S1
Electronic Supplementary Info
Mono-, di- and tetrarhenium Fischer carbene complexes with thienothiophene substituents
Zandria Lamprecht,a Shankara Radhakrishnan,
a Alexander Hildebrandt,
b Heinrich Lang,
b David C. Liles,
a Nora-
ann Weststrate,a,
and Simon Lotza
and Daniela I. Bezuidenhout,a,c*
a. Department of Chemistry, University of Pretoria, Private Bag X20, Hatfield 0028, Pretoria, South Africa.
b. Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie, Anorganische Chemie, D-09107 Chemnitz, Germany.
c. Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg 2050, South Africa.
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2017
S2
Contents:
Figure S1: Atom numbering scheme used in NMR spectral assignment. ................................................................................ S4
Figure S2: 1H NMR spectrum of 1a in CDCl3. ............................................................................................................................ S5
Figure S3: 13
C NMR spectrum of 1a in CDCl3. ........................................................................................................................... S5
Figure S4: 2D [1H,
13C] HSQC NMR spectrum of 1a in CDCl3. ................................................................................................... S6
Figure S5: 1H NMR spectrum of 2a in CDCl3. ............................................................................................................................ S6
Figure S6: 13
C NMR spectrum of 2a in CDCl3. ........................................................................................................................... S7
Figure S7: 1H NMR spectrum of 3a in CDCl3. ............................................................................................................................ S7
Figure S8: 13
C NMR spectrum of 3a in CDCl3. ........................................................................................................................... S8
Figure S9: 2D [1H,
13C] HSQC NMR spectrum of 3a in CDCl3. ................................................................................................... S8
Figure S10: 1H NMR spectrum of 4a in CDCl3. .......................................................................................................................... S9
Figure S11: 13
C NMR spectrum of 4a in CDCl3. ......................................................................................................................... S9
Figure S12: 1H NMR spectrum of 5a in CDCl3. ........................................................................................................................ S10
Figure S13: 13
C NMR spectrum of 5a in CDCl3. ....................................................................................................................... S10
Figure S14: 2D [1H,
13C] HSQC NMR spectrum of 5a in CDCl3. ............................................................................................... S11
Figure S15: 1H NMR spectrum of 1b in CDCl3. ........................................................................................................................ S11
Figure S16: 13
C NMR spectrum of 1b in CDCl3. ....................................................................................................................... S12
Figure S17: 2D [1H,
13C] HSQC NMR spectrum of 1b in CDCl3. ............................................................................................... S12
Figure S18: 1H NMR spectrum of 3b in CDCl3. ........................................................................................................................ S13
Figure S19: 13
C NMR spectrum of 3b in CDCl3. ....................................................................................................................... S13
Figure S20: 2D [1H,
13C] HSQC NMR spectrum of 3b in CDCl3. ............................................................................................... S14
Figure S21: Cyclic voltammograms of 1a at positive potentials (red) and negative potentials (blue), at a glassy carbon
electrode, scan rate 0.1 Vs-1
in CH2Cl2 with the internal standard marked as FcH. ................................................................ S15
Figure S22: Cyclic voltammograms of 2a at positive potentials (red) and negative potentials (blue), at a glassy carbon
electrode, scan rate 0.1 Vs-1
in CH2Cl2 with the internal standard marked as FcH. ................................................................ S15
Figure S23: Cyclic voltammograms of 3a at positive potentials (red) and negative potentials (blue), at a glassy carbon
electrode, scan rate 0.1 Vs-1
in CH2Cl2 with the internal standard marked as FcH. ................................................................ S15
Figure S24: Cyclic voltammograms of 5a at positive potentials (red) and negative potentials (blue), at a glassy carbon
electrode, scan rate 0.1 Vs-1
in CH2Cl2 with the internal standard marked as FcH. ................................................................ S16
Figure S25: Cyclic voltammograms of 1b at positive potentials (red) and negative potentials (blue), at a glassy carbon
electrode, scan rate 0.1 Vs-1
in CH2Cl2 with the internal standard marked as FcH. ................................................................ S16
Figure S26: Cyclic voltammograms of 3b at positive potentials (red) and negative potentials (blue), at a glassy carbon
electrode, scan rate 0.1 Vs-1
in CH2Cl2 with the internal standard marked as FcH. ................................................................ S16
Figure S27: SEC-IR of 1a upon reduction. Red: neutral compound; blue: reduced compound. ............................................ S17
Figure S28: SEC-IR of 3a upon reduction. Red: neutral compound; blue: reduced compound. ............................................ S17
Figure S29: Intramolecular and intermolecular interactions found in the crystal packing of 3a and 3b. .............................. S18
Table S1: Crystal data and structure refinement for complexes 1a, 2a, 3a, 5a, 1b and 3b. .................................................. S19
Table S2: Chemical potential (µ), hardness/MO energy gap (ƞ) and electrophilicity index (ω) reported in eV for 1a, 1b, 3a
and 3b. ................................................................................................................................................................................... S20
Table S3: Major experimental UV-Vis transitions their corresponding calculated molecular orbitals for 1a. ....................... S21
Figure S30: Normal Transition orbitals (NTOs) for the major absorption bands of 1a. ......................................................... S21
Figure S31: Normal Transition orbitals (NTOs) for the major absorption bands of 1a−−−−. ........................................................ S22
Figure S32: Spin population of 1a−−−− and 1a
+ on the left and right hand side respectively. ..................................................... S22
Table S4: Major experimental UV-Vis transitions their corresponding calculated molecular orbitals for 1b…….……………….S23
Figure S33: Normal Transition orbitals (NTOs) for the major absorption bands of 1b. ......................................................... S23
Figure S34: Normal Transition orbitals (NTOs) for the major absorption bands of 1b−−−−. ........................................................ S24
Figure S35: Spin population of 1b−−−− and 1b
+ on the left and right hand side respectively. ..................................................... S24
Figure S36: Changes in UV-Vis absorption spectrum of 2a during the reduction event in CH2Cl2 containing 0.1 M
NnBu4[B(C6F5)4] electrolyte, applied voltage range: -1.1 to -1.4 V; The inset shows the appearance of a 1600 nm
Intervalence charge transfer (IVCT) feature at an applied voltage -1.4 V. (Legend: Increasing cathodic voltages from black to
light green) ............................................................................................................................................................................. S25
S3
Figure S37: Changes in UV-Vis absorption spectrum of 3a during the reduction event in CH2Cl2 containing 0.1 M
NnBu4[B(C6F5)4] electrolyte, applied voltage range: -1.1 to -1.4 V (Legend: Increasing cathodic voltages from black to light
green)..................................................................................................................................................................................... S25
Figure S38: Changes in UV-Vis absorption spectrum of 3b during the reduction event in CH2Cl2 containing 0.1 M
NnBu4[B(C6F5)4] electrolyte, applied voltage range: -1.1 to -1.4 V (Legend: Increasing cathodic voltages from black to light
green)..................................................................................................................................................................................... S26
S4
ReX
COC
CO
COOC
EtO S
X = Re(CO)5, Br, Cl
S
ReX
COC
CO
COOC
Me2N/EtO S
5
4
3
2
4'
5'
S
ReX
COC
CO
COOC
EtO S
S
5
4
3
2
4'
5'
ReX
COC
CO
COOC
EtO S
5
4
3
2
S
Re
X
C
OC
CO
CO
CO
OEt
Re
X
C
OC
CO
CO
CO
OEt
5
4
1a, 3a, 5a 2a, 4a
1b, 3b 2b
5
4
3
2 5
4
Figure S1: Atom numbering scheme used in NMR spectral assignment.
S5
Figure S2: 1H NMR spectrum of 1a in CDCl3.
Figure S3: 13
C NMR spectrum of 1a in CDCl3.
1.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
3.11
2.04
1.02
0.99
1.00
A (s)
7.99
B (d)
7.36
C (d)
7.30
D (q)
4.58
E (t)
1.63
7.26
CDCl3
102030405060708090110130150170190210230250270290f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
14.55
77.00 CDCl3
77.63
121.03
127.30
129.50
145.14
146.26
161.09
192.30
291.10
S6
Figure S4: 2D [1H, 13C] HSQC NMR spectrum of 1a in CDCl3.
Figure S5: 1H NMR spectrum of 2a in CDCl3.
1.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
3.11
2.15
1.00
A (s)8.02
B (q)4.54
C (t)1.64
7.26 CDCl3
S7
Figure S6: 13C NMR spectrum of 2a in CDCl3.
Figure S7: 1H NMR spectrum of 3a in CDCl3.
2030405060708090100110120130140150160170180190200210220230240250260270280290f1 (ppm)
-5E+06
0
5E+06
1E+07
2E+07
2E+07
2E+07
3E+07
4E+07
4E+07
4E+07
5E+07
6E+07
6E+07
6E+07
7E+07
14.48
77.00 CDCl3
78.05
127.43
144.90
149.36
162.49
291.61
1.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
3.34
2.38
1.06
1.09
1.00
A (d)
7.42
B (d)7.40
C (s)
8.81
D (q)
5.31
E (t)
1.69
7.26 CDCl3
S8
Figure S8: 13C NMR spectrum of 3a in CDCl3.
Figure S9: 2D [1H, 13C] HSQC NMR spectrum of 3a in CDCl3.
2030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
15.02
77.00 CDCl3
79.11
121.89
130.56
140.77
147.71
152.11
158.28
184.14
184.33
185.59
270.21
S9
Figure S10: 1H NMR spectrum of 4a in CDCl3.
Figure S11: 13C NMR spectrum of 4a in CDCl3.
3.82
2.21
1.00
7.26 CDCl3
2030405060708090100110120130140150160170180190200210220230240250260270280f1 (ppm)
-2E+07
0
2E+07
4E+07
6E+07
8E+07
1E+08
1E+08
1E+08
2E+08
2E+08
2E+08
2E+08
2E+08
3E+08
3E+08
3E+08
3E+08
S10
Figure S12: 1H NMR spectrum of 5a in CDCl3.
Figure S13: 13C NMR spectrum of 5a in CDCl3.
3.58
3.50
0.98
1.04
1.00
7.26
CDCl3
46.85
53.54
77.00 CDCl3
112.34
120.20
128.38
136.39
145.82
156.99
189.13
193.69
194.87
197.79
242.08
S11
Figure S14: 2D [1H, 13C] HSQC NMR spectrum of 5a in CDCl3.
Figure S15: 1H NMR spectrum of 1b in CDCl3.
3.22
2.20
1.01
1.01
1.00
7.26
CDCl3
S12
Figure S16: 13C NMR spectrum of 1b in CDCl3.
Figure S17: 2D [1H, 13C] HSQC NMR spectrum of 1b in CDCl3.
14.58
77.00 CDCl3
77.55
119.75
126.19
132.76
139.40
144.68
159.55
193.29
292.25
S13
Figure S18: 1H NMR spectrum of 3b in CDCl3.
Figure S19: 13C NMR spectrum of 3b in CDCl3.
3.25
2.18
1.03
1.10
1.00
7.26
CDCl3
15.05
77.00 CDCl3
79.07
120.11
138.10
140.12
140.75
149.91
156.93
184.17
184.37
185.60
270.93
S14
Figure S20: 2D [1H, 13C] HSQC NMR spectrum of 3b in CDCl3.
S15
Figure S21: Cyclic voltammograms of 1a at positive potentials (red) and negative potentials (blue), at a glassy carbon electrode, scan rate 0.1 Vs-1 in CH2Cl2 with the internal standard marked as FcH.
Figure S22: Cyclic voltammograms of 2a at positive potentials (red) and negative potentials (blue), at a glassy carbon electrode, scan rate 0.1 Vs-1 in CH2Cl2 with the internal standard marked as FcH.
Figure S23: Cyclic voltammograms of 3a at positive potentials (red) and negative potentials (blue), at a glassy carbon electrode, scan rate 0.1 Vs-1 in CH2Cl2 with the internal standard marked as FcH.
S16
Figure S24: Cyclic voltammograms of 5a at positive potentials (red) and negative potentials (blue), at a glassy carbon electrode, scan rate 0.1 Vs-1 in CH2Cl2 with the internal standard marked as FcH.
Figure S25: Cyclic voltammograms of 1b at positive potentials (red) and negative potentials (blue), at a glassy carbon electrode, scan rate 0.1 Vs-1 in CH2Cl2 with the internal standard marked as FcH.
Figure S26: Cyclic voltammograms of 3b at positive potentials (red) and negative potentials (blue), at a glassy carbon electrode, scan rate 0.1 Vs-1 in CH2Cl2 with the internal standard marked as FcH.
S17
18001900200021002200
1995,963
2102,029
1972,821
2088,529
A'4
A'1
-1600 mV
Wavenumber cm-1
-1100 mV
Figure S27: SEC-IR of 1a upon reduction. Red: neutral compound; blue: reduced compound.
18001900200021002200
2001,748
1972,821
A'2-1500 mV
Wavenumber cm-1
-1100 mV
Figure S28: SEC-IR of 3a upon reduction. Red: neutral compound; blue: reduced compound.
S18
Figure S29: Intramolecular and intermolecular interactions found in the crystal packing of 3a and 3b.
2.964
2.964
2.991
2.947
2.809
2.787
Intramolecular interactions Intermolecular interactions
3b
3a
S19
Table S1: Crystal data and structure refinement for complexes 1a, 2a, 3a, 5a, 1b and 3b.
1a 2a 3a 5a 1b 3b
Empirical formula C18H8O10Re2S2 C30H12O20Re4S2 C13H8BrO5ReS2 C13H9ClNO4ReS2 C18H8O10Re2S2 C13H8BrO5ReS2
Formula weight 820.76 1501.32 574.42 528.98 820.76 574.42
Temperature/K 150(2) 150(2) 150(2) 294(2) 150(2) 150(2)
Crystal system monoclinic monoclinic monoclinic monoclinic monoclinic orthorhombic
Space group P21/c P21/n P21/c P21 P21/n P212121
a/Å 9.6980(5) 10.1212(7) 17.2340(9) 6.5331(8) 9.6861(4) 7.3951(4)
b/Å 13.1478(6) 13.5273(11) 6.4087(4) 11.7969(16) 12.7974(5) 14.2116(10)
c/Å 17.4834(9) 14.1208(12) 16.2660(8) 10.8497(15) 17.8103(8) 15.5998(11)
α/° 90 90 90 90 90 90
β/° 106.099(2) 96.857(4) 116.6180(17) 91.742(5) 104.336(2) 90
γ/° 90 90 90 90 90 90
Volume/Å3 2141.84(19) 1919.5(3) 1606.13(15) 835.80(19) 2138.96(16) 1639.48(19)
Z 4 2 4 2 4 4
ρcalcg/cm3 2.545 2.598 2.376 2.102 2.549 2.327
μ/mm-1 11.542 12.76 10.331 7.692 11.557 10.121
F(000) 1512 1368 1072 500 1512 1072
Crystal size/mm3 0.314 × 0.263 ×
0.216 0.360 × 0.080 ×
0.040 0.194 × 0.169 ×
0.163 0.219 × 0.183 ×
0.101 0.210 × 0.190 ×
0.170 0.380 × 0.260 ×
0.220
Radiation MoKα
(λ = 0.71073)
MoKα
(λ = 0.71073)
MoKα
(λ = 0.71073)
MoKα
(λ = 0.71073)
MoKα
(λ = 0.71073)
MoKα
(λ = 0.71073)
2Θ range for data collection/°
4.85 to 63.298 4.696 to 54.198 5.01 to 65.296 5.102 to 54.2 4.398 to 61.014 5.222 to 56.694
Index ranges
-14 ≤ h ≤ 14,
-19 ≤ k ≤ 19,
-25 ≤ l ≤ 25
-12 ≤ h ≤ 12,
-17 ≤ k ≤ 17,
-18 ≤ l ≤ 18
-26 ≤ h ≤ 26,
-9 ≤ k ≤ 9,
-24 ≤ l ≤ 24
-8 ≤ h ≤ 8,
-15 ≤ k ≤ 15,
-13 ≤ l ≤ 13
-13 ≤ h ≤ 13,
-18 ≤ k ≤ 18,
-25 ≤ l ≤ 25
-9 ≤ h ≤ 9,
-18 ≤ k ≤ 18,
-20 ≤ l ≤ 20
Reflections collected
110751 16102 84514 17956 99281 78470
Independent reflections
7210
[Rint = 0.1020, Rsigma = 0.0438]
4222
[Rint = 0.0608, Rsigma = 0.0412]
5897
[Rint = 0.0828, Rsigma = 0.0389]
3683
[Rint = 0.0725, Rsigma = 0.0677]
6527
[Rint = 0.0947, Rsigma = 0.0368]
4087
[Rint = 0.0950, Rsigma = 0.0322]
Data/restraints/
parameters 7210/0/291 4222/0/290 5897/0/200 3683/51/224 6527/0/290 4087/12/201
Goodness-of-fit
on F2 1.061 1.061 1.06 0.94 1.066 1.178
Final R indexes
[I>=2σ (I)]
R1 = 0.0296, wR2 = 0.0665
R1 = 0.0303, wR2 = 0.0563
R1 = 0.0315, wR2 = 0.0487
R1 = 0.0354, wR2 = 0.0565
R1 = 0.0247, wR2 = 0.0497
R1 = 0.0269, wR2 = 0.0612
Final R indexes
[all data]
R1 = 0.0432, wR2 = 0.0713
R1 = 0.0396, wR2 = 0.0589
R1 = 0.0468, wR2 = 0.0520
R1 = 0.0574, wR2 = 0.0623
R1 = 0.0359, wR2 = 0.0531
R1 = 0.0287, wR2 = 0.0617
Largest diff. peak/hole / e Å-3
1.64/-1.99 0.98/-1.43 1.50/-1.73 1.16/-0.61 1.21/-1.88 0.98/-2.15
Flack parameter 0.025(17) 0.406(13)
CCDC No. 1554899 1554895 1554898 1554896 1554900 1554897
S20
Table S2: Chemical potential (µ), hardness/MO energy gap (ƞ) and electrophilicity index (ω) reported in eV for 1a, 1b, 3a and 3b.
1a 1b 3a 3b
ELUMO -3.3214235 -3.3861866 -3.3616964 -3.4561199
EHOMO -6.3603926 -6.3620253 -6.4657008 -6.4363124
µ -4.84090805 -4.87410595 -4.9136986 -4.94621615
ƞ 3.0389691 2.9758387 3.1040044 2.9801925
ω 7.7112962 7.983265 7.7784793 8.209219
S21
Table S3: Major experimental UV-Vis transitions their corresponding calculated molecular orbitals for 1a.
Major Contributing Excitation (%) Transition energy
(nm)
Oscillator
Strength
λλλλexp (nm) εεεεexp (M-1
cm-1
)
1a HOMO → LUMO (98) 493 0.223 450 14835
HOMO−1→LUMO (80) HOMO →LUMO+3 (12)
393 0.219 390 12265
HOMO→LUMO+1 (29) HOMO→LUMO+3 (49)
341 0.228 320 20995
(1a)−−−− HOMOα→LUMO+7α (32)
HOMOα→LUMO+8α (51)
538 0.0187 540 315
HOMOα→LUMO+12α (20),
HOMOβ→LUMOβ (17), HOMOβ→LUMO+3β (19)
403 0.1039 390 6100
Figure S30: Normal Transition orbitals (NTOs) for the major absorption bands of 1a.
S22
Figure S31: Normal Transition orbitals (NTOs) for the major absorption bands of 1a−−−−.
Figure S32: Spin population of 1a−−−− and 1a
+ on the left and right hand side respectively.
S23
Table S4: Major experimental UV-Vis transitions their corresponding calculated molecular orbitals for 1b.
Major Contributing Excitation (%) Transition energy
(nm)
Oscillator
Strength
λλλλexp (nm) εεεεexp (M-1
cm-1
)
1b HOMO→LUMO (99)
497 0.2773 455 14165
H-1→LUMO (82)
406 0.3036 395 12546
H-5→LUMO (10)
HOMO→L+1 (14)
HOMO→L+3 (50)
338 0.1797 322 18907
(1b)−−−− HOMO(A) →L+5(A) (57)
HOMO(A) →L+8(A) (10)
HOMO(A)->L+9(A) (10)
528 0.0126 540 391
H-1(A) →L+1(A) (14)
HOMO(A) →L+8(A) (14)
HOMO(B) →LUMO(B) (19) HOMO(B) →L+2(B) (35)
434
0.1213 405 18793
Figure S33: Normal Transition orbitals (NTOs) for the major absorption bands of 1b.
S24
Figure S34: Normal Transition orbitals (NTOs) for the major absorption bands of 1b
−−−−.
Figure S35: Spin population of 1b−−−− and 1b
+ on the left and right hand side respectively.
S25
Figure S36: Changes in UV-Vis absorption spectrum of 2a during the reduction event in CH2Cl2 containing 0.1 M NnBu4[B(C6F5)4] electrolyte, applied voltage range: -1.1 to -1.4 V; The inset shows the appearance of a 1600 nm
Intervalence charge transfer (IVCT) feature at an applied voltage -1.4 V. (Legend: Increasing cathodic voltages from black to
light green)
Figure S37: Changes in UV-Vis absorption spectrum of 3a during the reduction event in CH2Cl2 containing 0.1 M
NnBu4[B(C6F5)4] electrolyte, applied voltage range: -1.1 to -1.4 V (Legend: Increasing cathodic voltages from black to light
green)
S26
Figure S38: Changes in UV-Vis absorption spectrum of 3b during the reduction event in CH2Cl2 containing 0.1 M
NnBu4[B(C6F5)4] electrolyte, applied voltage range: -1.1 to -1.4 V (Legend: Increasing cathodic voltages from black to light
green)