M.H. Garcia et al. / Journal of Organometallic Chemistry 694 (2009) 2888–2897
2895
3
3
excess of thiophene ligand derivative. Furthermore, the desired
product co-precipitated with TlCl was solubilized with dichloro-
methane and filtered to remove the thallium salt. The solvent
was evaporated under vacuum and the solid obtained was recrys-
tallized together with previous isolated residue from dichloro-
methane/n-hexane or dichloromethane/diethyl ether giving the
desired complexes as orange-reddish microcrystalline products.
1H and 13C NMR data relative to dppe and (+)-diop coordinated
phosphines are very similar in the ruthenium(II) compounds, and
are described below.
6.55 (d, 1H, H3, JHH = 4.2), 6.98 (d, 1H, H4, JHH = 3.9), 7.16 (d,
3
3
1H, H11, JHH = 4.5), 7.19 (d, 1H, H7, JHH = 3.9), 7.32 (d, 1H, H8,
3JHH = 3.9), 7.85 (d, 1H, H12, JHH = 4.2); 13C NMR (CD2Cl2): d
3
82.84 (g
5-C5H5), 107.11 (C2), 121.03 (NC), 123.84 (C8), 124.63
(C7), 127.85 (C11), 128.05 (C4), 130.23 (C12), 136.59 (C9), 136.80
(C6), 139.96 (C3), 143.84 (C10), 144.36 (C5), 150.27 (C13); 31P
NMR (CD2Cl2): d 79.8. Anal. Calc. for C44H35F6N2O2P3S3Ru: C,
51.41; H, 3.43, N, 2.72; S, 9.36. Found: C, 51.58; H, 3.36, N, 2.67;
S, 9.19%.
Compounds 1a and 2a. For dppe: 1H NMR (CDCl3): 2.56–2.68 (m,
4H, CH2), 7.22–7.29 (m, 4H, C6H5), 7.43–7.54 (m, 8H, C6H5), 7.58 (t,
4.2.4. RuCp((+)-diop)(NC{SC4H2}NO2)PF6 (1b)
56% yield, orange-reddish, recrystallized from CH2Cl2/n-hexane,
3
3
4H, C6H5, JHH = 7.5), 7.78 (m, 4H, C6H5, JHH = 8.5); 13C NMR
m.p. 162 °C (dec.). Molar conductivity (
(KBr) cmꢁ1 (N„C) 2205. 1H NMR (CDCl3): d 4.52 (s, 5H, g5
C5H5), 7.42 (d, 1H, H3, JHH = 4.2), 7.80 (d, 1H, H4, JHH = 4.2); 13C
X
ꢁ1 cm2 molꢁ1) 88.5. IR
1
(CDCl3): d 28.08 (t, CH2, JCP = 23.0), 129.12 and 129.50 (t, Cmeta
,
:
t
-
3JCP = 4.8), 130.58 and 133.03 (t, Cortho 2JCP = 4.8), 130.64 and
,
3
3
131.27 (s, Cpara), 136.98 (t, Cipso
,
1JCP = 2.8).
NMR (CDCl3): d 84.73 (g
5-C5H5), 113.78 (C2), 121.24 (NC),
Compound 3a. For dppe: 1H NMR (CD2Cl2): d 2.58–2.66 (m, 4H,
128.51 (C4), 139.61 (C3), 155.02 (C5); 31P NMR (CDCl3): d 35.5
(2d, JPAPB = 38.1). Anal. Calc. for C41H39F6N2O4P3SRu: C, 51.09; H,
4.08, N, 2.91; S, 3.33. Found: C, 50.95; H, 4.36, N, 2.86; S, 3.02%.
CH2), 7.26–7.32 (m, 4H, C6H5), 7.46–7.50 (m, 6H, C6H5), 7.57–
7.62 (m, 6H, C6H5), 7.76–7.82 (m, 4H, C6H5); 13C NMR (CD2Cl2): d
1
28.23 (t, CH2, JCP = 22.8), 129.41 and 129.66 (t, Cmeta
,
3JCP = 4.9),
130.98 and 131.55 (s, Cpara), 131.09 and 133.36 (t, Cortho
,
4.2.5. RuCp((+)-diop)(NC{SC4H2}2NO2)PF6 (2b)
2JCP = 4.8), 137.25 (t, Cipso 1JCP = 2.8).
,
48% yield, orange-reddish, recrystallized from CH2Cl2/diethyl
Compounds 1b and 2b. For (+)-diop: 1H NMR (CDCl3): d 1.14 (s,
3H, CH3), 1.31 (s, 3H, CH3), 2.31–2.41 (m, 1H, CH), 2.58–2.68 (m,
1H, CH), 3.10–3.31 (m, 2H, CH2), 3.48–3.64 (m, 2H, CH2), 7.11–
7.18 (m, 4H, C6H5), 7.40–7.46 (m, 6H, C6H5), 7.54–7.60 (m, 4H,
C6H5), 7.66–7.72 (m, 4H, C6H5), 7.85–7.92 (m, 2H, C6H5); 13C
NMR (CDCl3): d 26.73 (s, CH3), 26.90 (s, CH3), 29.04 (d, CH2,
ether, m.p. 205–206 °C. Molar conductivity (
X
ꢁ1 cm2 molꢁ1) 86.2.
IR (KBr) cmꢁ1 (N„C) 2210. 1H NMR (CDCl3): d 4.48 (s, 5H, g5
:
t
-
3
3
C5H5), 7.20 (d, 1H, H7, JHH = 4.2), 7.32 (d, 1H, H4, JHH = 3.6), 7.59
(d, 1H, H3, 3JHH = 3.6), 7.86 (d, 1H, H8, 3JHH = 4.2); 13C NMR (CDCl3):
d 84.18 (g
5-C5H5), 108.91 (C2), 122.80 (NC), 125.38 (C7), 126.97
(C4), 128.70 (C8), 140.97 (C3), 141.27 (C6), 141.93 (C5), 151.41
(C9); 31P NMR (CDCl3): d 35.8 (2d, JPAPB = 38.1). Anal. Calc. for
C45H41F6N2O4P3S2Ru: C, 51.68; H, 3.95, N, 2.68; S, 6.13. Found: C,
51.82; H, 4.12, N, 2.59; S, 5.98%.
1
2
1JCP = 21.4), 30.75 (d, CH2, JCP = 3.4), 75.58 (d, CH, JCP = 11.7),
2
78.36 (d, CH, JCP = 6.2), 109.06 (s, C(CH3)2), 128.82–134.34 (m,
C6H5), 138.78 (d, Cipso, ,
1JCP = 47.6), 141.06 (d, Cipso 1JCP = 46.4).
Compound 3b. For (+)-diop: 1H NMR (CD2Cl2): d 1.06 (s, 3H, CH3),
1.26 (s, 3H, CH3), 2.32–2.43 (m, 1H, CH), 2.60–2.67 (m, 1H, CH),
3.15–3.25 (m, 2H, CH2), 3.58–3.70 (m, 2H, CH2), 7.38–7.48 (m,
10H, C6H5), 7.54–7.80 (m, 8H, C6H5), 7.85–7.91 (m, 2H, C6H5); 13C
NMR (CD2Cl2): d 26.85 (s, CH3), 26.98 (s, CH3), 29.19 (d, CH2,
4.2.6. RuCp((+)-diop)(NC{SC4H2}3NO2)PF6 (3b)
40% yield, red, recrystallized from CH2Cl2/diethyl ether, m.p.
145 °C (dec.). Molar conductivity (
cmꢁ1 (N„C) 2215. 1H NMR (CD2Cl2): d 4.41 (s, 5H,
7.17 (d, 1H, H11, JHH = 4.5), 7.20 (d, 1H, H4, JHH = 4.5), 7.26 (d,
X
ꢁ1 cm2 molꢁ1) 81.9. IR (KBr)
:
t
g
5-C5H5),
1
2
3
3
1JCP = 21.0), 32.00 (d, CH2, JCP = 29.0), 75.80 (d, CH, JCP = 11.6),
2
3
3
78.72 (d, CH, JCP = 9.4), 109.41 (s, C(CH3)2), 129.10–134.83 (m,
1H, H7, JHH = 4.2), 7.27 (d, 1H, H3, JHH = 3.9), 7.35 (d, 1H, H8,
3
C6H5), 138.93 (d, Cipso
,
1JCP = 41.8), 141.92 (d, Cipso
,
1JCP = 38.4).
3JHH = 3.9), 7.87 (d, 1H, H12, JHH = 4.5); 13C NMR (CD2Cl2): d
84.20 (g
5-C5H5), 106.77 (C2), 123.96 (C8), 124.87 (NC), 125.27
4.2.1. [RuCp(dppe)(NC{SC4H2}NO2)PF6 (1a)
78% yield, red, recrystallized from CH2Cl2/n-hexane, m.p. 224–
226 °C. Molar conductivity (
ꢁ1 cm2 molꢁ1) 87.4. IR (KBr) cmꢁ1
(N„C) 2220. 1H NMR (CDCl3): d 4.87 (s, 5H, 5-C5H5), 7.00 (d,
1H, H3, JHH = 4.5), 7.61 (d, 1H, H4, JHH = 4.5); 13C NMR (CDCl3):
(C7), 128.18 (C11), 128.13 (C4), 130.46 (C12), 136.50 (C9), 137.00
(C6), 140.58 (C3), 143.80 (C10), 145.32 (C5), 150.49 (C13); 31P
X
:
NMR (CD2Cl2):
d
36.0 (2d, JPAPB = 38.1). Anal. Calc. for
t
g
C49H43F6N2O4P3S3Ru: C, 52.17; H, 3.84, N, 2.48; S, 8.53. Found: C,
52.29; H, 3.92, N, 2.39; S, 8.37%.
3
3
d
83.27
(g
5-C5H5), 113.84 (C2), 118.55 (NC), 128.04 (C4),
g
138.62 (C3), 154.51 (C5); 31P NMR (CDCl3): d 79.3. Anal. Calc.
4.3. Electrochemical studies
for C36H31F6N2O2P3SRu: C, 50.06; H, 3.62, N, 3.24; S, 3.71. Found:
C, 50.32; H, 3.65, N, 3.08; S, 3.42%.
The electrochemistry instrumentation consisted of a EG&A
Princeton Applied Research Model 273A Potentiometer and exper-
iments were monitored in a PC computer loaded with Model 270
Electrochemical Analysis Software 3.00 of EG&A from Princeton
Applied Research. Potentials were referred to a calomel electrode
containing a saturated solution of potassium chloride. The working
electrode was a 2-mm piece of platinum wire for voltammetry. The
secondary electrode was a platinum wire coil. Cyclic voltammetry
experiments were performed at room temperature and ꢁ20 °C in a
PAR polarographic cell. Solutions studied were 1 mM in solute and
0.1 M in tetrabutylammonium hexafluorophosphate as supporting
electrolyte. The electrochemical system was checked with a 1 mM
solution of ferrocene in acetonitrile and dichloromethane for
which the ferrocinium/ferrocene electrochemical parameters
(Ep/2 = 0.38 V in acetonitrile and Ep/2 = 0.41 V in dichloromethane;
4.2.2. RuCp(dppe)(NC{SC4H2}2NO2)PF6 (2a)
72% yield, orange; recrystallized from CH2Cl2/n-hexane, m.p.
255 °C (dec.). Molar conductivity (
cmꢁ1 (N„C) 2225. 1H NMR (CDCl3): d 4.85 (s, 5H,
6.76 (d, 1H, H3, JHH = 4.2), 7.07 (d, 1H, H4, JHH = 4.2), 7.13 (d,
X
ꢁ1 cm2 molꢁ1) 86.8. IR (KBr)
:
t
g
5-C5H5),
3
3
3
3
1H, H7, JHH = 4.2), 7.83 (d, 1H, H8, JHH = 4.2); 13C NMR (CDCl3):
d 82.74 (
5-C5H5), 109.81 (C2), 120.37 (NC), 125.14 (C7), 126.44
g
(C4), 128.14 (C8), 140.37 (C3), 141.14 (C5), 141.71 (C6), 151.22
(C9); 31P NMR (CDCl3): d 79.6. Anal. Calc. for C40H33F6N2O2P3S2Ru:
C, 50.80; H, 3.52, N, 2.96; S, 6.78. Found: C, 50.92; H, 3.64, N, 2.88;
S, 6.51%.
4.2.3. RuCp(dppe)(NC{SC4H2}3NO2)PF6 (3a)
68% yield, red, recrystallized from CH2Cl2/diethyl ether, m.p.
DE = 60–70 mV; Ia/Ic = 1) were in good agreement with the litera-
ture [33,34]. The electrolyte was purchased from Aldrich Chemical
Co., recrystallized from ethanol, washed with diethyl ether, and
246–247 °C. Molar conductivity (
X
ꢁ1 cm2 molꢁ1) 84.3. IR (KBr)
cmꢁ1 (N„C) 2215. 1H NMR (CD2Cl2): d 4.84 (s, 5H, 5-C5H5),
:
t
g