Gaining New Vitality: Chemistry of Monovalent Aluminum Species
Presenter: Tongtong LiuSupervisor: Prof. Zhangjie Shi
Fudan University2020-11-27
1
3
Background
Bauxite
Bayer process
Alumina(Al2O3) Aluminium
Electrolysis
H. Yamamoto, K. Oshima, Wiley-VCH, Weinheim, 2004, pp. 189 - 306
Aluminium trihalides (AlX3)
R X
O AlX3R R R
O
CHO
AlCl3CHO
Halogenated Alkylaluminium (AlR3-xXx)
O
OO
ROTBDPS
O
OO
ROTBDPS
HEt2AICI-Ph3P
NNN
Ar Ar
AlCl N
NNAr ArAl
Sandro Gambarotta et al. J. Am. Chem. Soc. 2005, 127, 17204.
4
BackgroundTrialkylaluminiums (AlR3)
A. H. Hoveyda et al. Angew. Chem. Int. Ed. 2008, 47, 7358. S. Xu et al. et al. Chin. J. Org. Chem. 2003, 10, 1049.
Triarylaluminiums (AlAr3)
H. M. Gau et al. Angew. Chem. Int. Ed. 2007, 46, 5373. D. W. Stephan et al. J. Am. Chem. Soc. 2013, 135, 17.
5
Background
Rich oxidation statesOxidation addition Reductive elimination
Cross-CouplingCatalytic HydrogenationOlefin MetathesisOxidation Reaction etc.
7
Background
formal oxidation states
0 +1 +2 +30 +2
1s2 2s2 2p6 3s2 3p1
1s2s3s 3p
2pOxidation addition
σ donor
8
Background
formal oxidation states
0 +1 +2 +3
Considerably less commonRare catalytic reaction
0 +1 +2
H. Schnöckel et al. Angew. Chem. Int. Ed. Engl. 1991, 30, 564.H. W. Roesky et al. Angew. Chem. Int. Ed. Engl. 2000, 39, 4274.S. Aldridge et al. Nature 2018, 557, 92.
1s2 2s2 2p6 3s2 3p1
10
2 Al + Cl2(g)1000 oC
2 AlCl(g)
W. Klemm et al. Z. Anorg. Allg. Chem. 1948, 256, 15.
H. Schnöckel et al. Inorg. Chem. 1989, 28, 2895.
The Al(I) with Cp* ligand
11
H. Schnöckel et al. Angew. Chem. Int. Ed. Engl. 1991, 30, 564.
H. W. Roesky et al. Angew. Chem. Int. Ed. Engl. 1993, 32, 1729.
The Al(I) with Cp* ligand
12
The Al(I) with Cp* ligandDerivatives
H. W. Roesky H. Schnöckel
H. Schnöckel H. W. Roesky R. A. Fischer
Angew. Chem. Int. Ed. 1998, 37, 1952. J. Organomet.Chem. 1998 , 561, 203.
J. Organomet.Chem. 1999 , 579, 373. Organometallics 2003, 22, 3637. Z. Anorg. Allg. Chem. 2005, 631, 2756.
H. Schnöckel
Organometallics 1998, 17, 1894.
[(t-Bu)3SiAl]4
[(Me3Si)3SiAl]4
Cp*3Al3AlN(SiMe3)2[(Me3Si)3CAl]4
[2,6-iPr2C6H3N(SiMe3)Al]4[Al(C5Me4Ph)]4
13
The Al(I) with Cp* ligandReactivity
R. Ahlrichs et al. Angew. Chem. Int. Ed. 1994, 33, 199.M. Kaupp et al. Inorg. Chem. 2016, 55 ,4915.
14A. H. Cowley et al. J. Chem. Soc., Dalton Trans. 1998, 1937
NH
H2C Al3+
Al3+
HN
CH2
Cp*
Cp*
AlN
AlN
Al
Al
Cp* N
Cp* N
Cp*Cp*
SiMe3
SiMe3
SiMe3
SiMe3
N
Al N
AlR
RCp*
Cp*
R = Si(i-Pr)3SiPh3Si(t-Bu)3
(Cp*Al)4-2 N2
4 Me3SiN3
(Cp*Al)4 toluene-4 N2
24 R3SiN3
(Cp*Al)4
2 MesN3
H. W. Roesky et al. Angew. Chem. Int. Ed. 1994, 33, 969.H. W. Roesky et al. Organometallics. 1996, 15, 5252.
toluene/60 °CN
AlN MesMes
Cp*
4N NMes Mes4(Cp*Al)4
The Al(I) with Cp* ligandReactivity
15H. Schnöckel et al. Angew. Chem. Int. Ed. 1996, 35, 2875.H. Schnöckel et al. Z. Anorg. Allg. Chem. 2000, 626, 1557.
H. W. Roesky et al. Angew. Chem. Int. Ed. 1995, 34, 919.
The Al(I) with Cp* ligandReactivity
16A. H. Cowley et al. Chem. Commun. 2001, 75.S. Schulz et al. Organometallics 2006, 25 ,5487.
The Al(I) with Cp* ligandFunction as Ligands
T. K. Woo et al. Organometallics 2003, 22, 1266.
17R. A. Fischer et al. Angew. Chem. Int. Ed. 2004, 43, 2299.
Ni(cod)2 [Ni(AlCp*)3] Ni
AlCp*
Et3Si
H
AlCp*
AlCp*
M
AlCp*
*CpAlAlCp*
AlCp*
Ni
AlCp*
*CpAlAlCp*
AlCp*
NMe2
Pd
Me2N Cl
Cl
-2 cod
HSiEt3
C6H6
n-hexane
C6H6- HSiEt3
partial decomposition
1/4 Cp*Aln-hexane - HSiEt3
hexane, 80 °C- TMEDA
- AlCp* Cl2
M = Ni; Pd
3 Cp*Al
1/4 Cp*Al
H1/4 Cp*Al
5 AlCp*
The Al(I) with Cp* ligandFunction as Ligands
18
R. A. Fischer et al. Chem.-Eur. J. 2005, 11, 1636.R. A. Fischer et al. Dalton Trans., 2009, 322.R. A. Fischer et al. Inorg. Chem. 2017, 56, 3517.
The Al(I) with Cp* ligandFunction as Ligands
20
The Al(I) with β-diketiminates
C. Cui, H. W. Roesky et al. Angew. Chem. Int. Ed. 2000, 39, 4274.C. Cui et al. Organometallics 2007, 26, 1039.
NH
NAr
Ar
AlMe3
-CH4 NAl
NAr
Ar
Me
Me
2 I2-2 MeI N
AlN
Ar
Ar
I
I
2 K, toluene-2 KI N
AlN
Ar
Ar
NH
Nt-Bu
t-Bu
Ar
Ar
AlEt3
-EtH NAl
Nt-Bu
t-Bu
Ar
Ar
Et
Et
2 I2-2 MeI N
AlN
t-Bu
t-Bu
Ar
Ar
I
I
2 K, toluene-2 KI N
AlN
t-Bu
t-Bu
Ar
Ar
Ar = 2,6-iPr2C6H3
21
H. W. Roesky et al. Angew. Chem. Int. Ed. 2004, 43, 3443.H. W. Roesky et al. Angew. Chem. Int. Ed. 2004, 43, 6190.H. W. Roesky et al. J. Am. Chem. Soc. 2005, 127, 10170.C. Cui et al. Organometallics 2007, 26, 1039.
The Al(I) with β-diketiminatesReactivity (with P4, S8, O2, and H2O)
22H. W. Roesky et al. Organometallics 2005, 24, 6420.
NAl
NAr
ArN N
NNR
RN
AlN
Ar
Ar
2 RN3, toluene
- N2 NAl
NAr
Ar
N
Trip
Trip
2,6-Trip2C6H3N3
toluene, -N2
NAl
NAr
Ar
NR
N N NR
Ar = 2,6-iPr2C6H3 Trip = 2,4,6-iPr3C6H2
R
2,6-Trip2C6H3
SiMe3
SiPh3
The Al(I) with β-diketiminatesReactivity (with azides)
H. W. Roesky et al. Angew. Chem. Int. Ed. 2000, 39, 4531.P. P. Power, H. W. Roesky et al. J. Am. Chem. Soc. 2001, 123, 9091.
NAl
NAr
ArN
AlN
Ar
Ar
N Sitoluene, -N2
t-BuSi(N3)3N3
N3
t-BuN
AlN
Ar
Ar
N3N Si
t-BuN3
NAl
NAr
Ar
N3
N
N3
N NAl
NAr
Ar
Si
Si
N3 t-Bu
t-Bu N3
Ar = 2,6-iPr2C6H3
[2+2]cycloaddition 1/2
23H. W. Roesky et al. Eur. J. Inorg. Chem. 2006, 128, 5100.
The Al(I) with β-diketiminatesReactivity (with other nitrogenous compounds)
P. P. Power et al. Angew. Chem. 2005, 117, 5220.H. W. Roesky et al. J. Am. Chem. Soc. 2006, 128 ,5100.
NAl
NAr
Ar
N
NNAl
NAr
Ar
Ph
Ph
Ph
Ph-N2
2 Ph2CN2, 80 °C
Ar = 2,6-iPr2C6H3oxidative addition
Ph2C=N-N=CPh2 2 Ph2CN2
H. W. Roesky et al. Eur. J. Inorg. Chem. 2004, 2004, 4046.
24M. R. Crimmin et al. Angew. Chem. Int. Ed. 2015, 51, 15994.G. I. Nikonov et al. Organometallics 2015, 34 ,5363.
G. I. Nikonov et al. J. Am. Chem. Soc. 2014, 136, 9195.G. I. Nikonov et al. Inorg.Chem. 2016, 55, 9099.
The Al(I) with β-diketiminatesReactivity (with molecules containing σ-bonds)
25
The Al(I) with β-diketiminatesReactivity (with unsaturated bonds)
G. I. Nikonov et al. Angew. Chem. Int. Ed. 2016, 55, 13306.
G. I. Nikonov et al. J. Am. Chem. Soc. 2017, 139, 8804.G. I. Nikonov et al. Inorg.Chem. 2016, 56 ,5993.
26
H. W. Roesky et al. Eur. J. Inorg. Chem. 2004, 2004, 4046.H. W. Roesky et al. Chem. Commun.2017, 53, 2543.H. W. Roesky et al. Angew. Chem. Int. Ed. 2005, 44, 7072.R. Kinjo et al. Chem.-Eur. J. 2016, 22 ,1922.
NAl
NAr
Ar
Ar=2,6-iPrC6H3
2PhB(OH)2
toluene NAl
NAr
Ar
HO
BPh
OH
HO
BO
HPh
-H2, -H2O
NAl
NAr
Ar
O
O B
BO
The Al(I) with β-diketiminatesReactivity (with other reagents)
H. W. Roesky et al. J. Am. Chem. Soc. 2006, 128, 12406.
30S. Aldridge et al. J. Am. Chem. Soc. 2019, 141, 11000.
O
tBu
tBu
N
N
Al
Dipp
Dipp
K
KO
tBu
tBu
N
N
Al
Dipp
Dipp 2,2,2 - cryptTetrahydrofuran
r.t., 30 min
Dipp
Dipp
Al
N
N
tBu
tBu
O
1 2
K(2,2,2-crypt)
N O
O
N
O
OO
O
2,2,2 - crypt
The Al(I) anionsC-C Bond Activation of Benzene
31
Dipp
Dipp
Al
N
N
tBu
tBu
O
2 Me2SnCl2 (2 equiv.)C6H6
r.t., 18 h
Dipp
Dipp
Al
N
N
tBu
tBu
OCl
ClSn Sn
Cl Cl
Me Me
MeMe
3 6 7
S. Aldridge et al. J. Am. Chem. Soc. 2019, 141, 11000
The Al(I) anionsC-C Bond Activation of Benzene
34S. Aldridge et al. Angew. Chem. Int. Ed. 2020, 59, 4897.
The Al(I) anionsMolecular Aluminium Imide
35S. Aldridge et al. Angew. Chem. Int. Ed. 2020, 59, 4897.
The Al(I) anionsMolecular Aluminium Imide
36S. Aldridge et al. Angew. Chem. Int. Ed. 2020, 59, 4897.
The Al(I) anionsMolecular Aluminium Imide
37S. Aldridge et al. Nat. Chem. 2019, 11, 237.
Dipp
Dipp
Al
N
N
tBu
tBu
OO
N
N
Dipp
Dipp
tBu
tBu
Al Al
tBu
tBu
Dipp
Dipp
N
N
O
K
K
Au
AuI
PPh3
PPh3
2 Ph3PAuI
- KI - KI
Dipp
Dipp
Al
N
N
tBu
tBu
O
tBu3PAuIAu PtBu3
19 20
The Al(I) anionsNucleophilic Gold Complex
41M. P. Coles et al. Angew. Chem. Int. Ed. 2020, 59, 12806.
NSiO
Si NAl
N SiO
SiNAl
K
K
iPr
iPr
iPr
iPr
iPr
iPr
iPriPr
CS2 (2 equiv)
NSiO
Si NAl
N SiO
SiNAl
iPr
iPr
iPr
iPr
iPr
iPr
iPriPr
NSiO
Si NAl
iPr
iPr
iPriPr
S
SC S
K4
OEt2
CS2 (4 equiv)SS S
SC
C
K
K
29
30
The Al(I) anionsC-C Bond Formation
44S. Harder et al. Angew. Chem. Int. Ed. 2020, 59, 15982.
S. Harder et al. Angew. Chem. Int. Ed. 2018, 57, 14169.S. Harder et al. Angew. Chem. Int. Ed. 2019, 58, 15496.
The Al(I) anionsDiamido Aluminyl Systems
45S. Harder et al. Angew. Chem. Int. Ed. 2020, 59, 15982.
N AlNAr
Ar
RK
C6H6, 5 °C, 3 h
-RH, 2x NAl
NAr
Ar
NAl
NAr
ArK
K
KCH(SiMe3)2
34
The Al(I) anionsDiamido Aluminyl Systems
46R. Kinjo et al. J. Am. Chem. Soc. 2020, 142, 9057.
The Al(I) anionsAlkyl Amino Aluminyl Systems
AlN
Me3Si SiMe3
Ad
[K(12C4)2]
BH3 SMe2 (3.0 eq.)
Et2O, r.t., 36 h75%
AlN
Me3Si SiMe3
Ad
HBB
H
H
H
HH
[K(12C4)2]
38 39
47
The Al(I) anionsAlkyl Amino Aluminyl Systems
R. Kinjo et al. J. Am. Chem. Soc. 2020, 142, 9057.
AlN
Me3Si SiMe3
Ad
[K(12C4)2]
SiH3Ph(1.1 eq.)
Et2O, r.t., 5 min66%
AlN
Me3Si SiMe3
Ad
SiH2Ph
H
[K(12C4)2]
AlN
Me3Si SiMe3
Ad
NH2
H
[K(12C4)2]NH3 (excess)
(2.5 eq.)
Et2O, r.t., 4 h33%
AlN
Me3Si SiMe3
Ad
[K(12C4)2]
Et2O, _50 C, 5 min44%
40
41
42
48
The Al(I) anionsAlkyl Aluminyl Systems
M. Yamashita et al. Nat. Chem. 2020, 12, 36.
Al
Me3Si SiMe3
SiMe3Me3Si
K(tol)2
r.t., 2.5 h79%
Al
Me3Si SiMe3
SiMe3Me3Si
K(tol)2H
MeOTf
Toluene_35 C
84%
Me3Si SiMe3
SiMe3Me3Si
Al Me
ClMe3Si SiMe3
SiMe3Me3Si
AlK(tol)2
Me3Si SiMe3
SiMe3Me3Si
Al Cl+
Me3Si SiMe3
SiMe3Me3Si
Al
FF
FF
F
F
(x equiv.)
Toluene _35 Cx = 0.5; 48, 70%x = 1; 47: 48 = 4 :3x = 10, 47:48 = 3 : 1
Me3SiMe3Si
SiMe3Me3Si
Al
F
K(tol)2
F FF
FF
Me3SiMe3Si
SiMe3Me3Si
Al
F
K(tol)2
+SiMe3SiMe3
Me3Si SiMe3
Al
F
(tol)2K
FF
F F
44
45
46
47 48
49
M. Yamashita and co-authors, Chem. Eur. J. 2020, 26, 4520.
Al
Me3Si SiMe3
SiMe3Me3Si
Al =
Al
anthracene(3.0 equiv.)
(5.0 equiv)Ph Ph
(3.0 equiv)
(1.0 equiv)
AlK(tol)2
Al K(tol)2
Ph
Ph(Z) or (E)
K(OEt2)2
1)
2) [2.2.2]-cryptandPh
Al
Ph
trans-5 (85%)
(sole product)
68%
Al
[K[2.2.2]-cryptand] +
M. Yamashita et al. Chem. Eur. J. 2020, 26, 2174.
The Al(I) anionsAlkyl Aluminyl Systems
50
H. Braunschweig et al. J. Am. Chem. Soc. 2019, 141, 16954.
P. P. Power et al. J. Am. Chem. Soc. 2020, doi.org/10.1021/jacs.0c10222.
Other Monomeric Al(I) species
[LiAlH3AriPr8]
3 CH3IEt2O, 0 oC
-LiI-3 CH4
AlI2AriPr8
Na/NaClhexane
iPr
iPr
iPr
iPr
iPr
iPr
iPr
iPr
Al
51
Summary
Synthesis reactivity(Cp*Al)4
Aluminyl Anion
Small molecule activation
Function as ligand
Reactions with organic reagents
Prospect
Catalysis
New ligand
Chiral ligandSmall moleculetransformation
Catalysis
New reaction