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TRANSCRIPT
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
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
Red-brown crystalline compound; m.p. 62-63 °C; (139 mg, 38% yield); 1H NMR
(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-
isomer 1H NMR (400.1 MHz, CDCl3) 4.23 (s, 5H), 4.41 (s, 2H), 4.51 (s, 2H), 7.40
(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-
isomer 1H NMR (400.1 MHz, CDCl3) 4.20 (s, 5H), 4.44 (s, 2H), 4.78 (s, 2H), 7.10
(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
Red-brown crystalline compound; m.p. 48-49 °C; (105 mg, 35% yield); 1H NMR
(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
Red-brown crystalline compound; m.p. 59-61 °C; (190 mg, 50% yield); 1H NMR
(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
Red-brown crystalline compound; m.p. 59-61 °C; (427 mg, 74% yield); 1H NMR
(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
Acquisition Time (sec) 0.9999 Comment Imported from UXNMR. Date 03 Mar 2012 12:03:38
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
13C NMR spectrum of 2 (100.6 MHz, CDCl3)
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
Chemical Shift (ppm)
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
Acquisition Time (sec) 0.4999 Comment Imported from UXNMR. Date 09 Dec 2014 15:50:08
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
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
13C NMR spectrum of 3 (100.6 MHz, CDCl3)
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
Chemical Shift (ppm)
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
File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\SD-012.H_001001r Frequency (MHz) 400.13
Nucleus 1H Number of Transients 4 Original Points Count 16384 Points Count 65536
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
1H NMR spectrum of 4 (400.1 MHz, CDCl3) 2 Jul 2015
FW 358.9627 Formula C13H10BrF3Fe
Acquisition Time (sec) 0.4999 Comment Imported from UXNMR. Date 13 Nov 2014 20:13:52
File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\SD-012.C_002001r Frequency (MHz) 100.61
Nucleus 13C Number of Transients 131 Original Points Count 12076 Points Count 65536
Pulse Sequence zgpg30 Solvent DEUTERIUM OXIDE Sweep Width (Hz) 24154.59
Temperature (degree C) 27.000
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
13C NMR spectrum of 4 (100.6 MHz, CDCl3)
S15
2 Jul 2015
FW 358.9627 Formula C13H10BrF3Fe
Acquisition Time (sec) 1.0000 Date Nov 14 2014
File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\19F\SD-012_20141114_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) 50.000
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
Chemical Shift (ppm)
74.9225.33
C6F6
-67.0
8
-60.2
2
19F NMR spectrum of 4 (376.3 MHz, CDCl3)
S16
2 Jul 2015
FW 314.5114 Formula C13H10ClF3Fe
Acquisition Time (sec) 2.5559 Comment Imported from UXNMR. Date 18 Nov 2014 15:18:30
File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\SD-013.H_001001r Frequency (MHz) 400.13
Nucleus 1H Number of Transients 12 Original Points Count 16384 Points Count 65536
Pulse Sequence zg30 Solvent CHLOROFORM-D Sweep Width (Hz) 6410.26
Temperature (degree C) 27.000
Fe
F
F
F
Cl
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
1H NMR spectrum of 5 (400.1 MHz, CDCl3) 2 Jul 2015
FW 314.5114 Formula C13H10ClF3Fe
Acquisition Time (sec) 0.4999 Comment Imported from UXNMR. Date 18 Nov 2014 15:25:16
File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\SD-013.C_002001r Frequency (MHz) 100.61
Nucleus 13C Number of Transients 234 Original Points Count 12076 Points Count 65536
Pulse Sequence zgpg30 Solvent CHLOROFORM-D Sweep Width (Hz) 24154.59
Temperature (degree C) 27.000
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
0.05
0.10
Inte
nsity
136.0
8136.0
6
131.1
8131.1
4
13C NMR spectrum of 5 (100.6 MHz, CDCl3)
S17
2 Jul 2015
FW 314.5114 Formula C13H10ClF3Fe
Acquisition Time (sec) 1.0000 Date Nov 21 2014
File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\19F\SD-013_20141121_01\FLUORINE_01 Frequency (MHz) 376.31
Nucleus 19F Number of Transients 64 Original Points Count 89286 Points Count 131072
Pulse Sequence s2pul Solvent CHLOROFORM-D Sweep Width (Hz) 89285.71 Temperature (degree C) 50.000
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
Chemical Shift (ppm)
75.0024.96
C6F6
-68.9
8
-62.4
1
19F NMR spectrum of 5 (376.3 MHz, CDCl3)
S18
Acquisition Time (sec) 2.2807 Comment Imported from UXNMR. Date 10 Mar 2012 13:46:22
File Name D:\NMR\OUTPUT\2012\03.ì àðò\BM-181.H_001001r Frequency (MHz) 400.13 Nucleus 1H Number of Transients 4
Original Points Count 16384 Points Count 65536 Pulse Sequence zg30 Solvent CHLOROFORM-D
Sweep Width (Hz) 7183.91 Temperature (degree C) 24.960
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
Sweep Width (Hz) 24154.59 Temperature (degree C) 24.960
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
13C NMR spectrum of 6 (100.6 MHz, CDCl3)
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
Original Points Count 16384 Points Count 65536 Pulse Sequence zg30 Solvent CHLOROFORM-D
Sweep Width (Hz) 7183.91 Temperature (degree C) 23.760
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
1H NMR spectrum of 7 (400.1 MHz, CDCl3)
Acquisition Time (sec) 0.9999 Comment Imported from UXNMR. Date 24 Apr 2012 16:48:04
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
Sweep Width (Hz) 24154.59 Temperature (degree C) 25.360
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
13C NMR spectrum of 7 (100.6 MHz, CDCl3)
S20
4 Jul 2015
Acquisition Time (sec) 2.2807 Comment Imported from UXNMR. Date 24 Apr 2012 15:33:12
File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\SN8.H_001001r Frequency (MHz) 400.13
Nucleus 1H Number of Transients 9 Original Points Count 16384 Points Count 65536
Pulse Sequence zg30 Solvent CHLOROFORM-D Sweep Width (Hz) 7183.91
Temperature (degree C) 25.260
15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
1H NMR spectrum of 8 (400.1 MHz, CDCl3)
4 Jul 2015
Acquisition Time (sec) 0.9999 Comment Imported from UXNMR. Date 25 Apr 2012 12:34:08
File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\SN8.C_002001r Frequency (MHz) 100.61
Nucleus 13C Number of Transients 200 Original Points Count 24153 Points Count 65536
Pulse Sequence zgpg30 Solvent CHLOROFORM-D Sweep Width (Hz) 24154.59
Temperature (degree C) 24.260
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
13C NMR spectrum of 8 (100.6 MHz, CDCl3)
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
Nucleus 19F Number of Transients 1 Original Points Count 34018 Points Count 65536
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
Chemical Shift (ppm)
-56.4
4-55.8
0-55.5 -56.0 -56.5
Chemical Shift (ppm)
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
19F NMR spectrum of 8 (376.3 MHz, CDCl3)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Pulse Sequence s2pul Solvent acetone Sweep Width (Hz) 27173.91 Temperature (degree C) 26.000
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Pulse Sequence s2pul Solvent acetone Sweep Width (Hz) 78125.00 Temperature (degree C) 26.000
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Nucleus 1H Number of Transients 4 Original Points Count 16384 Points Count 65536
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
1H NMR spectrum of 10 (400.1 MHz, CDCl3) 3 Jul 2015
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
Nucleus 13C Number of Transients 64 Original Points Count 12076 Points Count 65536
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
13C NMR spectrum of 10 (100.6 MHz, CDCl3)
S25
3 Jul 2015
Acquisition Time (sec) 2.9295 Comment Imported from UXNMR. Date 20 Dec 2014 13:08:08
File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\BM-688_001001r Frequency (MHz) 400.13
Nucleus 1H Number of Transients 8 Original Points Count 16384 Points Count 65536
Pulse Sequence zg30 Solvent DMSO-D6 Sweep Width (Hz) 5592.84 Temperature (degree C) 27.000
13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Acquisition Time (sec) 0.4999 Comment Imported from UXNMR. Date 20 Dec 2014 13:10:54
File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\BM-688_002001r Frequency (MHz) 100.61
Nucleus 13C Number of Transients 64 Original Points Count 12076 Points Count 65536
Pulse Sequence zgpg30 Solvent DMSO-D6 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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
13C NMR spectrum of 11 (100.6 MHz, CDCl3)
S26
4 Jul 2015
Acquisition Time (sec) 2.9295 Comment Imported from UXNMR. Date 20 Dec 2014 13:29:52
File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\BM-690_001001r Frequency (MHz) 400.13
Nucleus 1H Number of Transients 8 Original Points Count 16384 Points Count 65536
Pulse Sequence zg30 Solvent DMSO-D6 Sweep Width (Hz) 5592.84 Temperature (degree C) 27.000
13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Acquisition Time (sec) 0.4999 Comment Imported from UXNMR. Date 20 Dec 2014 13:37:26
File Name D:\BN\Docs (BN)\vasiliy\Manusr\Belstein_Ferrocene\SPEC_Fcd\BM-690_002001r Frequency (MHz) 100.61
Nucleus 13C Number of Transients 256 Original Points Count 12076 Points Count 65536
Pulse Sequence zgpg30 Solvent DMSO-D6 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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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
Nucleus 19F Number of Transients 256 Original Points Count 178571 Points Count 262144
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
Chemical Shift (ppm)
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
Chemical Shift (ppm)
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.
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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