Supporting Information A new approach to ferrocene derived ... · PDF fileS1 Supporting Information for A new approach to ferrocene derived alkenes via copper-catalyzed olefination

S1

Supporting Information

for

A new approach to ferrocene derived alkenes via

copper-catalyzed olefination

Vasily M. Muzalevskiy1, Aleksei V. Shastin1,2, Alexandra D. Demidovich1, Namiq G.

Shikhaliev3, Abel M. Magerramov3, Victor N. Khrustalev4,5, Rustem D. Rakhimov1,

Sergey Z. Vatsadze1 and Valentine G. Nenajdenko1,5*

Address: 1Department of Chemistry, Lomonosov Moscow State University, Moscow

119991, Russia, 2Institute of Problems of Chemical Physics, Russian Academy of

Sciences, Chernogolovka, Moscow region, 142432 Russia, 3Baku State University,

Department of Chemistry, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan, 4Peoples’

Friendship University of Russia, 6 Miklukho-Maklay Street, Moscow 117198, Russia

and 5A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy

of Sciences, 28 Vavilov Street, Moscow 119991, Russia

Email: Valentine G. Nenajdenko* - [email protected]

* Corresponding author

Experimental details, analytical data and copies of NMR spectra of

all synthesized compounds, X-ray data of compound 8

Table of contents

General remarks S2–S3

Reaction of ferrocene carbaldehyde with polyhalogenalkanes S3

Reaction of acetylferrocene and 1,1’-diacetylferrocene hydrazones with

polyhalogenalkanes S3

Compound characterization data S4–S9

Copies of all NMR spectra S10–S27

X-ray structure determination of 8 S28–S37

mailto:[email protected]

S2

General remarks. All reactions were monitored by thin-layer chromatography

carried out on Merck silica gel plates. Column chromatography was performed on

silica gel (Merck, 63–200 mesh). 1H NMR and 13C NMR spectra were recorded on a

Bruker AMX 400 spectrometer at 400 and 100 MHz, respectively. 19F NMR spectra

were recorded on an AGILENT 400-MR 400 spectrometer (377 МHz). Compounds

were dissolved in CDCl3, acetone-d6 and benzene-d6. Tetramethylsilane and C6F6

were used as internal standards. IR spectra were recorded on a ThermoNicolet IR

200 spectrometer. Mass spectra (HRMS (ESI)) were measured on a MicroTof Bruker

Daltonics instrument. Electrochemical measurements were carried out using a IPC

2000 potentiostat. Platinum (d = 2.8 mm) discs pressed in Teflon served as working

electrodes; a 0.05 M solution of Bu4NBF4 as the supporting electrolyte, and an

Ag/AgCl/KCl(sat.) electrode was the reference electrode. All the measurements were

carried out under argon.

Dimethylformamide for electrochemical measurements (reagent grade) was stirred

with anhydrous K2CO3 (20 g L−1) for 4 days at 20 C, decanted from the solid

phase, and then purified by successive refluxing and vacuum distillation (bp 42 C,

10 Torr) over CaH2 (10 g L−1) and anhydrous CuSO4 (10 g L−1). The purified solvent

was stored over 4 Å molecular sieves. All other reagents were of reagent grade and

were either used as such or distilled prior to use. Ferrocene carbaldehyde [1],

acetylferrocene [2], 1,1’-diacetylferrocene [3] and corresponding hydrazones [4] were

prepared as it was previously published. The NMR data of 1 [5] and 2 [6] are in

agreement with those in the literature.

Reaction of ferrocene carbaldehyde with polyhalogenalkanes (PHA). One neck

50 mL round bottomed flask was charged with 0.228 g (1 mmol) of ferrocene

carbaldehyde, 10 mL of ethylene glycol, 0.25 mL (5 mmol) of N2H4·H2O and stirred 1

h until the aldehyde disappeared (TLC control). Next, 0.38 mL (4.4 mmol) of 1,2-

S3

ethylenediamine and 0.0086 g (0.05 mmol) of CuCl2·2H2O was added, stirred for 1–2

min and then 6 mmol of corresponding PHA was added in one portion under cooling

with a crashed ice bath. The reaction mixture was maintained overnight at room

temperature, poured into 50 mL of water and extracted with CH2Cl2 (3 × 20 mL). The

combined extract was additionally washed with 20 mL of water and dried over

Na2SO4. Solvents were evaporated in vacuo, the residue was purified by passing

through a short silica gel pad using a 3:1 mixture of hexane and CH2Cl2 as an eluent.

Reaction of acetylferrocene and 1,1’-diacetylferrocene hydrazones with

polyhalogenalkanes. 1 mmol of hydrazone, 10 mL of DMSO, 5 equiv of the

corresponding base, and 0.1 equiv of CuCl were mixed together in a one neck 50 mL

round bottomed flask and stirred for 5 min. Next, 5 mmol of the corresponding PHA

was added in one portion under cooling with crashed ice bath. The reaction mixture

was maintained overnight at room temperature and then quenched and purified by

exactly the same steps as in case of ferrocene carbaldehyde olefination.

S4

1-(2,2-Dichlorovinyl)ferrocene (1):

Fe

HCl

Cl

Red-brown crystalline compound; m.p. 52-54 °C; (174 mg, 62% yield); 1H NMR

(400.1 MHz, CDCl3) 4.18 (s, 5H), 4.29 (t, JHH= 1.9 Hz, 2H), 4.58 (t, JHH= 1.9 Hz,

2H), 6.53 (s, 1H, CH=CCl2); 13C NMR (CDCl3, 100.6 MHz) 69.1 (2 CH), 69.2 (7

CH), 77.7 (Cq), 116.1 (CH=CCl2), 127.2 (CH=CCl2).

1-(2,2-Dibromovinyl)ferrocene (2):

Fe

HBr

Br


(400.1 MHz, CDCl3) 4.19 (s, 5H), 4.29 (t, JHH= 1.9 Hz, 2H), 4.66 (t, JHH= 1.9 Hz,

2H), 7.15 (s, 1H, CH=CBr2); 13C NMR (CDCl3, 100.6 MHz) 69.0 (2 CH), 69.2 (2

CH), 69.3 (5 CH), 79.5 (Cq), 83.5 (CH=CBr2), 135.5 (CH=CBr2).

1-(2,3,3,3-Tetrafluoroprop-1-enyl)ferrocene (3):

Fe

HCF3

F

Red-brown oil, obtained as a mixture of Z,E-isomers (74:26); (137 mg, 46% yield); Z-

isomer 1H NMR (400.1 MHz, CDCl3) 4.16 (s, 5Н), 4.35 (s, 2Н), 4.54 (s, 2Н), 6.21

(d, 2JHF = 36.5 Hz, 1Н); 13C NMR (CDCl3, 100.6 MHz) 69.5 (5 CH), 69.8 (d, 4JCF=

3.7 Hz, 2 CH(cpd)), 70.1 (2 CH), 72.6 (Cq), 111.3 (CH=CF-CF3), 118.9 (q, 1JCF=

271.3 Hz, CF3); 19F NMR (376.3 MHz, CDCl3) -137.3-137.1 (m, 1F, F), -72.8 (d,

2JFF=10.2 Hz, 3F, CF3); E-isomer 1H NMR (400.1 MHz, CDCl3) 6.48 (d, 2JHF = 16.2

Hz, 1Н); 13C NMR (CDCl3, 100.6 MHz) 69.4 (5 CH), 70.0 (2 CH), 70.6 (d, 4JCF= 7.7

Hz, 2 CH(cpd)), 72.6 (Cq), 114.9 (dq, 2JCF= 24.0 Hz, 3JCF= 2.7 Hz, CH=CF-CF3); 19F

S5

NMR (376.3 MHz, CDCl3) -129.7-129.9 (m, 1F, F), -67.9 (d, 2JFF=5.5 Hz, 3F, CF3);

HRMS (ESI): m/z calcd for C13H10F4Fe [M+]: 298.0063; found: 298.0063.

1-(2-Bromo-3,3,3-trifluoroprop-1-enyl)ferrocene (4):

Fe

HCF3

Br

Red-brown oil, obtained as a mixture of Z,E-isomers (75:25), (152 mg, 42% yield); Z-

isomer 1H NMR (400.1 MHz, CDCl3) 4.22 (s, 5H), 4.46 (s, 2H), 4.86 (s, 2H), 7.40

(s, 1H, CH=CBrCF3); 13C NMR (CDCl3, 100.6 MHz) 69.61 (5 CH), 70.6 (2 CH),

70.7 (2 CH), 75.5 (Cq), 104.0 (q, 2JCF= 36.9 Hz, C-CF3), 121.4 (q, 1JCF= 270.5 Hz,

CF3), 134.7 (q, 3JCF= 4.8 Hz, CH=CBr-CF3); 19F NMR (376.3 MHz, CDCl3) -67.1; E-


(s, 1H, CH=CBrCF3); 13C NMR (CDCl3, 100.6 MHz) 69.57 (5 CH), 70.2 (q, 5JCF=

3.0 Hz, 2 CH(cpd)), 70.8 (2 CH), 121.0 (q, 1JCF= 272.0 Hz, CF3), 140.4 (q, 3JCF= 2.6

Hz, CH=CBr-CF3); 19F NMR (376.3 MHz, CDCl3) -60.2; IR (cm–1) ν 1655 (C=C);

HRMS (ESI): m/z calcd for C13H10BrF3Fe [M+]:357.9263; found: 357.9262.

1-(2-Chloro-3,3,3-trifluoroprop-1-enyl)ferrocene (5):

Fe

HCF3

Cl

Red-brown oil, obtained as a mixture of Z,E-isomers (75:25), (131 mg, 42% yield); Z-


(s, 1H, CH=CClCF3); 13C NMR (CDCl3, 100.6 MHz) 69.6 (5 CH), 70.65 (2 CH),

70.70 (2 CH), 74.6 (Cq), 114.7 (q, 2JCF= 36.7 Hz, C-CF3), 121.3 (q, 1JCF= 270.9 Hz,

CF3), 131.2 (q, 3JCF= 4.1 Hz, CH=CCl-CF3); 19F NMR (376.3 MHz, CDCl3) -69.0; E-

isomer 1H NMR (400.1 MHz, CDCl3) 4.40 (s, 2H), 4.49 (s, 2H), 6.92 (s, 1H,

CH=CClCF3); 13C NMR (CDCl3, 100.6 MHz) 70.2 (q, 5JCF= 2.6 Hz, 2 CH(cpd)), 75.5

S6

(Cq), 121.0 (q, 1JCF= 272.0 Hz, CF3), 136.1 (q, 3JCF= 1.8 Hz, CH=CCl-CF3); 19F NMR

(376.3 MHz, CDCl3) -62.4; IR (cm–1) ν 1655 (C=O); HRMS (ESI): m/z calcd for

C13H10ClF3Fe [M+]: 313.9767; found: 313.9774.

1-(1,1-Dichloroprop-1-en-2-yl)ferrocene (6):

Fe

Cl

Cl


(400.1 MHz, CDCl3) 2.29 (s, 3Н, CH3), 4.21 (s, 5Н), 4.33 (s, 2Н), 4.62 (s, 2Н); 13C

NMR (CDCl3, 100.6 MHz) 21.8 (CH3), 68.4 (2 CH), 68.9 (7 CH), 83.2 (Cq), 112.7

(C=CCl2), 131.4 (C=CCl2); HRMS (ESI): m/z calcd for C13H12Cl2Fe [M+]: 293.9661;

found: 293.9668.

1-(1,1-Dibromoprop-1-en-2-yl)ferrocene (7):

Fe

Br

Br


(400.1 MHz, CDCl3) 2.32 (s, 3H, CH3), 4.20 (s, 5H), 4.30 (t, JHh= 1.9 Hz, 2H), 4.60

(t, JHh= 1.9 Hz, 2H); 13C NMR (CDCl3, 100.6 MHz) 26.1 (CH3), 68.6 (2 CH), 69.4

(52 CH), 69.6 (2 CH), 83.1 (Cq), 85.7 (C=CBr2), 138.3 (C=CBr2); HRMS (ESI): m/z

calcd for C13H12Br2Fe [M+]: 383.8631; found: 383.8629.

1-(3-Bromo-4,4,4-trifluorobut-2-en-2-yl)ferrocene (8):

Fe

CF3

Br

Red-brown crystalline compound; m.p. 55-57 °C; obtained as a mixture of Z,E-

isomers (47:53), (235 mg, 64% yield); For the mixture of isomers 1H NMR (400.1

MHz, CDCl3) 2.41 (q, 5JHF= 2.7 Hz, 3H, CH3), 2.46 (q, 5JHF= 1.9 Hz, 3H, CH3), 4.20

S7

(s, 5H), 4.21 (s, 5H), 4.34 (t, JHH= 1.7 Hz, 2H), 4.39 (t, JHH= 1.7 Hz, 2H), 4.41 (s, 2H),

4.69 (t, JHH= 1.7 Hz, 2H); 13C NMR (CDCl3, 100.6 MHz) 22.0 (q, 4JCF= 2.9 Hz,

CH3), 29.7 (CH3), 69.1 (2 CH), 69.2 (4 CH), 69.5 (5 CH), 69.6 (5 CH), 70.3 (2 CH),

84.6 (Cq), 85.5 (Cq), 103.4 (q, 2JCF= 36.1 Hz, C-CF3), 106.0 (q, 2JCF= 37.6 Hz, C-

CF3), 121.1 (q, 1JCF= 272.2 Hz, CF3), 121.8 (q, 1JCF= 273.1 Hz, CF3), 145.2 (q, 3JCF=

2.2 Hz, CMe=CBr-CF3), 145.4 (q, 3JCF= 2.6 Hz, CMe=CBr-CF3); 19F NMR (376.3

MHz, CDCl3) -56.4, -55.8; IR (cm–1) ν 1605 (C=C); HRMS (ESI): m/z calcd for

C14H12BrF3Fe [M+]: 371.9420; found: 371.9412.

1-(3-Chloro-4,4,4-trifluorobut-2-en-2-yl)ferrocene (9):

Fe

CF3

Cl

Red-brown oil; obtained as a mixture of Z,E-isomers (58:42); (75 mg, 22% yield); for

the mixture of isomers 1H NMR (400.1 MHz, acetone-d6) 2.41 (q, 5JHF= 2.8 Hz, 3H,

CH3), 2.47 (q, 5JHF= 2.0 Hz, 3H, CH3), 4.23 (s, 5H), 4.26 (s, 5H), 4.40 (t, JHH= 1.8 Hz,

2H), 4.46 (t, JHH= 1.8 Hz, 4H), 4.78 (t, JHH= 1.9 Hz, 2H); 13C NMR (acetone-d6, 100.6

MHz) 20.6 (q, 4JCF= 3.0 Hz, CH3), 25.6 (CH3), 70.1 (CH), 70.4 (CH), 70.5 (CH),

70.6 (CH), 71.2 (CH), 83.7 (Cq), 84.5 (Cq), 112.6 (q, 2JCF= 36.5 Hz, C-CF3), 122.3 (q,

1JCF= 271.6 Hz, CF3), 122.9 (q, 1JCF= 272.4 Hz, CF3), 144.2 (q, 3JCF= 1.7 Hz,

CMe=CCl-CF3), 145.0 (q, 3JCF= 2.0 Hz, CMe=CCl-CF3); 19F NMR (376.3 MHz,

acetone-d6) -56.5, -56.7 (q, 5JHF= 2.6 Hz); HRMS (ESI): m/z calcd for C14H12ClF3Fe

[M+]: 327.9924; found: 327.9920.

1,1’-bis(1,1-Dichloroprop-1-en-2-yl)ferrocene (10):

Fe

Cl

ClCl

Cl

S8

Red-brown viscous oil; (237 mg, 58% yield); 1H NMR (400.1 MHz, CDCl3) 2.26 (s,

6Н, CH3), 4.39 (s, 4Н), 4.69 (s, 4Н); 13C NMR (CDCl3, 100.6 MHz) 22.1 (2 CH3),

71.1 (4 CH), 71.2 (4 CH), 84.9 (2 Cq), 113.4 (2 C=CCl2), 132.7 (2 C=CCl2); IR (cm–1)

ν 1589 (C=C); HRMS (ESI): m/z calcd for C16H14Cl4Fe [M+]: 403.9166; found:

403.9166.

1,1’-bis(1,1-Dibromoprop-1-en-2-yl)ferrocene (11):

Fe

Br

BrBr

Br


(400.1 MHz, CDCl3) 2.24 (s, 6H, CH3), 4.35 (s, 4H), 4.68 (s, 4H); 13C NMR (CDCl3,

100.6 MHz) 25.9 (2 CH3), 70.3 (4 CH), 70.9 (4 CH), 83.9 (2 Cq), 86.9 (2 C=CBr2),

137.4 (2 C=CBr2); IR (cm–1) ν 1562 (C=C); HRMS (ESI): m/z calcd for C16H14Br4Fe

[M+]: 581.7134; found: 581.7136.

1,1’-bis(3-Bromo-4,4,4-trifluorobut-2-en-2-yl))ferrocene (12):

Fe

Br

F3CBr

CF3

Red-brown liquid, obtained as a mixture of Z,Z-Z,E-E,E -isomers (~25:50:25), (365

mg, 65% yield); For the mixture of isomers 1H NMR (400.1 MHz, C6D6) 2.10-2.19

(m, 6H, 2CH3), 3.92-3.97 (m, 2H), 3.98-4.04 (m, 2H), 4.13-4.18 (m, 2H), 4.37-4.43

(m, 2H); 13C NMR (C6D6, 100.6 MHz) 21.6 (CH3), 21.7 (CH3), 28.2 (CH3), 28.3

(CH3), 70.7 (CH), 70.8 (CH), 70.9 (5 CH), 71.0 (CH), 71.9 (CH), 85.8 (Cq), 85.9 (Cq),

86.58 (Cq), 86.63 (Cq), 104.5 (q, 2JCF= 36.5 Hz, C-CF3), 104.6 (q, 2JCF= 36.5 Hz, C-

CF3), 106.9 (q, 2JCF= 37.2 Hz, C-CF3), 107.1 (q, 2JCF= 37.2 Hz, C-CF3), 121.8 (q,

1JCF= 272.4 Hz, CF3), 122.37 (q, 1JCF= 273.1 Hz, CF3), 122.41 (q, 1JCF= 273.1 Hz,

CF3), 144.8 (q, 3JCF= 1.5 Hz, CMe=CBr-CF3), 144.9 (q, 3JCF= 1.8 Hz, CMe=CBr-CF3),

S9

145.1 (CMe=CBr-CF3); 19F NMR (376.3 MHz, C6D6) -55.7 (q, 5JHF= 2.7 Hz), -55.6

(q, 5JHF= 2.7 Hz,) -54.9; IR (cm–1) ν 1597 (C=C); HRMS (ESI): m/z calcd for

C18H14Br2F6Fe [M+]: 559.8692; found: 559.8692.

S10

3 Jul 2015

Acquisition Time (sec) 2.2807 Comment Imported from UXNMR. Date 03 Mar 2012 11:56:06

File Name D:\BN\output\2012\03.ì àðò\BM-179.H_001001r Frequency (MHz) 400.13 Nucleus 1H Number of Transients 5

Original Points Count 16384 Points Count 65536 Pulse Sequence zg30 Solvent CHLOROFORM-D

Sweep Width (Hz) 7183.91 Temperature (degree C) 23.660

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2

Chemical Shift (ppm)

Chloroform-d

6.5

3

4.5

84.3

04.2

94.1

8

4.60 4.55 4.50 4.45 4.40 4.35 4.30 4.25

[x 1

0-1

]

0

0.5

1.0

1.5

2.0

2.5

2.051.99

4.2

94.2

94.3

04.5

84.5

84.5

9 Fe

Cl

Cl

1H NMR spectrum of 1 (400.1 MHz, CDCl3) 3 Jul 2015


File Name D:\BN\output\2012\03.ì àðò\BM-179.C_002001r Frequency (MHz) 100.61 Nucleus 13C

Number of Transients 150 Original Points Count 24153 Points Count 65536 Pulse Sequence zgpg30

Solvent CHLOROFORM-D Sweep Width (Hz) 24154.59 Temperature (degree C) 23.660

230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10


Chloroform-d

127.2

3

116.1

2

77.7

1

69.2

469.0

6

78 77 76 75 74 73 72 71 70 69 68 67 66


0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Inte

nsity

Chloroform-d

69.0

669.2

4

77.7

1

Fe

Cl

Cl

13C NMR spectrum of 1 (100.6 MHz, CDCl3)

S11

16 May 2014

Acquisition Time (sec) 2.5559 Comment Imported from UXNMR. Date 15 May 2014 19:12:18

File Name D:\BN\output\2014\05.ì àé\BM-485.H_001001r Frequency (MHz) 400.13 Nucleus 1H Number of Transients 4



14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1


5.112.081.00

Chloroform-d

4.1

94.2

9

4.6

6

7.1

5

Br

BrFcd

4.65 4.60 4.55 4.50 4.45 4.40 4.35 4.30 4.25 4.20 4.15


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Inte

nsity

5.112.092.08

4.6

6

4.2

9

4.1

9

Fe

Br

Br

1H NMR spectrum of 2 (400.1 MHz, CDCl3) 16 May 2014

Acquisition Time (sec) 0.4999 Comment Imported from UXNMR. Date 15 May 2014 19:15:48

File Name D:\BN\output\2014\05.ì àé\BM-485.C_002001r Frequency (MHz) 100.61 Nucleus 13C

Number of Transients 65 Original Points Count 12076 Points Count 65536 Pulse Sequence zgpg30

Solvent DEUTERIUM OXIDE Sweep Width (Hz) 24154.59 Temperature (degree C) 27.000

230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10


Chloroform-d

69.0

369.2

569.3

2

79.5

383.4

8

135.5

1

69.5 69.4 69.3 69.2 69.1 69.0 68.9 68.8 68.7


0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Inte

nsity

69.3

2

69.2

5

69.0

3

Fe

Br

Br


S12

2 Jul 2015

Acquisition Time (sec) 2.5559 Comment Imported from UXNMR. Date 09 Dec 2014 15:25:54

File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\SD-016.H_001001r Frequency (MHz) 400.13

Nucleus 1H Number of Transients 5 Original Points Count 16384 Points Count 65536

Pulse Sequence zg30 Solvent CHLOROFORM-D Sweep Width (Hz) 6410.26

Temperature (degree C) 27.000

14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1


0.490.130.07

Chloroform-d

4.1

64.3

54.5

4

6.1

76.2

66.4

66.5

1

Fe

F

F

F

F

1H NMR spectrum of 3 (400.1 MHz, CDCl3)

2 Jul 2015


File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\SD-016.C_002001r Frequency (MHz) 100.61

Nucleus 13C Number of Transients 848 Original Points Count 12076 Points Count 65536

Pulse Sequence zgpg30 Solvent CHLOROFORM-D Sweep Width (Hz) 24154.59


230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10


Chloroform-d

69.5

270.1

172.5

5

111.3

1114.7

1114.9

8117.5

8120.2

7

Fe

F

F

F

F

116.0 115.5 115.0 114.5 114.0 113.5 113.0 112.5 112.0 111.5 111.0


0.05

0.10

Inte

nsity

115.0

3114.9

8114.9

5114.9

0114.7

4114.7

1

111.3

1

72.5 72.0 71.5 71.0 70.5 70.0 69.5


0.25

0.50

0.75

1.00

Inte

nsity

72.5

5

70.7

170.6

3

70.1

170.0

5 69.8

269.7

9

69.5

269.4

5


S13

2 Jul 2015

Acquisition Time (sec) 1.0000 Date Dec 9 2014

File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\19F\SD-016_20141209_01\FLUORINE_01 Frequency (MHz) 376.31

Nucleus 19F Number of Transients 16 Original Points Count 89286 Points Count 131072

Pulse Sequence s2pul Solvent CHLOROFORM-D Sweep Width (Hz) 89285.71 Temperature (degree C) 40.000

30 20 10 0 -10 -20 -30 -40 -50 -60 -70 -80 -90 -100 -110 -120 -130 -140 -150 -160 -170 -180 -190 -200 -210


0.52 0.180.17 0.05

C6F6

-162.9

0

-137.2

2-1

37.1

6

-72.8

2

-67.9

2

Fe

F

F

F

F

19F NMR spectrum of 3 (376.3 MHz, CDCl3)

S14

2 Jul 2015

FW 358.9627 Formula C13H10BrF3Fe

Acquisition Time (sec) 2.5559 Comment Imported from UXNMR. Date 13 Nov 2014 20:09:44



Pulse Sequence zg30 Solvent DMSO-D6 Sweep Width (Hz) 6410.26 Temperature (degree C) 27.000

Fe

F

F

F

Br

14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1


5.151.470.75

4.2

24.2

34.4

6

4.8

6

7.1

5

7.4

0

7.5 7.0 6.5 6.0 5.5 5.0 4.5


0

0.25

0.50

0.75

1.00

Inte

nsity

5.152.691.470.75 0.25

7.4

0

7.1

5

4.8

6

4.5

14.4

64.4

1

4.2

34.2

2






Pulse Sequence zgpg30 Solvent DEUTERIUM OXIDE Sweep Width (Hz) 24154.59


Fe

F

F

F

Br

230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10


Chloroform-d

69.6

170.6

370.7

6

75.4

7

103.4

5103.8

1104.1

8104.5

5117.3

1119.6

6120.0

0122.3

6122.6

9125.3

8

134.6

7

140.3

9

142 141 140 139 138 137 136 135 134


0.05

0.10Inte

nsity

140.3

9140.3

6

134.7

2134.6

7134.6

2134.5

8

127 126 125 124 123 122 121 120 119 118 117 116 115


0.1

0.2

Inte

nsity

125.3

8

122.6

9

122.3

6

120.0

0

119.6

6

117.3

1

110 108 106 104 102 100 98


0.05

0.10

Inte

nsity

104.5

5

104.1

8103.8

1103.4

5

71.0 70.5 70.0 69.5 69.0


0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Inte

nsity

70.7

670.7

070.6

3

70.2

670.2

3

69.6

169.5

7


S15

2 Jul 2015


Acquisition Time (sec) 1.0000 Date Nov 14 2014




Fe

F

F

F

Br

30 20 10 0 -10 -20 -30 -40 -50 -60 -70 -80 -90 -100 -110 -120 -130 -140 -150 -160 -170 -180 -190 -200 -210


74.9225.33

C6F6

-67.0

8

-60.2

2


S16

2 Jul 2015

FW 314.5114 Formula C13H10ClF3Fe






Fe

F

F

F

Cl

14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1


5.221.480.75

Chloroform-d

4.2

04.4

04.4

44.4

9

4.7

8

6.9

27.1

0

7.0 6.5 6.0 5.5 5.0 4.5 4.0


0

0.25

0.50

0.75

1.00

Inte

nsity

5.221.48 1.360.75 0.25

Chloroform-d

7.1

0

6.9

2

4.7

8

4.4

94.4

44.4

0

4.2

0








Fe

F

F

F

Cl

230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10


Chloroform-d

69.5

570.6

5

74.6

375.5

1

114.5

2114.8

8115.2

5117.2

6119.6

9119.9

6122.4

0122.6

5125.3

3131.1

8

136.0

8

76 75 74 73 72 71 70 69


0.25

0.50

0.75

1.00

Inte

nsity

75.5

1

74.6

3

70.7

0 70.6

5

70.2

370.2

0

69.5

5

128 126 124 122 120 118 116 114


0.05

0.10

Inte

nsity

125.3

3

122.6

5122.4

0

119.9

6119.6

9

117.2

6

115.2

5114.8

8114.5

2114.1

5

136 135 134 133 132 131


0.05

0.10

Inte

nsity

136.0

8136.0

6

131.1

8131.1

4


S17

2 Jul 2015


Acquisition Time (sec) 1.0000 Date Nov 21 2014




Fe

F

F

F

Cl

30 20 10 0 -10 -20 -30 -40 -50 -60 -70 -80 -90 -100 -110 -120 -130 -140 -150 -160 -170 -180 -190 -200 -210


75.0024.96

C6F6

-68.9

8

-62.4

1


S18


File Name D:\NMR\OUTPUT\2012\03.ì àðò\BM-181.H_001001r Frequency (MHz) 400.13 Nucleus 1H Number of Transients 4



15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2

ppm

4.84 3.002.00

2.2

9

4.2

14.3

3

4.6

24.5 4.0 3.5 3.0 2.5

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

4.84 3.002.902.00

4.6

2

4.3

3

4.2

1

2.2

9

Fe

Cl

Cl

CH3

1H NMR spectrum of 6 (400.1 MHz, CDCl3) Acquisition Time (sec) 0.9999 Comment Imported from UXNMR. Date 10 Mar 2012 13:31:34

File Name D:\NMR\OUTPUT\2012\03.ì àðò\BM-181.C_002001r Frequency (MHz) 100.61 Nucleus 13C Number of Transients 101

Original Points Count 24153 Points Count 65536 Pulse Sequence zgpg30 Solvent CHLOROFORM-D


230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10

ppm

21.8

2

68.3

968.8

9

83.1

7

112.7

2

131.4

4

86 84 82 80 78 76 74 72 70 68 66 64

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

83.1

7

68.8

968.3

9

Fe

Cl

Cl

CH3


S19

Fe

Br

Br

CH3

Acquisition Time (sec) 2.2807 Comment Imported from UXNMR. Date 19 Apr 2012 21:29:28

File Name D:\NMR\OUTPUT\2012\04.àï ðåëü\SN4.H_001001r Frequency (MHz) 400.13 Nucleus 1H Number of Transients 3



8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0

ppm

5.00 2.981.99

Chloroform-d

2.3

2

4.2

0

4.3

04.3

1

4.5

94.6

04.6

0

4.60 4.55 4.50 4.45 4.40 4.35 4.30 4.25 4.20 4.15

0

0.25

0.50

0.75

1.00

5.002.011.99

4.6

0 4.6

04.5

9

4.3

1 4.3

04.3

0

4.2

0

FcdCMe=CBr2



File Name D:\NMR\OUTPUT\2012\04.àï ðåëü\SN4.C_002001r Frequency (MHz) 100.61 Nucleus 13C Number of Transients 97

Original Points Count 24153 Points Count 65536 Pulse Sequence zgpg30 Solvent CHLOROFORM-D


192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8

ppm

Chloroform-d

26.0

9

68.6

369.4

469.5

6

76.6

877.0

077.3

2

83.0

9

85.7

3

138.2

6

86 84 82 80 78 76 74 72 70 68

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Chloroform-d

85.7

3

83.0

9

77.3

277.0

076.6

8 69.5

669.4

4

68.6

3

FcdCMe=CBr2

Fe

Br

Br

CH3


S20

4 Jul 2015


File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\SN8.H_001001r Frequency (MHz) 400.13




15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2


Chloroform-d

2.3

92.4

12.4

6

4.2

04.2

14.3

44.3

9

4.6

94.75 4.70 4.65 4.60 4.55 4.50 4.45 4.40 4.35 4.30 4.25 4.20 4.15


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Inte

nsity

4.511.91 1.481.02

4.7

0 4.6

94.6

9 4.4

14.4

0 4.3

9

4.3

44.3

4

4.2

14.2

04.1

9

2.50 2.45 2.40


0

0.1

0.2

0.3

0.4

0.5

Inte

nsity

1.51 1.49

2.4

72.4

6

2.4

1

2.4

1

2.4

0

2.3

9

FeBr

CH3

F

F

F


4 Jul 2015


File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\SN8.C_002001r Frequency (MHz) 100.61




230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10


Chloroform-d

21.9

7

29.6

7

69.2

169.5

670.2

5

84.5

885.4

9

102.8

5103.2

2103.5

8103.9

4105.3

2105.7

3106.1

1106.4

9119.7

7120.4

5122.4

7123.1

6123.8

9125.8

8

145.1

5145.4

1

70.0 69.5 69.0


0.25

0.50

0.75

1.00

Inte

nsity

70.2

5

69.5

669.4

9

69.2

1

69.0

8

128 126 124 122 120 118 116 114 112 110 108 106 104 102


0

0.01

0.02

0.03

0.04

0.05

0.06

Inte

nsity

125.8

8

123.8

9

123.1

6

122.4

7

120.4

5

119.7

7

106.4

9106.1

1105.7

3105.3

2

103.9

4103.5

8103.2

2102.8

5

FeBr

CH3

F

F

F


S21

4 Jul 2015

Acquisition Time (sec) 0.2449 Comment /volc L26881.019 CDCl3; 300.0K; 17.04.2012 Date 25 Apr 2012 11:50:24

File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\19F\SN-8.{19F}\50549024.{19F}\50549024.{19F}_019000fid Frequency (MHz) 282.39


Pulse Sequence zg Solvent CHLOROFORM-D Sweep Width (Hz) 138888.89 Temperature (degree C) 27.500

200 180 160 140 120 100 80 60 40 20 0 -20 -40 -60 -80 -100 -120 -140 -160 -180 -200 -220 -240 -260 -280 -300


-56.4

4-55.8

0-55.5 -56.0 -56.5


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Inte

nsity

0.530.47

-55.8

0

-56.4

4

FeBr

CH3

F

F

F


S22

10 Jul 2015

Acquisition Time (sec) 5.0000 Date Jul 9 2015 File Name D:\BN\output\F19\2015.07.09\BM-SO-029_20150709_01\PROTON_01

Frequency (MHz) 399.97 Nucleus 1H Number of Transients 8 Original Points Count 30048 Points Count 32768

Pulse Sequence s2pul Solvent acetone Sweep Width (Hz) 6009.62 Temperature (degree C) 26.000

14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1


5.67 3.982.27

Acetone-d6

4.7

84.7

8

4.4

64.2

64.2

3

2.4

72.4

22.4

0

4.8 4.7 4.6 4.5 4.4 4.3


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Inte

nsity

5.674.324.082.27 1.81

4.2

3

4.2

6

4.4

04.4

04.4

1

4.4

64.4

7

4.7

84.7

84.7

9

2.50 2.45 2.40 2.35


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

Inte

nsity

3.983.002.4

02.4

12.4

22.4

2

2.4

62.4

72.4

72.4

8

FeCl

CH3

F

F

F

1H NMR spectrum of 9 (400.1 MHz, acetone-d6) 10 Jul 2015

Acquisition Time (sec) 1.5000 Date Jul 9 2015 File Name D:\BN\output\F19\2015.07.09\BM-SO-029-C_20150709_01\CARBON_01

Frequency (MHz) 100.58 Nucleus 13C Number of Transients 600 Original Points Count 40761 Points Count 65536


250 240 230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20


Acetone-d6

127.1

3126.3

3124.4

2123.6

3121.7

1120.9

3119.0

1118.2

3112.7

4112.3

8

84.5

083.6

7

71.1

670.6

070.4

370.0

9

25.6

1

20.6

2

20.75 20.50 20.25


0.01

0.02

0.03

0.04

0.05

0.06

Inte

nsity

20.5

920.6

220.6

620.6

9

71.0 70.5 70.0


0.1

0.2

0.3

0.4

0.5

Inte

nsity

70.0

470.0

9

70.3

8

70.4

3

70.6

0

71.1

6

130 128 126 124 122 120 118 116 114 112 110 108


0.01

0.02

0.03

0.04

0.05

0.06

Inte

nsity

112.3

8112.7

4

118.2

3

119.0

1120.9

3

121.7

1

123.6

3

124.4

2

126.3

3

127.1

3 FeCl

CH3

F

F

F

13C NMR spectrum of 9 (100.6 MHz, acetone-d6)

S23

10 Jul 2015

Acquisition Time (sec) 3.3554 Date Jul 9 2015 File Name D:\BN\output\F19\2015.07.09\BM-SO-029-F_20150709_01\FLUORINE_01

Frequency (MHz) 376.31 Nucleus 19F Number of Transients 8 Original Points Count 262144 Points Count 262144


24 16 8 0 -8 -16 -24 -32 -40 -48 -56 -64 -72 -80 -88 -96 -104 -112 -120 -128 -136 -144 -152 -160 -168 -176 -184


58.00

C6F6

-56.4

6 -56.7

0

-56.30 -56.35 -56.40 -56.45 -56.50 -56.55 -56.60 -56.65 -56.70 -56.75 -56.80 -56.85 -56.90 -56.95


0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

0.11

0.12

Inte

nsity

58.0042.10-5

6.7

1-5

6.7

1-5

6.7

0-5

6.6

9

-56.4

6Fe

Cl

CH3

F

F

F

19F NMR spectrum of 9 (376.3 MHz, acetone-d6)

S24

3 Jul 2015

Acquisition Time (sec) 2.5559 Comment Imported from UXNMR. Date 30 Jun 2015 18:25:14

File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\BM-683.H_001001r Frequency (MHz) 400.13


Pulse Sequence zg30 Solvent Acetone Sweep Width (Hz) 6410.26 Temperature (degree C) 27.000

14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1


6.004.00

Acetone-d6

4.6

9

4.3

9

2.2

6

4.85 4.80 4.75 4.70 4.65 4.60 4.55 4.50 4.45 4.40 4.35 4.30 4.25 4.20 4.15


0

0.1

0.2

0.3

0.4

0.5

Inte

nsity

4.004.00

4.3

9

4.6

9

Fe

Cl

Cl

CH3

CH3

Cl

Cl


Acquisition Time (sec) 0.4999 Comment Imported from UXNMR. Date 30 Jun 2015 18:29:04

File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\BM-683.C_002001r Frequency (MHz) 100.61


Pulse Sequence zgpg30 Solvent DMSO-D6 Sweep Width (Hz) 24154.59 Temperature (degree C) 27.000

192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0


Acetone-d6

Acetone-d6

132.7

1

113.3

5

84.8

9

71.2

271.0

5

22.1

3

Fe

Cl

Cl

CH3

CH3

Cl

Cl

72.0 71.5 71.0 70.5 70.0 69.5


0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Inte

nsity

71.0

5

71.2

2


S25

3 Jul 2015


File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\BM-688_001001r Frequency (MHz) 400.13



13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1


6.004.004.00

Chloroform-d

4.6

8

4.3

5

2.2

4

5.0 4.5 4.0 3.5 3.0 2.5 2.0


0

0.25

0.50

0.75

1.00

Inte

nsity

6.004.004.00

2.2

4

4.3

5

4.6

8

Fe

Br

Br

CH3

CH3

Br

Br

1H NMR spectrum of 11(400.1 MHz, CDCl3)

3 Jul 2015





230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10


Chloroform-d

137.4

1

86.8

583.9

1

70.8

670.3

4

25.8

7

88 86 84 82 80 78 76 74 72 70 68


0.25

0.50

0.75

1.00

Inte

nsity

Chloroform-d

70.3

4

70.8

6

83.9

1

86.8

5

Fe

Br

Br

CH3

CH3

Br

Br


S26

4 Jul 2015





13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1


4.302.132.10

Chloroform-d

2.1

22.1

32.1

42.1

7

3.9

33.9

33.9

64.0

04.0

24.1

74.3

84.4

2

4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Inte

nsity

2.132.10 1.90 1.83

4.4

24.4

14.3

84.3

8 4.1

74.1

4

4.0

34.0

24.0

2 4.0

03.9

93.9

63.9

53.9

33.9

3

2.25 2.20 2.15 2.10 2.05


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Inte

nsity

4.301.69

2.1

7 2.1

7

2.1

42.1

42.1

32.1

32.1

22.1

1

FeBr

CH3

CH3

Br

F

F

F

F

F

F

1H NMR spectrum of 12 (400.1 MHz, C6D6)

4 Jul 2015





230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10


Benzene-d6

21.6

728.2

128.3

2

70.7

470.8

971.8

7

85.8

286.5

886.6

3

103.9

7104.3

3104.6

9106.4

0106.8

8107.2

5117.7

1120.4

1121.0

2123.1

2

123.7

7127.7

6128.0

0128.2

4

144.7

8145.0

5

71.5 71.0 70.5


0.25

0.50

0.75

1.00

Inte

nsity

71.8

7

71.0

170.8

970.8

670.7

4

87.0 86.5 86.0 85.5


0.25

0.50

0.75

1.00

Inte

nsity

86.6

386.5

8

85.8

585.8

2

125 120 115 110 105


0

0.05

0.10

Inte

nsity

126.4

4125.8

2

123.7

7 123.1

2121.0

5121.0

2 120.4

1

118.3

4117.7

1

107.5

2107.4

0107.2

5106.8

8106.4

0105.1

4104.7

7104.6

9104.4

1104.3

3103.9

7

145.5 145.0 144.5 144.0 143.5


0

0.05

0.10

Inte

nsity

145.0

5144.8

7144.8

5144.7

8144.7

6 FeBr

CH3

CH3

Br

F

F

F

F

F

F

13C NMR spectrum of 12 (100.6 MHz, C6D6)

S27

4 Jul 2015

Acquisition Time (sec) 2.0000 Date Dec 15 2014

File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\19F\BM-690_20141215_01\FLUORINE_01 Frequency (MHz) 376.31


Pulse Sequence s2pul Solvent BENZENE-D6 Sweep Width (Hz) 89285.71 Temperature (degree C) 40.000

30 20 10 0 -10 -20 -30 -40 -50 -60 -70 -80 -90 -100 -110 -120 -130 -140 -150 -160 -170 -180 -190 -200


0.90

C6F6

-55.6

2-5

5.6

1-5

4.9

4

-54.4 -54.5 -54.6 -54.7 -54.8 -54.9 -55.0 -55.1 -55.2 -55.3 -55.4 -55.5 -55.6 -55.7 -55.8 -55.9 -56.0 -56.1 -56.2 -56.3


0

0.25

0.50

0.75

1.00

Inte

nsity

0.90 0.53 0.47

-54.9

4

-55.6

1-5

5.6

2-5

5.6

7-5

5.6

8-5

5.6

9-5

5.7

0

FeBr

CH3

CH3

Br

F

F

F

F

F

F

19F NMR spectrum of 12 (376.3 MHz, C6D6)

S28

X-ray structure determination. [7] Data were collected on a Bruker APEX-II CCD

diffractometer ((Mo K)-radiation, graphite monochromator, ω and φ scan mode) and

corrected for absorption using the SADABS program [8]. For details, see Table S1. The

structure was solved by direct methods and refined by full-matrix least squares technique on

F2 with anisotropic displacement parameters for non-hydrogen atoms. The Br and CF3

substituents are disordered over two same sites with the occupancies of 0.9(E-isomer):0.1(Z-

isomer). The hydrogen atoms were placed in calculated positions and refined within the

riding model with fixed isotropic displacement parameters (Uiso(H) = 1.5Ueq(C) for the CH3-

group and Uiso(H) = 1.2Ueq(C) for the other groups). All calculations were carried out using

the SHELXTL program [9]. Crystallographic data for 8 have been deposited with the

Cambridge Crystallographic Data Center. CCDC 905424 contains the supplementary

crystallographic data for this paper. These data can be obtained free of charge from the

Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: +44 1223 336033;

email: [email protected] or www.ccdc.cam.ac.uk).

Figure S1: Molecular structure of 8 (50% ellipsoids). The minor Z isomer is depicted by

dashed lines.

mailto:[email protected]

http://www.ccdc.cam.ac.uk/

S29

Table S1: Crystallographic data for 8.

___________________________________________________________________________

__

Compound 8

___________________________________________________________________________

__

Empirical formula C14H12BrF3Fe

Fw 373.00

T, K 100(2)

Crystal size, mm 0.30 x 0.20 x 0.05

Crystal system Monoclinic

Space group P21/c

a, Å 7.6257(4)

b, Å 8.5982(5)

c, Å 19.6528(11)

, deg. 90

, deg. 93.128(1)

, deg. 90

V, Å3

1286.66(12)

Z 4

dc, g · cm-3

1.926

F(000) 736

, mm1

4.294

2max, deg. 58

Index range -10 < = h < = 10

-11 < = k < = 11

-26 < = l < = 26

No. of rflns collected 15214

No. of unique rflns 3407 (Rint = 0.0470)

No. of rflns with I > 2(I) 2663

Data/restraints/parameters 3407 / 38 / 170

R1; wR2 (I > 2(I)) 0.0545; 0.1369

R1; wR2 (all data) 0.0722; 0.1456

GOF on F2 1.002

S30

Tmin; Tmax 0.350; 0.800

Table S2: Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Å2 x 103)

For 8. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

________________________________________________________________________________

Atom x y z U(eq)

________________________________________________________________________________

Br(1) 3703(1) 2546(1) -1037(1) 27(1)

Br(1') 6824(2) 2577(2) 128(2) 27(1)

Fe(1) 2333(1) 1691(1) 1839(1) 16(1)

F(1) 6899(2) 3458(2) 576(1) 28(1)

F(2) 7192(2) 3174(2) -495(1) 28(1)

F(3) 6903(2) 1164(2) 138(1) 28(1)

F(1') 4550(4) 1279(2) -1107(1) 28(1)

F(2') 4616(4) 3780(2) -1177(1) 28(1)

F(3') 2197(2) 2612(4) -976(2) 28(1)

C(1) 3549(1) 2961(1) 1114(1) 17(1)

C(2) 4784(1) 1990(1) 1493(1) 18(1)

C(3) 4775(1) 2418(1) 2197(1) 20(1)

C(4) 3536(2) 3645(2) 2244(2) 21(1)

C(5) 2792(2) 3972(2) 1581(1) 20(1)

C(6) 513(4) 207(4) 1385(2) 26(1)

C(7) 1779(4) -639(4) 1805(2) 23(1)

C(8) 1708(4) -72(4) 2483(2) 22(1)

C(9) 420(4) 1126(4) 2483(2) 24(1)

C(10) -324(4) 1291(4) 1805(2) 25(1)

C(11) 3196(1) 2853(1) 378(1) 19(1)

C(12) 4389(1) 2693(1) -94(1) 17(1)

C(13) 6325(2) 2606(1) 35(1) 19(1)

C(13') 3934(3) 2590(2) -842(1) 19(1)

C(14) 1271(3) 2944(1) 148(2) 30(1)

________________________________________________________________________________

S31

Table S3: Bond lengths [Å] and angles [°] for 8.

__________________________________________________________________________________________

Br(1)-C(12) 1.9033(11)

Br(1')-C(12) 1.8867(18)

Fe(1)-C(2) 2.0396(12)

Fe(1)-C(9) 2.041(3)

Fe(1)-C(8) 2.047(3)

Fe(1)-C(7) 2.048(3)

Fe(1)-C(3) 2.0517(13)

Fe(1)-C(10) 2.053(3)

Fe(1)-C(6) 2.053(3)

Fe(1)-C(4) 2.054(2)

Fe(1)-C(1) 2.0566(14)

Fe(1)-C(5) 2.0604(17)

F(1)-C(13) 1.3449(19)

F(2)-C(13) 1.3548(18)

F(3)-C(13) 1.3276(16)

F(1')-C(13') 1.3372(19)

F(2')-C(13') 1.3378(19)

F(3')-C(13') 1.336(2)

C(1)-C(5) 1.412(2)

C(1)-C(2) 1.4360(16)

C(1)-C(11) 1.460(2)

C(2)-C(3) 1.432(3)

C(2)-H(2) 1.0000

C(3)-C(4) 1.422(2)

C(3)-H(3) 1.0000

C(4)-C(5) 1.419(4)

C(4)-H(4) 1.0000

C(5)-H(5) 1.0000

C(6)-C(10) 1.419(5)

C(6)-C(7) 1.434(5)

C(6)-H(6) 1.0000

C(7)-C(8) 1.422(5)

C(7)-H(7) 1.0000

C(8)-C(9) 1.424(5)

C(8)-H(8) 1.0000

C(9)-C(10) 1.426(5)

C(9)-H(9) 1.0000

C(10)-H(10) 1.0000

C(11)-C(12) 1.3401(16)

C(11)-C(14) 1.514(2)

C(12)-C(13) 1.4863(16)

C(12)-C(13') 1.4950(17)

C(14)-H(14A) 0.9800

C(14)-H(14B) 0.9800

C(14)-H(14C) 0.9800

C(2)-Fe(1)-C(9) 159.35(11)

C(2)-Fe(1)-C(8) 123.23(10)

C(9)-Fe(1)-C(8) 40.76(13)

C(2)-Fe(1)-C(7) 107.69(10)

C(9)-Fe(1)-C(7) 68.55(14)

C(8)-Fe(1)-C(7) 40.64(13)

C(2)-Fe(1)-C(3) 40.97(9)

C(9)-Fe(1)-C(3) 121.76(12)

C(8)-Fe(1)-C(3) 104.58(11)

C(7)-Fe(1)-C(3) 119.44(10)

C(2)-Fe(1)-C(10) 158.59(12)

C(9)-Fe(1)-C(10) 40.77(14)

C(8)-Fe(1)-C(10) 68.50(14)

C(7)-Fe(1)-C(10) 68.49(14)

C(3)-Fe(1)-C(10) 159.72(12)

C(2)-Fe(1)-C(6) 122.91(12)

C(9)-Fe(1)-C(6) 68.44(14)

C(8)-Fe(1)-C(6) 68.54(14)

C(7)-Fe(1)-C(6) 40.95(13)

C(3)-Fe(1)-C(6) 156.62(11)

C(10)-Fe(1)-C(6) 40.44(14)

C(2)-Fe(1)-C(4) 68.15(8)

C(9)-Fe(1)-C(4) 105.91(12)

C(8)-Fe(1)-C(4) 118.74(12)

C(7)-Fe(1)-C(4) 154.19(12)

C(3)-Fe(1)-C(4) 40.53(7)

C(10)-Fe(1)-C(4) 124.68(12)

C(6)-Fe(1)-C(4) 162.49(12)

S32

C(2)-Fe(1)-C(1) 41.04(5)

C(9)-Fe(1)-C(1) 157.00(10)

C(8)-Fe(1)-C(1) 161.91(10)

C(7)-Fe(1)-C(1) 126.65(10)

C(3)-Fe(1)-C(1) 68.93(7)

C(10)-Fe(1)-C(1) 123.22(11)

C(6)-Fe(1)-C(1) 110.37(11)

C(4)-Fe(1)-C(1) 67.97(9)

C(2)-Fe(1)-C(5) 68.11(5)

C(9)-Fe(1)-C(5) 121.02(11)

C(8)-Fe(1)-C(5) 154.83(12)

C(7)-Fe(1)-C(5) 163.90(12)

C(3)-Fe(1)-C(5) 68.34(7)

C(10)-Fe(1)-C(5) 109.38(11)

C(6)-Fe(1)-C(5) 127.17(12)

C(4)-Fe(1)-C(5) 40.35(10)

C(1)-Fe(1)-C(5) 40.10(6)

C(5)-C(1)-C(2) 107.46(16)

C(5)-C(1)-C(11) 128.65(12)

C(2)-C(1)-C(11) 123.89(11)

C(5)-C(1)-Fe(1) 70.09(9)

C(2)-C(1)-Fe(1) 68.84(7)

C(11)-C(1)-Fe(1) 125.98(5)

C(3)-C(2)-C(1) 108.31(12)

C(3)-C(2)-Fe(1) 69.97(7)

C(1)-C(2)-Fe(1) 70.11(6)

C(3)-C(2)-H(2) 125.8

C(1)-C(2)-H(2) 125.8

Fe(1)-C(2)-H(2) 125.8

C(4)-C(3)-C(2) 106.95(18)

C(4)-C(3)-Fe(1) 69.80(9)

C(2)-C(3)-Fe(1) 69.06(8)

C(4)-C(3)-H(3) 126.5

C(2)-C(3)-H(3) 126.5

Fe(1)-C(3)-H(3) 126.5

C(5)-C(4)-C(3) 108.8(2)

C(5)-C(4)-Fe(1) 70.08(11)

C(3)-C(4)-Fe(1) 69.66(10)

C(5)-C(4)-H(4) 125.6

C(3)-C(4)-H(4) 125.6

Fe(1)-C(4)-H(4) 125.6

C(1)-C(5)-C(4) 108.53(17)

C(1)-C(5)-Fe(1) 69.80(8)

C(4)-C(5)-Fe(1) 69.57(10)

C(1)-C(5)-H(5) 125.7

C(4)-C(5)-H(5) 125.7

Fe(1)-C(5)-H(5) 125.7

C(10)-C(6)-C(7) 107.9(3)

C(10)-C(6)-Fe(1) 69.8(2)

C(7)-C(6)-Fe(1) 69.31(19)

C(10)-C(6)-H(6) 126.0

C(7)-C(6)-H(6) 126.0

Fe(1)-C(6)-H(6) 126.0

C(8)-C(7)-C(6) 107.9(3)

C(8)-C(7)-Fe(1) 69.66(18)

C(6)-C(7)-Fe(1) 69.74(19)

C(8)-C(7)-H(7) 126.1

C(6)-C(7)-H(7) 126.1

Fe(1)-C(7)-H(7) 126.1

C(7)-C(8)-C(9) 108.0(3)

C(7)-C(8)-Fe(1) 69.69(19)

C(9)-C(8)-Fe(1) 69.40(19)

C(7)-C(8)-H(8) 126.0

C(9)-C(8)-H(8) 126.0

Fe(1)-C(8)-H(8) 126.0

C(8)-C(9)-C(10) 108.1(3)

C(8)-C(9)-Fe(1) 69.84(19)

C(10)-C(9)-Fe(1) 70.05(19)

C(8)-C(9)-H(9) 125.9

C(10)-C(9)-H(9) 125.9

Fe(1)-C(9)-H(9) 125.9

C(6)-C(10)-C(9) 108.1(3)

C(6)-C(10)-Fe(1) 69.80(19)

C(9)-C(10)-Fe(1) 69.18(19)

C(6)-C(10)-H(10) 126.0

C(9)-C(10)-H(10) 126.0

Fe(1)-C(10)-H(10) 126.0

C(12)-C(11)-C(1) 126.57(9)

C(12)-C(11)-C(14) 118.88(16)

C(1)-C(11)-C(14) 114.55(15)

S33

C(11)-C(12)-C(13) 126.36(11)

C(11)-C(12)-C(13') 123.79(12)

C(11)-C(12)-Br(1') 122.85(12)

C(13')-C(12)-Br(1') 113.37(14)

C(11)-C(12)-Br(1) 121.29(9)

C(13)-C(12)-Br(1) 112.34(10)

F(3)-C(13)-F(1) 107.31(15)

F(3)-C(13)-F(2) 106.37(14)

F(1)-C(13)-F(2) 105.05(13)

F(3)-C(13)-C(12) 113.08(11)

F(1)-C(13)-C(12) 112.62(13)

F(2)-C(13)-C(12) 111.87(13)

F(3')-C(13')-F(1') 107.49(19)

F(3')-C(13')-F(2') 107.48(19)

F(1')-C(13')-F(2') 107.40(18)

F(3')-C(13')-C(12) 111.51(18)

F(1')-C(13')-C(12) 111.40(16)

F(2')-C(13')-C(12) 111.34(15)

C(11)-C(14)-H(14A) 109.5

C(11)-C(14)-H(14B) 109.5

H(14A)-C(14)-H(14B) 109.5

C(11)-C(14)-H(14C) 109.5

H(14A)-C(14)-H(14C) 109.5

H(14B)-C(14)-H(14C) 109.5

__________________________________________________________________________________________

S34

Table S4: Anisotropic displacement parameters (Å2 x 103) for 8. The anisotropic

displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ]

______________________________________________________________________________

Atom U11 U22 U33 U23 U13 U12

______________________________________________________________________________

Br(1) 29(1) 35(1) 18(1) -2(1) 0(1) 2(1)

Br(1') 29(1) 35(1) 18(1) -2(1) 0(1) 2(1)

Fe(1) 15(1) 15(1) 18(1) 1(1) 2(1) -1(1)

F(1) 20(1) 36(1) 29(1) 3(1) 3(1) -1(1)

F(2) 20(1) 36(1) 29(1) 3(1) 3(1) -1(1)

F(3) 20(1) 36(1) 29(1) 3(1) 3(1) -1(1)

F(1') 20(1) 36(1) 29(1) 3(1) 3(1) -1(1)

F(2') 20(1) 36(1) 29(1) 3(1) 3(1) -1(1)

F(3') 20(1) 36(1) 29(1) 3(1) 3(1) -1(1)

C(1) 16(1) 17(1) 17(1) 2(1) 1(1) -2(1)

C(2) 14(1) 22(1) 20(1) 1(1) 2(1) -2(1)

C(3) 15(1) 24(2) 20(1) 2(1) -1(1) -4(1)

C(4) 27(2) 19(1) 18(1) 1(1) 5(1) -5(1)

C(5) 21(1) 17(1) 22(1) -1(1) 5(1) -1(1)

C(6) 21(1) 24(2) 32(2) 1(1) -1(1) -4(1)

C(7) 23(1) 19(1) 28(2) 0(1) 3(1) -1(1)

C(8) 23(1) 16(1) 29(2) 6(1) 4(1) -1(1)

C(9) 23(1) 21(1) 30(2) 2(1) 10(1) 0(1)

C(10) 18(1) 22(1) 36(2) 3(1) 3(1) 0(1)

C(11) 6(1) 27(1) 23(1) 3(1) -2(1) -2(1)

C(12) 18(1) 19(1) 14(1) -1(1) -2(1) -1(1)

C(13) 6(1) 27(1) 23(1) 3(1) -2(1) -2(1)

C(13') 6(1) 27(1) 23(1) 3(1) -2(1) -2(1)

C(14) 17(1) 49(2) 24(2) 3(2) 0(1) 3(2)

______________________________________________________________________________

S35

Table S5: Hydrogen coordinates (x 104) and isotropic displacement parameters (Å2 x 103) for 8.

___________________________________________________________________________________

Atom x y z U(iso)

___________________________________________________________________________________

H(2) 5526 1160 1298 22

H(3) 5507 1950 2581 24

H(4) 3229 4179 2673 25

H(5) 1871 4772 1467 24

H(6) 270 66 883 31

H(7) 2571 -1478 1649 28

H(8) 2444 -442 2887 27

H(9) 90 1742 2888 29

H(10) -1259 2048 1651 30

H(14A) 1091 3795 -180 45

H(14B) 572 3134 543 45

H(14C) 905 1960 -68 45

___________________________________________________________________________________

S36

Table S6: Torsion angles [°] for 8.

__________________________________________________________________________________________

C(5)-C(1)-C(2)-C(3) -0.07(6)

C(11)-C(1)-C(2)-C(3) -179.70(5)

Fe(1)-C(1)-C(2)-C(3) -59.77(6)

C(5)-C(1)-C(2)-Fe(1) 59.71(7)

C(11)-C(1)-C(2)-Fe(1) -119.93(6)

C(1)-C(2)-C(3)-C(4) 0.06(6)

Fe(1)-C(2)-C(3)-C(4) -59.80(6)

C(1)-C(2)-C(3)-Fe(1) 59.86(5)

C(2)-C(3)-C(4)-C(5) -0.04(10)

Fe(1)-C(3)-C(4)-C(5) -59.36(9)

C(2)-C(3)-C(4)-Fe(1) 59.33(6)

C(2)-C(1)-C(5)-C(4) 0.04(10)

C(11)-C(1)-C(5)-C(4) 179.66(8)

Fe(1)-C(1)-C(5)-C(4) 58.96(9)

C(2)-C(1)-C(5)-Fe(1) -58.92(5)

C(11)-C(1)-C(5)-Fe(1) 120.70(7)

C(3)-C(4)-C(5)-C(1) 0.00(12)

Fe(1)-C(4)-C(5)-C(1) -59.11(8)

C(3)-C(4)-C(5)-Fe(1) 59.10(8)

C(10)-C(6)-C(7)-C(8) 0.2(4)

Fe(1)-C(6)-C(7)-C(8) 59.5(2)

C(10)-C(6)-C(7)-Fe(1) -59.3(2)

C(6)-C(7)-C(8)-C(9) -0.5(4)

Fe(1)-C(7)-C(8)-C(9) 59.0(2)

C(6)-C(7)-C(8)-Fe(1) -59.5(2)

C(7)-C(8)-C(9)-C(10) 0.6(4)

Fe(1)-C(8)-C(9)-C(10) 59.8(2)

C(7)-C(8)-C(9)-Fe(1) -59.2(2)

C(7)-C(6)-C(10)-C(9) 0.2(4)

Fe(1)-C(6)-C(10)-C(9) -58.8(2)

C(7)-C(6)-C(10)-Fe(1) 59.0(2)

C(8)-C(9)-C(10)-C(6) -0.5(4)

Fe(1)-C(9)-C(10)-C(6) 59.2(2)

C(8)-C(9)-C(10)-Fe(1) -59.7(2)

C(5)-C(1)-C(11)-C(12) 136.97(8)

C(2)-C(1)-C(11)-C(12) -43.48(7)

Fe(1)-C(1)-C(11)-C(12) -130.63(5)

C(5)-C(1)-C(11)-C(14) -42.75(9)

C(2)-C(1)-C(11)-C(14) 136.80(7)

Fe(1)-C(1)-C(11)-C(14) 49.64(7)

C(1)-C(11)-C(12)-C(13) -0.55(6)

C(14)-C(11)-C(12)-C(13) 179.16(7)

C(1)-C(11)-C(12)-C(13') -179.99(6)

C(14)-C(11)-C(12)-C(13') -0.28(7)

C(1)-C(11)-C(12)-Br(1') 0.00(5)

C(14)-C(11)-C(12)-Br(1') 179.71(7)

C(1)-C(11)-C(12)-Br(1) 179.28(3)

C(14)-C(11)-C(12)-Br(1) -1.01(5)

C(11)-C(12)-C(13)-F(3) 89.27(15)

Br(1)-C(12)-C(13)-F(3) -90.58(15)

C(11)-C(12)-C(13)-F(1) -32.60(14)

Br(1)-C(12)-C(13)-F(1) 147.56(11)

C(11)-C(12)-C(13)-F(2) -150.65(11)

Br(1)-C(12)-C(13)-F(2) 29.50(13)

C(11)-C(12)-C(13')-F(3') -2.6(2)

Br(1')-C(12)-C(13')-F(3') 177.41(18)

C(11)-C(12)-C(13')-F(1') -122.70(16)

Br(1')-C(12)-C(13')-F(1') 57.31(18)

C(11)-C(12)-C(13')-F(2') 117.43(17)

Br(1')-C(12)-C(13')-F(2') -62.56(18)

S37

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Supporting Information A new approach to ferrocene derived ... · PDF fileS1 Supporting Information for A new approach to ferrocene derived alkenes via copper-catalyzed olefination

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