of the studied complexes on the rate and selectivity of the
specified reactions are discussed. Possible mechanisms of the
dioxygen, substrates and intermediates activation and the
peculiarities of formed catalytic systems caused by structure and
composition of initial complexes, and also character of substrates
and reaction products are considered. The structures of DBE, BAld
and BAc complexes (XRSA), singled out in the conditions of the
reaction 1 catalysis by Cu, Fe, Co and Pd pivalates are discussed.
Possible mechanisms of these complexes formation are offered. The
assumption about the promotion of catalytic reactions 5 and 6 by
corresponding alcohols is come out. The catalysts demonstrated high
selectivity in reactions 1 and 2 are revealed. That allows to
realize coupled oxidation of СН to the CHE or СН-on. In the case of
Co and Cu complexes the dependence of reaction 7 rate from the
hydrogen peroxide and the catalyst (Cat) concentrations has extreme
character. That specifies in essential passivation of the initial
metal-complex at certain ratio Н2О2:Cat. It is revealed that
selectivity on products of reaction 3 are approximated by two- or
three-parameter equations, arguments of which are rates of reaction
7 in water or in aqueous emulsion of DBE. Close connections of
reaction 6 rate with the rates of reaction 7 and СННР formation in
reaction 2 in the presence of Co-complexes are found out. The
assumption is come out that formation and decomposition of О-О
bonds in these reactions occurs on the same «catalytic centers».
Acknowledgements - This work was executed in frame of the Projects
of INTAS (00-0172 and 03-51-4532), Ukrainian Fund of Basic
Researches (F7/463-2001) and Joint Competition «National Academy of
Sciences of Ukraine –Russian Fund of Basic Researches» (№ 32-08).
e-mail: [email protected]; [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S12
NOVEL COMPLEXES OF CYCLIC AND MACROCYCLIC
AMINOMETHYLPHOSPHINES WITH TRANSITION METALS
A. Karasika, E. Musinaa, A. Baluevaa, S. Ignat’evaa, K.
Kanunnikova, I. Strel’nika, R. Naumova, O. Naumovaa, E.
Hey-Hawkinsb, O. Sinyashina.
a A. E. Arbuzov Institute of Organic and Physical Chemistry of
Kazan Scientific Center of
Russian Academy of Sciences, 420088, Arbuzov str, 8, Kazan,
RUSSIA. b Institut für Anorganische Chemie der Universität Leipzig,
Johannisallee 29, 04103 Leipzig,
GERMANY.
Various types of P,N-containing heterocycles and macrocycles [1]
form a wide variety of transition metal complexes. For example
meso-1,3,6-azadiphosphacycloheptanes 1 [2] form chelate neutral 2
and charged complexes 3 much faster than rac-heterocycles 1
form
oligomeric complexes; that phenomenon was used for the
separation of stereoisomers. The new 14-membered corand 4 formed by
the condensation of
1,2-bis(phenylphosphino)ethane, formaldehyde and isopropylamine
gives mononuclear macrocyclic complex 5 with platinum (II)
dichloride, whereas 16-membered corands form mixtures of
polynuclear macrocyclic comple-xes (e.g. 6) and metal complexes of
the 1-aza-3,7-diphospha-cyclooctanes (7, 8).
28-, 36- and 38-membered P,N-containing cyclophanes form stable
binuclear bis-P,P-chelate complexes. The metal ions of the
P-menthyl substituted complexes 9 being located outside the the
cavity according to X-ray data. So these different types of
P,N-containing ligands may be considered as a potential basis for
the catalytic and molecular recognition systems. [1] A. A. Karasik,
A.S. Balueva, O. G. Sinyashin. C. R. Chimie, 2010, in press, doi:
10.1016/j.crci.2010.04.006 [2] A. A. Karasik, A.S. Balueva, E.I.
Moussina et al. Heteroatom Chem, 2008, 19, 125-132
Acknowledgements: This work is supported by RFBR
(09-03-12264-ofi-m, 10-03-00380-а, 09-03-91338-DFG_a) and by
Federal Agency of Science and Innovations (state contract
02.740.11.0633) e-mail: [email protected]
R'
HR
Ph
Ph
NP P+ +R
H
Ph
PhN PP
1-meso
R'
1-rac1 1-rac2
R'
HR
Ph
PhNP P
** *
R'
RH
Ph
PhN PP
M
ClCl
R'
RH
Ph
PhN PP
M
RH
Ph
Ph NPP
R'
[M] 1/2 [M]
[M]
oligomers
R = Ph, C6H4OMe-p
R' = Me, Et[M] = MCl2(COD), MCl2
M = Pt, Pd, Ni
2+
2 Cl-2
3
CH3
CH3Ph
PhCH3
CH3
PhPh
NP
P
N
P
P
CH3
CH3
Ph
PhCH3
CH3
PhPh
NP
P
N
P
PPt
2+
2 Cl-
PtCl2(COD)
4 5
PH
PHPh
Ph
2 CH2O,i-PrNH2
P
P N
N XX
P
PN
NXX
Ar
Ar
M
M
R
R
R
R
ClCl
ClCl
XAr
XO O
M = Pt; Pd= , R = Ment
PP
N
Ni
Mes
Mes
Br Br
Ph8
;
976
PP
N
Cu
Mes
Mes
I
I
Ph
PP
N
Cu
Mes
Mes
Ph
P
P
N
N
P
P
Ar
Ar
Ar
Ar
M M
Ar'
Ar'M = CuI Ar = Ph, Mes;
Ar' = Ph, Py
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S13
LUMINESCENT METALLOCOMPLEXES OF FUNCTIONALIZED PYRIDINES: FROM
LIGAND DESIGN TOWARDS SPECIAL PROPERTIES
D.N. Kozhevnikova,b, D.S. Kopchuk,b M.Z. Shafikovb and A.M.
Prokhorovb
aI. Postovsky Institute of Organic Synthesis of Ural Branch of
Russian Academy of Sciences,
S. Kovalevskoy 20, Ekaterinburg, 620990,RUSSIA bUral Federal
University, Mira 19, Ekaterinburg, 620002, RUSSIA
Design of organic ligands is one of the most powerful tools for
tunning properties of transition metal complexes. Target changes in
the ligand structure could give or improve accessary properties:
solubility, self-organizing, liquid crystallinity etc., in addition
to main desired property: luminescence, catalysis, recognition etc.
We discuss methods for synthesis of substituted mono-, bi- and
terpyridines which allow wide modification of these well-known
ligands. Any synthesis is based on transformation of 1,2,4-triazine
precursors towards desired pyridines through aza Diels–Alder
reaction. The main advantage of such approach is wide diversity of
substituents, which control different properties of target
zinc(II), platinum(II), iridium(III), europium(III) complexes. In
particular, liquid crystal properties can be added to luminescence
of cyclometallated Pt(II) or Ir(III) complexes of 2-arylpyridines 1
by introduction of alkyl and cycloalkyl substituents.
5’-Aryl-2,2’-bipyridine-6-carboxylates were found to give
neutral lanthanide(III) complexes 2. The cyclopentane ring in one
of the pyridine rings increase dramatically solubility of the
complexes, e.g. Eu(III), in organic solvents. At the same time, the
aromatic substituents play the key role in intra- and intercomplex
π,π-interactions, which affect luminescent properties. In
particular, unusual for europium(III) complexes excimer
luminescence was registered. Formation of excimers was proved by
measurements of luminescence spectra of DCM solutions of the
complexes at different concentrations. Introduction of iminoacetate
moieties gave ligands for luminescent europium complexes 3 –
potential biolabels. Acknowledgements. This work was supported by
Russian Foundation For Basic Researches e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S14
ORGANOMETALLIC CLUSTERS WITH PARTLY MULTIPLE BONDS BETWEEN
TRANSITION AND NONTRANSITION ELEMENTS
A.A.Pasynskii
N. S. Kurnakov Institute of General and Inorganic Chemistry of
Russian Academy of
Sciences, 119991, Leninsky prosp., 31, Moscow, RUSSIA. The role
of vacant and half-occupied orbitals in electron-deficient
complexes is discussed at the formation of partly multiple strictly
shortened bonds between transision (M) and nontransition (E)
elements with participation of lone pairs of the latest. These bond
coud be regulated at the addition of the metalcontaining fragments
to such lone pairs. It influences on spin-spin exchange
interactions via bridge ligands. It is shown that multiple М-E
bonds ( М = Cr, Mn, Re; Э= S, Se, Te) are coordinated with
Pt-containing fragments as olefins giving new types of mixed-metal
clusters. The same complexes could be prepared by
Pt-transmetallation of СрMn(СО)2 or Fe(CO)3 containing clusters
[1]. The formally ordinary М-E bond’s distances are strictly
shortened if E are nontransition elements of III-V periods where
the antibonding orbitals of E-X could participate in additive М-E
interactions (with E-X bond lengths elongation) or the vacant
d-orbitals of E ared used for additive М-E interactions (without
E-X bond lengths elongation). It is important that the elements M
and E which participate in partly multiple M-E bonds retain at the
cluster’s thermolyses but in the case of carbonyl-chalcogenide or
carbonyl-pnicogenide clusters the presence of excess of metal atoms
in respect to chalcogen atoms results electronecompensated CO group
disruption with metal carbides and -oxides formation. It gives the
opportunity to regulate the composition of inorganic products of
cluster pyrolises particulary at the preparation of Pt-containing
mixed-metal electrocatalysts for fuel cells. In stannylated
clusters the formally ordinary М-Sn bonds are strongly shortened
and in the presence of tin-chalcogen bonds the latter retain at
W(CO)5 addition to S atom but the Sn-Se bonds are disrupted in this
situation with pure W-Se-containing complexes formation. The strong
shortening of Pt-Sn and Ru-Sn bond lengths takes place even at the
М/Sn ratio 1:5 or 1:3 respectively. The positive influence of the
M-Sn bonding on catalytical reactions of olefine metatheses or
alcohol oxidation is discussed. Finally the new type of
Te-containing complexes are discussed where the presence of very
short M-Te bonds (even at М:Те ratio 1:3) is combined with additive
interaction between halogen atoms at M with Te atoms at M.
Acknowledgements: this work was financially supported by RFBR
(grant № 09-03-00961). [1]. A.A. Pasynskii, I. V. Skabitsky, Yu. V.
Torubaev, S.S.Shapovalov// J.Organomet.Chem. 2009. V.694. N21.P.
3373-3375. e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S15
INTERPLAY OF ASSOCIATIVE AND DISSOCIATIVE ONE-ELECTRON PROCESSES
IN ORGANOMETALLIC CHEMISTRY: ACCESS TO PRECISION
POLYMERS WITH CONTROLLED FUNCTIONALITY
Rinaldo Poli a, Antoine Debuigneb and Christophe
Detrembleurb
a Laboratoire de Chimie de Coordination, 205, route de Narbonne,
F-31077 Toulouse, France and Institut Universitaire de France, 103,
bd Saint-Michel, 75005 Paris, FRANCE.
b Center for Education and Research on Macromolecules (CERM),
University of Liège, Sart-Tilman, B6, 4000 Liège, BELGIUM
Transition metal complexes may be implicated in controlled
radical polymerization, a booming area for the development of high
added-value polymer materials. They may be catalysts in “atom
transfer radical polymerization” (ATRP), trapping agents in
“organometallic radical polymerization” (OMRP), catalysts for chain
transfer to monomer (CCT), and transfer agents for “degenerative
transfer polymerization” (DTP).1 This lecture will focus on the
interplay of OMRP and DTP for the controlled polymerization of a
difficult monomer, vinyl acetate (VAc), for which ATRP has not
provided a satisfactory level of control. Understanding the key
role of solvent coordination (Scheme 1) has allowed us to develop
the precision polymerization of this monomer2 and the synthesis of
well defined block-copolymers with a PVAc block,3 as well as an
efficient diene-induced radical coupling process leading to
mid-chain functionalized macromolecules.4
References [1] Poli, R. Angew. Chem., Int. Ed. Engl. 2006, 45,
5058–5070. [2] (a) S. Maria, H. Kaneyoshi, K. Matyjaszewski and R.
Poli, Chem. Eur. J. 2007, 13, 2480-2492. (b) Debuigne,
A.; Poli, R.; Jérôme, R.; Jérôme, C.; Detrembleur, C., ACS Symp.
Ser. 2009, 1024, 131-148. [3] A. Debuigne, C. Michaux, C. Jérôme,
R. Jérôme, R. Poli and C. Detrembleur, Chem. Eur. J. 2008, 14,
7623-
7637. [4] (a) Debuigne, A.; Poli, R.; Winter, J. D.; Laurent,
P.; Gerbaux, P.; Dubois, P.; Jean-Paul, W.; Jérôme, C.;
Detrembleur, C., Chem. Eur. J. 2010, 16, 1799-1811. (b) A.
Debuigne, R. Poli, J. D. Winter, P. Laurent, P. Gerbaux, J.-P.
Wathelet, C. Jérôme and C. Detrembleur, Macromolecules 2010, 43,
2801-2813.
Acknowledgements – We are grateful to the CNRS and to the ANR
(Grant No. NT05–2 42140) for funding and to CICT for franting free
computational time. e-mail: [email protected]
+ Co(acac)2PVAcn Co(acac)2-PVAcn•V-70
kdR0
• VAc+ Co(acac)2PVAcn Co(acac)2-PVAcn
•V-70kd
R0• VAc
kpVAc
Co(acac)2-PVAcmPVAcm
•
PVAcn•
DTP
V-70kd
R0•
VAc
kpVAc
Co(acac)2-PVAcmPVAcm
•
PVAcn•
DTP
V-70kd
R0•
VAc
Co(acac)2(L)2-L
+L
+L-L +L-Lslow(CoIII inert)fast(CoII labile)
OMRP
Co(acac)2(L) Co(acac)2(L)-PVAcn
PVAcn•
+
kp VAc
Co(acac)2(L)2-L
+LCo(acac)2(L)2
-L
+L
+L-L +L-Lslow(CoIII inert)fast(CoII labile)
OMRP
Co(acac)2(L) Co(acac)2(L)-PVAcn
PVAcn•
+
kp VAc
+L-L +L-Lslow(CoIII inert)fast(CoII labile)
OMRP
Co(acac)2(L) Co(acac)2(L)-PVAcn
PVAcn•
+
kp VAc
PVAcn•PVAcn•
Scheme 1: OMRP/DTP interplay in the controlled radical
polymerization of VAc
-
International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S16
ORGANIC LIGHT-EMITTING DIODES – THE CURRENT STATE OF
INVESTIGATIONS AND DEVELOPMENTS
V.F. Razumov
Institute of Problems of Chemical Physics of Russian Academy of
Sciences, 142432, acad. Semenov av., 1, Chernogolovka, Moscow
region, RUSSIA.
Organic light-emitting diodes (OLEDs) are double charge
injection devices, requiring the simultaneous supply of both
electrons and holes to the electroluminescent (EL) material
sandwiched between two electrodes. The simplest OLED configuration,
where an organic emitter layer is sandwiched between a transparent
anode and a metallic cathode, gives very poor efficiency. The use
of two or more different materials, e.g. electron- or hole-
transport materials (ETM or HTM) permits to improve the efficiency.
Among these materials the special place is occupied by organic
heterocyclic compositions and metallocomplexes. One of the first in
this row was tris(8-hydroxyquinoline)aluminum (Alq3), presented in
1987 by Tang as an emitter and electron-transport material. Today
derivatives of diarylsubstituted 1,3,4- oxadiazoles are widely
used. They are the basis both of electron-transport and luminescent
layers. More effective luminescent and electron-transport materials
than oxadiazoles are triarylsubstituted 1,2,4-triazoles. Recently
the great attention is given to condensed pyrasolochinolines which
can be used both in the form of individual layers and dopants.
Other large class of electron transport materials is
metallocomplexes with aluminium, zinc, iridium and platinum as
metals. Derivatives of 8-gidroksihinolin,
2-gidroksifenil-2-benzazols and some others are used as ligands.
Chinolinat aluminium possesses good electron transport properties,
a high photoluminescence and quite good electrophysical
characteristics. Zinc complexes of benzoxazole, benzothiazole and
benzimidazole derivatives also are rather perspective electron
transport luminescent materials. They concede Alq/3 on brightness,
but surpass this "reference" complex by one order in mobility of
negative charges. Recently the great interest is given to use of
colloidal semiconductor quantum dots (QDs). Incorporating QDs into
OLED structures as emitting materials is connected with their
specific properties: i)high quantum yield of photoluminescence
which is perspective for obtaining high-luminance LEDs; ii)narrow
spectral distribution of QD luminescence bands which is important
for display applications; iii)possibility to obtain QD luminescence
in any visible spectral region (blue, green, red) which is
important for full-color displays and for white light sources. In
this report the review of modern achievements of use of organic
heterocyclic and metallocomplex compounds in OLEDs is
presented.
e-mail: [email protected]
-
International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S17
RELATIONSHIPS OF KINETIC AND THERMODYNAMIC PARAMETERS OF
DIHYDROGEN BONDING AND PROTON TRANSFER TO TRANSITION METAL
HYDRIDES
E.S. Shubina, N.V. Belkova and L.M. Epstein
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian
Academy of Sciences, 119991, Vavilov Street 28, Moscow, RUSSIA
. Рroton transfer involving transition metal hydrides and/or
heterolytic splitting of dihydrogen are important steps in many
catalytic processes, including ionic hydrogenation and reduction of
H+ to H2. Protonation of metal hydride complexes is generally
recognized as the most common method of [M(η2-H2)] preparation.[1]
Detailed studies of the mechanism of proton transfer to transition
metal hydrides have firmly shown that, in spite of its apparent
simplicity, the process involves several steps and proceeds via
various hydrogen bonded intermediates of molecular or ionic type
(Scheme 1).[2-4] M-H + H-A M-H···H-A [M(η2-H2)]+···A- [M(η2-H2)]+
// A-
molecularcomplex
hydrogen bonded ion pair
solvent separated ion pair
M-H + H-A M-H···H-A [M(η2-H2)]+···A- [M(η2-H2)]+ // A-M-H + H-A
M-H···H-A [M(η2-H2)]+···A- [M(η2-H2)]+ // A-
molecularcomplex
hydrogen bonded ion pair
solvent separated ion pair
Scheme 1. The analysis of the recent results on proton transfer
to transition metal hydrides will be presented. The balance of the
transition metal atom electron richness and of ligand electronic
and steric properties determines the proton transfer pathway and
structure of the intermediates and of the reaction products. The
relationships of kinetic and thermodynamic parameters of dihydrogen
bonding, MH···HA, proton transfer, yielding [M(η2-H2)] species, and
subsequent steps such as[M(η2-H2)] to [M(H)2] isomerization or H2
evolution will be analysed.
Hydrogen bond strength, hydride ligands proton accepting ability
will be shown to correlate with the kinetics and thermodynamics of
the proton transfer. The experimental data backed up by the
theoretical results allow discussing the possible types of
potential energy profiles. Factors such as proton donor and solvent
nature, cooperative effect, temperature etc. will be shown to
determine stability of the species involved. The knowledge acquired
gives wide scope for tuning the reactivity of hydride and
dihydrogen complexes and for governing the reaction pathway.
[1] G. J. Kubas, Chem. Rev. 2007, 107, 4152-4205 [2] N. V.
Belkova, E. S. Shubina, L. M. Epstein, Acc. Chem. Res. 2005, 38,
624-631. [3] N. V. Belkova, L. M. Epstein, E. S. Shubina, ARKIVOC
2008, iv, 120-138. [4] M. Besora, A. Lledos, F. Maseras, Chem. Soc.
Rev. 2009, 38, 957-966 Acknowledgements - The work was supported by
the Division of Chemistry and Material Science of RAS and RFBR
(08-03-00464) . e-mail: [email protected]
-
International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S18
YTTERBIUM COMPLEXES WITH REDOX-ACTIVE DIIMINE LIGANDS: FAIRLY
RICH CHEMISTRY AND PROMISING PRECURSORS FOR NEW MATERIALS
A. Trifonov, B. Shestakov
G. A. Razuvaev Institute of Organometallic Chemistry of Russian
Academy of Sciences,
603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA.
Combination of diimine ligands possessing diverse coordination
and redox properties with lanthanide metals which have two stable
oxidation states (especially with ytterbium) have resulted in
development of rich and intriguing organometallic chemistry. The
reductive reactivity of ytterbocenes towards α,α’-diimines proved
to be sterically and electronically tunable; depending on the
extent of encumbering of the metal atom coordination sphere and the
nature of metal-ligand bonding these reactions can occur with metal
atom oxidation, C-C bond formation, C-H bond activation, C=N bond
hydrogenation. Moreover, manipulation of steric crowding of the
ytterbium coordination sphere allows to switch the reductive
capacity of ytterbocenes in their reactions with α,α’-diimines from
one- to two-electron reduction.
An expansion of ytterbocene reductive chemistry due to
employment of α,α’-diimines reveals new for this field phenomena:
solvent mediated redox tranformations and temperature induced redox
isomery.1 All these phenomena will be discussed. New types of
reactions of ytterbocenes with diazabutadienes, iminopyridines,
7,7,8,8-tetracyanoquinodimethane and 1,2,4,5-tetracyanobenzene as
well as novel types of ytterbium complexes with diimines will be
reported. [1] Trifonov, A. A. Eur. J. Inorg. Chem. 2007, 3151.
Acknowledgements - This work was supported by the Russian
Foundation for Basic Research (Grant N 08-03-00391-а), Program of
the Presidium of the Russian Academy of Science (RAS), and RAS
Chemistry and Material Science Division. e-mail:
[email protected]
-
International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
S19
CORE-SHELL QUANTUM DOTS AND ORGANIC LIGHT EMITTING DEVICES
A.G. Vitukhnovsky, S.A. Shirokov, A.V. Ovchinnikov and S.A.
Ambrozevich
P.N. Lebedev Physics Institute RAS, Leninsky ave. 53, 119991
Moscow, RUSSIA. The ideas of fabrication of light emitting devices
based on organic matrices doped with inorganic semiconductor
quantum dots (QDs) are considered as challenging. The quantum dots
can be used as an active layer in organic light emitting diodes
(OLEDs). New hybrid OLEDs with embedded quantum dots (QD-OLEDs)
have improved life times, high color rendering index and low
fabrication cost. Another one branch of organic electronics which
involves quantum dots is a development of organic field effect
transistors (OFETs) which under certain conditions can also behave
as a light emitter devices – organic light emitting transistors
(OLETs) [1]. The key unit of QD OLED is a two-layer (core - shell)
nanocrystal (QD) covered with an organic layer preventing the
multiple nanocrystal aggregation. In the present work we review the
electronic properties of semiconductor QD taking into consideration
the hybrid band structure of core and shell semiconductors. Type I
and type II structures are discussed. It is shown that the type I
quantum dots have larger quantum efficiency that the quantum dots
of type II. The nanocrystals are investigated using luminescence
spectroscopy, luminescence decay with picosecond and femtosecond
time resolution, and by tracing the blinking fluorescence of a
single nanocrystal. The differences between the light emitting
properties of spherical and tetrapod-shaped nanocrystals are
revealed by means of photoluminescence decay experiment. The
tetrapod nanocrystal photoluminescence decay has a non-exponential
shape due to the limitation of the radiative recombination rate by
the tunneling of the electron over the potential barrier in the
junction point of the tetrapod core [2]. The possibilities to
implement OLEDs/OFETs with top-emitting and bottom-emitting
geometries are reported. Several problems of increasing the overall
performance of the organic devices (e.g. on-off current ratio
increase in an OFET) are discussed.
[1] R.Capelli, S.Toffanin,G.Generali et al., Nature Matrials,
2010, 9, 496. [2] A.G. Vitukhnovsky et al,, Phys. Lett. A, 2009,
373, 2287.
Acknowledgements - Authors acknowledge the Russian Foundation
for Basic Research, project 09-02-00546-a. e-mail:
[email protected]
-
International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
Oral Presentations
-
International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
O1
NORBORNENE-BASED METAL-CONTAINING POLYMERS. SYNTHESIS AND
LUMINESCENT PROPERTIES
L. N. Bochkarev a
aG. A. Razuvaev Institute of Organometallic Chemistry of Russian
Academy of Sciences,
603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Novel
functionalized norbornene monomers were synthesized: Ring opening
metathesis polymerization of functionalized norbornene monomers was
employed for preparation of lanthanide- and platinum-containing
polymers of the types: Photo- and electroluminescent properties of
the synthesized metal-containing polymers will be discussed.
Acknowledgements - this work was supported by the Russion Foundatin
for Basic Research (Project № 08-03-00436) e-mail:
[email protected]
C=OO
NN N
NN
CH3 O
O
O=C
N
C=OO
NN N
Eu
S
O O
CF3 3
C=OO
NN N
Tb
NN
CH3
O O
3
OOLn
(CH2)5
OOH N
N
2
n
Ln = Tb, Eu
OO
(CH2)5
OOH N
N
2
n
OO
(CH2)5
OOH N
N
2
m
Tb Eu
(CH2)5
x
N
n : m : x = 1 : 1: 10
CH2
O O
Pt
n
(H2C)5N
m
m : n = 10 : 1
N
n
(H2C)5N
m
m : n = 10 : 1
NN
CH3 O
O
NPt
C=OO
NN N
Eu
S
O OCF3 3
n
N
m
m : n = 5 : 1
O=C
C=OO
NN N
Tb
n
O=C
N
m
m : n = 5 : 1
NN
CH3
O O
3
-
International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
O2
NEW 2,2’-BIPYRIDINE-BASED POLYDENTATE LIGANDS FOR NUCLEAR WASTES
SEPARATION
N. Borisovaa, E. Eroshkinaa, V. Gerasimchuka, K. Lisenkob, V.
Babainc, M. Reshetovaa and
Yu. Ustynyuka
aMoscow State University Chemistry Department, 119991, Leninskie
Gory, 1/3, Moscow, RUSSIA.
bA.N. Nesmeyanov Institute of Organoelement Compounds, 119991,
Vavilova st., 28, Moscow, RUSSIA.
cV.G. Khlopin Radium Institute, 194021, 2-nd Murinskiy Prospect,
28, S.-Petersburg, RUSSIA.
Separation of minor actinides (particularly americium and
curium) from rare earth elements is very important step of nuclear
spent fuel reprocessing strategies. The mail goal of this
investigation was synthesis and investigation of extraction
properties of the novel compounds based on 2,2’-bipyridyl unit. New
ligands for complexing of the posttransition metals were developed,
synthesized and characterized. We synthesized a number of amides
(1) bearing different substituents on amide moiety as well as at
the positions 4 and 4’ of pyridine rings. The reactions of the
amides 1 and lanthanides were studied in details by
spectrophotometry and NMR. Binding constants for all of the
lanthanide ions with amides of 2,2’-bipyridyl-6,6’-dicarboxylic
acid were found to lie within the range of 4
-
International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
O3
MICRO -RAMAN SPECTROSCOPY AS AN INDISPENSABLE METHOD OF
IDENTIFICATION AND STRUCTURAL INVESTIGATION OF VARIOUS
sp2-CARBON MATERIALS
S.S. Bukalov
Scientific and Technical Center on Raman Spectroscopy, A.N.
Nesmeyanov Institute of Organoelement Compounds,
The Russian Academy of Sciences, Vaviliva str. 28, Moscow119991
RUSSIA.
Various sp2-carbon materials and composites on their basis are
widely studied in
modern high technologies. In view of this, the methods for their
distinguishing and structural
studies are badly needed. These materials are made of graphene
layers of different geometry
packed as bundles or crystallites, whose characteristics and
sizes determine their macroscopic
properties. Micro-Raman spectroscopy on its modern level is one
of the most convenient,
adequate, nondestructive methods of such kind, because each type
of sp2-carbon material
exhibits its own diagnostic Raman spectrum of the first and
second order, that is characterized
by the line position, intensity, half-width and contour.
Moreover, Raman micro-mapping with
spatial resolution up to 1 µ allows one to get information about
the material degree of
ordering, its homogeneity or heterogeneity on macro and
micro-levels, and crystallite size.
In this report, the data on linear and spatial Raman
micro-mapping would be
juxtaposed for graphites of various genesis (both natural and
synthetic) and for other sp2-
carbons (glassy carbon, soot, nanotubes, fullerenes, shungite,
carbine, graphene). Evaluation
of application of the widely used König correlation [1] would be
also given.
[1] F. Tuinstra, J.L. Koenig. J. Chem. Phys. 53, 1126, 1970.
Acknowledgements -The authors acknowledge partial financial
support of the Russian Foundation for Basic Research (project
10-03-01115)
e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
O4
KINETICS AND MECHANISM OF ALCOHOLS SUBSTITUTION IN THE CHROMIUM
(III) COMPLEX of TETRAPHENYLPORPHIN
V.A.Burmistrov, I.P.Trifonova, A.V. Zaharov, O.I.Koifman
Ivanovo State University of Chemical Technology, Ivanovo,
Russia
Metal complexes of porphyrins (MP) are the traditional synthetic
objects modeling the
important biological macrocycles such as chlorophyll, haem and
others. In solutions a metal ion as active center of MP is able to
coordinate the molecules of the solvent. Thus the reaction of
ligation in the 6-th coordination position of octahedral complex is
the reaction of ligand exchange.
The study of solvent substitution in 6-th position of
(acetate)tetraphenylporphyrinatochromium (III) complex ((AcO)CrTPP)
by UV/Vis spectroscopy, 1H NMR and conductometry revealed that the
axial coordination is the consecutive substitution of two alcohol
molecules - at first from the outer coordination envelope and then
– from the inner one. The high stability of alcohol dimer in axial
position of octahedral complex is connected with strengthening of
H-bond due to coordination of amphiprotic ligand by chromium (III).
It provides the redistribution of electronic density from the
second alcohol molecules to metal ion and the strengthening of the
coordination bond.
The outer-sphere substitution of alcohol molecule on the
stronger electronodonor – imidazole results in reinforcement of the
Cr-ROH. The second lone pair of the last one is free and can
participate in donor-acceptor interaction, particularly in H-bond
formation with other alcohol monomer. On the base of inner-sphere
substitution study the solvolytic associative-dissociative
mechanism of axial exchange in 6-th coordination position of
(acetate)tetraphenylporphirinatochromium (III) in amphiprotic
environment was established. The main feature of the offered
mechanism is the activation of an axial exchange by the interaction
of a leaving ligand with a molecule of a solvent. The regression
analysis of multifactor kinetic experiment was carried out, kinetic
isotopic effects and activation parameters of process were studied.
All regularities established for (AcO)CrTPP were found to be
correct for (Cl)CrTPP as well.
The molecule of (chloro)chromium(III) porphyrin and its
derivatives have been studied by density functional theory (DFT)
computations utilizing the B3LYP hybrid method (Becke + Slater + HF
exchange and LYP + VWN5 correlation). All calculations described
above were performed using the PC GAMESS 7.1 version of the GAMESS
software package. Major bond lengths (Cr-Cl, Cr-N in the pyrrole
rings, and Cr-N or Cr-O in axial ligands) were obtained. Energies
of Cr-O and Cr-N bonds were evaluated by the dividing the optimized
structure of a complex with additional axial substituent into two
across Cr-O or Cr-N bond and single-point energies of these parts
((chloro)chromium(III) porphyrin and the substituent) were
calculated without reoptimizing the geometries. The sum of these
energies was subtracted from the energy of the whole complex, thus
giving the energy of homolytic bond breakage. According to our
calculations the Cr-N bond in (chloro)chromium(III) porphyrin
complex with imidazole is stronger than Cr-O bond in the ethanol
complex both in systems with only one imidazole or ethanol ligand
and in complexes with second imidazole or ethanol molecule attached
to the first via hydrogen bonding. Therefore, the DFT computations
unambiguously show that the substitution of ethanol with imidazole
is energetically favorable that is in agreement with the
experimental data. The intermediate complex with ethanol,
imidazole, and a second ethanol molecule attached to both first
ethanol and imidazole via two relatively weak hydrogen bonds, has
significantly weaker Cr-O bond. e-mail: [email protected]
-
International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
O5
SYNTHESIS OF NEW BENZOQUINONE-METHACRYLATES
S. Chesnokova, M.Shurygina a, M. Arsen’ev a, O. Markina a, N.
Druzhkov a, V. Cherkasov a
aG. A. Razuvaev Institute of Organometallic Chemistry of Russian
Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod,
RUSSIA.
Metal-containing polymers are compounds with potentially wide
area of application. Polymerization of monomers containing fragment
which is able to bind metals can be the method of theirs synthesis.
Quinoid structures are known to be used as ligands. The aim of this
work is synthesis and investigation of properties of new
methacrylate monomers containing sterically hindered benzoquinones;
study of polymerization of benzoquinone-methacrylates and creating
of metal-containing polymers on the basis of poly-o-quinones.
Methacrylate monomers were synthesized by two ways. Exchange
reaction of 3,6-di-tert-butyl-2-hydrogen-p-benzoquinone salts with
chloride anhydride of methacrylate acid lead to formation
p-benzoquinone-methacrylate (I) and o-benzoquinone-methacrylate
(IIa) with total yield close to quantitative (Scheme 1). It was
established that the ratio of products depends on reaction
conditions.
solvent:THF, C6H6, CH3CN
O
OX
t-Bu
t-BuO H2C
H3C O
Cl
O
O
t-Bu
t-BuO
OCH3
CH2
I
Ot-Bu
t-BuO
OH3C
CH2O
IIa
solvent
X: Li, Na, K, Et3N, NBu4
-XCl
Scheme 1.
Alkoxylation of 3,6-di-tert-butyl-o-benzoquinone by
hydroxymethacrylates was used for synthesis of four new
o-benzoquinone-methacrylates with different hydrocarbon bridges
(IIb-f, Scheme 2). All new p- and o-benzoquinone-methacrylate (I,
IIa-f) were isolated and characterized.
t-Bu
t-Bu
O
OH2C
CH3O R
O
OH
H2C
CH3O R
O
O
t-Bu
t-Bu
O
O+
MnO2, KOH
DMFA, 500C
R= -(CH2)2- (b); -(CH2)4- (c); -(CH2)6- (d); CH2 CH2
(f).IIb-f
Scheme 2.
New poly-o-benzoquinones were obtained by thermal free-radical
polymerization (AINA, 700С) of monomers IIb-f (in benzene and in
bulk) and characterized. The polymers are well soluble in polar
solvents and insoluble in hydrocarbons. The average number of links
in polymer chain is 28-29 (polydispersity coefficient – 1.66). It
was shown by EPR in solution that all poly-o-quinones are able to
complexation. Poly-o-semiquinone complexes of manganese, copper,
nickel and poly-catecholate of antimony were synthesis and
characterized. Acknowledgements -This work was supported by the
Russian Foundation for Basic Research (grant no 08-03-01045-a,
08-03-00668-a, 08-03-97055-r_povolzj’ye_a, 09-03-12268-ofi_m).
e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
O6
THE MECHANISMS OF CATALYTIC REACTIONS WITH THE PARTICIPATION OF
NORBORNADIENE
V. Flid, D. Dmitriev, E. Evstigneeva and R. Shamsiev
M. V. Lomonosov Moscow State Academy of Fine Chemical
Technology, 119571, Vernadskogo pr., 86, Moscow, RUSSIA.
Different mechanisms of catalytic reactions with the
participation of norbornadiene (NBD) are reported. They include
allylation, dimerization, co-dimerization, etc. The catalysts of
these reactions are the metals of 8B group of Periodic System
mainly. The complex study with the use of different methods (NMR,
IR, paramagnetic resonance spectroscopy, GC, GC-MS kinetics study),
quantum-chemical calculation were performed for understanding of
the mechanisms of the reactions with NBD participation.
Nonconventional allylation of norbornenes and norbornadiene is the
unique synthetic method allowing to introduce methylen-, vinyl- and
methylenecyclobutane fragments in NBD structure. The reaction
mechanism was offered for homogeneous and heterogeneous catalysts.
β-Hydride transfer with participation both allylic and NBD
fragments was confirmed by isotope methods. Ways of improving of
the reaction parameters – usage of non-traditional reaction media
(ionic liquids) and cluster-containing catalysts – had been studied
[1,2]. Norbornadiene dimerization as well its co-dimerization with
activated olefiens are very important and interesting reactions.
Resulting dimers and co-dimers find a wide range of applications,
including high-density high-energy jet fuel. The mechanism of the
processes and factors affecting its stereo selectivity were
thoroughly studied by kinetics, spectroscopic, and quantum chemical
methods. The activation parameters found in quantum-chemical
calculations are in the good agreement with the experimental ones.
Key intermediates and possible equilibrium reactions were proposed;
the specifics of regio- and stereo selectivity for different
substrates were explained. The influence of the organophosphorous
compounds as the additives to the catalytic systems allow
increasing the selectivity of the reaction sharply. The role of
phosphines in catalytic transformations, influence of electronic
and steric factors of the ligand were established [3]. In the
course of some reactions the paramagnetic Ni(I) intermediates were
found. The theoretical and experimental study of its role in
catalytic reactions was investigated. The time-concentration
dependence of these intermediates was established. It was shown,
that these complexes are very reactive. Their role in catalysis was
proposed [4]. [1] E. Evstigneeva, V. Flid, Rus. Chem. Bul., 2008,
4, 823. [2] N. Tsukada, T. Sato, Y. Inoue, Tetrahedron Letters,
2000, 41, 4181. [3] I. Efros, D. Dmitriev, V. Flid, Kinetika i
Kataliz, 2010, 3, 391 [4] Ya. Otman, O. Manulic, V.Flid. Kinetika i
Kataliz, 2008, 49, 502. Acknowledgements – Russian Foundation for
Basic Research Grant 08-03-00743 e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
O7
AB INITIO EVIDENCE FOR DITOPIC COORDINATION OF HETEROSILENES
SI=E (E = C, N, O, SI, P, S) TO METHYLENE BRIDGED LIGAND
CONTAINING
BOTH DONOR AND ACCEPTOR SITES
S.L. Guselnikova, V.G. Avakyana, V.F. Sidorkinb a Topchiev
Institute of Petrochemical Synthesis, RAS, 119991 GSP-1, Moscow,
RUSSIA
b Favorsky Irkutsk Institute of Chemistry, Siberian Branch of
RAS, 664033, Irkutsk, RUSSIA Previously we reported a complexation
of silene and dimethylsilene with ditopic ligands Me2N(CH2)nX (n =
0—2; X = BR2, SiR3, R = H, F, Cl) containing both donor and
acceptor sites, studied at MP4/6-311G(d,p)//MP2/6-31G(d,p)+ZPE
level of theory, to estimate their capability of simultaneously
binding the silene moiety into the self-assembly complexes.
Inasmuch as according to our predictions only silenes’ complexes
with Me2NCH2SiF3 could have an interesting synthetical application,
we extended our calculations to ditopic complexes of Me2NCH2SiF3
with heterosilenes Si=E (E = C, N, O, Si, P, S). The complexation
energies were predicted as follows for E = C, N, O, Si, P, S,
kcal/mol: –45.1, –53.6, –49.9, –23.3 (–21.3), –19.3, –21.6. The
nature of bonding in the ditopic complexes of heterosilenes is the
issue to discussion in terms of the structural and energetic
parameters, supported by the data of the AIM and ELF topological
analyses.
[1] Avakyan V.G. et al. Organometallics 2009, 28(4), 978-989.
E-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
O8
NEW TRANSFER HYDROGENATION CATALYSTS FOR CONVERSION OF ALCOHOLS
INTO SECONDARY AMINES AND ESTERS.
D. Gusev and M. Bertoli
Department of Chemistry, Wilfrid Laurier University, 75
University Ave. W., ON N2L 3C5,
CANADA. This work deals with the synthesis, structure and
reactivity studies of a series of outer-sphere transfer
hydrogenation catalysts from our group, which are shown in the
accompanying scheme:
The osmium complex 3 proved to be a particularly efficient
transfer hydrogenation catalyst; it is also active for
dehydrogenative coupling of primary alcohols. Without solvent, and
using low catalyst loadings of 0.1 – 0.2 mol%, we observed
high-yield formation of secondary amines from alcohols and primary
amines or ammonia. A ring-closing reaction of 5-aminopentanol
afforded piperidine:
Upon heating with 3, primary alcohols were converted into the
corresponding esters, releasing two equivalents of hydrogen. This
experimental research is supported by extensive NMR spectroscopic
and DFT computational studies, and the mechanistic features of the
catalytic reactions will be discussed. Acknowledgements - This work
was made possible by the Natural Sciences and Engineering Research
Council of Canada (NSERC), by the facilities of the Shared
Hierarchical Academic Research Computing Network (SHARCNET:
www.sharcnet.ca), and through the support by Wilfrid Laurier
University e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
O9
Tb, Sm, and Eu COMPLEXES CONTAINING HETEROCYCLIC LIGANDS: PHOTO
AND ELECTROLUMINESCENT PROPERTIES
Marina A. Katkova, Tatyana V. Balashova, Anatoly P. Pushkarev
and Mikhail N. Bochkarev
G. A. Razuvaev Institute of Organometallic Chemistry of Russian
Academy of Sciences,
603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Complexes of
rare earth metals with organic ligands present an astounding class
of emissive materials for OLEDs due to peculiarities of the
luminescence properties. Their structure-property relationships can
be used to recognize the fundamental characteristics of existing
devices. The first step in this way is the understanding of the
relation between their photoluminescent and electroluminescent
properties. For this purpose lanthanide (Tb, Sm, and Eu)
N,O-chelate complexes namely
Ln(III)-tris-2-(2-benzoimidazol-2-yl)phenolate,
Ln(III)-tris-2-(2-benzoxyazol-2-yl)phenolate, and
Ln(III)-tris-2-(2-benzothiazol-2-yl)phenolate have been prepared
and tested as photo- and electroluminescent compounds. PHOTO-
Ln = Tb3+ Sm3+ Eu3+
ELECTRO- Acknowledgements - This work was supported by the
Russian Foundation of Basic Research (Grants, 10-03-00190,
09-03-97016) e-mail: [email protected]
450.0 480 500 520 540 560 580 600 620 650.00.0
100
200
300
400
500
600
700
800
860.0
nm
Tb
550.0 560 580 600 620 640 660 680 700.00.0
5
10
15
20
25
30
35
40
45
50
55.0
nm
Sm
570.0 580 590 600 610 620 630 640 650 660 670.00.0
2
4
6
8
10
12
14
16
18
20
22
24
26.0
nm
Eu
0
5 0
1 0 0
1 5 0
2 0 0
2 5 0
3 0 0
3 5 0
4 0 0
4 5 0 5 0 0 5 5 0 6 0 0 6 5 0
0
500
1000
1500
2000
2500
3000
3500
550 570 590 610 630 650 670 690
?
ITO 100 nmTPD 25 nm
Yb 150 nmLnR3 50 nm
N
O
O
NO
ON
O
OLn
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
O10
NEW APPROACH TO CONFORMATIONAL ANALYSIS OF SANDWICH COMPLEXES ON
THE BASIS OF LASER THRESHOLD IONIZATION
SPECTROSCOPY COMBINED WITH DFT CALCULATIONS
S. Ketkova and H. Selzleb
aG. A. Razuvaev Institute of Organometallic Chemistry of Russian
Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod,
RUSSIA.
bTechnische Universität München, Lichtenbergerstr.4, Garching,
GERMANY For over 50 years transition metal complexes with
carbocyclic ligands ηn-CnHn (n = 4 - 8) and their substituted
derivatives have been attracting chemists as one of the most
interesting classes of organometallics. New possibilities appeared
for studying sandwich electronic structures as modern variants of
laser photoionization spectroscopy have been developed. The
resonance enhanced multiphoton ionization (REMPI), zero kinetic
energy (ZEKE) and mass-analyzed threshold ionization (MATI)
techniques provide unprecedented resolution in measuring energies
of electronic excited states and vibrational frequencies of
polyatomic molecules. Interpretation of the results obtained with
laser spectroscopy requires data on molecular parameters which can
be obtained with high-level DFT calculations. This concerns
especially the spectra of substituted sandwich systems revealing
rotational isomers. Recently we reported the MATI spectrum of
bis(η6-toluene)chromium in a supersonic jet1 assigned on the basis
of BPW91/TZVP computations. The individual rotational isomers of
the bisarene system in the gas phase have then been detected for
the first time. In this presentation we summarize the new results
of investigation of the (η6-Arene)2Cr (Arene = o,m,p-xylene,
ethylbenzene, cumene, t-butylbenzene) systems by the laser
threshold ionization spectroscopy combined with the DFT
calculations. Supersonic cooling of organometallic molecules and
employment of monochromatic laser radiation make it possible to
achieve unique accuracy (± 5 cm-1) in determination of ionization
energies (IEs) and vibrational frequencies. The data obtained
correspond to free neutral molecules and cations so they can serve
as a powerful experimental basis for verification of quantum
chemical calculations. Our computations reveal different
distributions of the rotational isomer relative energies for
(η6-RPh)2Cr (R = Me, Et, i-Pr, t-Bu) and these differences agree
very well with the experimental MATI peak separations and relative
intensities. The spectra of the complexes with o- and m-xylene show
three intense MATI bands in contrast to two strong peaks for the
toluene derivative. The MATI spectrum of the EtPh complex shows two
intense features like (η6-MePh)2Cr but their relative intensities
are inverted. The spectra of the i-PrPh and t-BuPh complexes show
only one MATI band. DFT explains these differences by the
rotational isomer relative energies. The high-resolution ionization
potentials of the sandwich compounds studied reveal a non-linear
dependence of IEs on the number of methyl groups in the
substituents. This effect arises from the changes in the zero point
energies of the sandwich neutral molecules and cations. [1] S.Yu.
Ketkov, H.L. Selzle, F.G.N. Cloke, Angew. Chem. Int. Ed. 2007, 46,
7072. Acknowledgements - This work was supported in part by RFBR
(Projects 08-03-97054, 09-03-97045), Russian Ministry for Science
and Education (Contract P-337), the Alexander von Humboldt
Foundation and DFG. e-mail: [email protected]
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International conference “Topical Problems of Organometallic and
Coordination Chemistry” September 3-9, 2010, N. Novgorod,
Russia
O11
IRON PENTACARBONYL FOR ORGANIC SYNTHESIS – REAGENT, SOLVENT,
CATALYST AND PROMOTER
K. A. Kochetkov, А. B. Тerent’ev, Т. Т. Vasil’eva, H. H.
Hambardzumyan,
О. V. Chahovskaya, N. Е. Mysova, Н. Н. Tomashevskaya
A. N. Nesmeyanov Institute of Organoelement Compounds of Russian
Academy of Sciences, 119991, Vavilova str, 28, Moscow, RUSSIA.
The use of transition metal assisted reactions is regarded as an
area of current interest in organic chemistry. Most metal complexes
widely used in the organic synthesis are either expensive or not
easily available. On the other hand, iron oxides, salts and
complexes are cheap and recently they have been proposed as
catalysts and promoters for organic synthesis, at the same time the
available metal carbonyls are used as reagents much more rarely.
Really iron pentacarbonyl is a very cheap and widely spread
compound.
Unfortunately during last years only several tens from more then
1600 reports using Fe(CO)5 have been dealing with synthetic organic
chemistry, specifically isomerization, hydrogenation, carbonylation
or transalkylation reactions. Most typically they have described
Fe(CO)5 mediated isomerization of alkenes resulting in cyclo- or
open structures via π-complexation of an iron carbonyl species to
the double bond. The carbonylation, as well as hydrogenation, is
also popular and can be achieved efficiently by coupling between RX
and iron carbonyl