G. Berthon-Gelloz et al. / Journal of Organometallic Chemistry 690 (2005) 6156–6168
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4.2.1. IMe–Pt(dvtms) (1)
1
Si–CH@ + @CH2 + adamantyl), 0.34 (s, 6H, SiCH3eq),
ꢀ0.25 (s, 6H, SiCH3ax); NMR 13C (75 MHz, CDCl3):
d = 180.3 (Pt–Ccar), 117.5 (C@CAN), 116.4 (C@CÆN),
Yield: 77%. H NMR (300 MHz, CDCl3): d = 7.00 (s,
4
2H, JPt–H = 11.8 Hz, HImi), 3.54 (s, 6H, N–CH3), 2.22
(d, 2H, 3J = 10.3 Hz, JPt–H ¼ 52:8 Hz, C@CH2eq),
59.9 (N–Cadamantyl), 59.2 (N–Cadamantyl), 43.2 (1JPt–C
=
2
Å
2.02–1.71 (m, 4H, @CH2ax@SiACH@), 0.34 (s, 6H, Si-
CH3eq), ꢀ0.29 (s, 6H, SiCH3ax); NMR 13C (75 MHz,
CDCl3): d = 179.8 (Pt–Ccar), 122.3 (C@CAN), 42.7 (C–
Si), 40.7 (NCH3), 34.5 (C@CHSi), 1.8 (SiCH3eq), ꢀ1.4 (Si-
CH3ax); 195Pt NMR (107 MHz, CDCl3): d = ꢀ5343 ppm.
IR (film, cmꢀ1): 2923 s, 1234 m, 1178 m, 992 m. MS
(APCI): m/z = 451–450–449 [MH ꢀ vinyl]+, 293–292–291
[MH ꢀ dvtms]+, 97 [IMe ꢀ H]+.
185.4 Hz, C–Si), 42.9 (CHadamantyl), 42.5 (CHadamantyl),
36.0 (CHadamantyl), 31.4 (1JPt–C = 123.6 Hz, C@CHSi),
30.2 (CH2 adamantyl), 30.0 (CH2 adamantyl), 1.8 (SiCH3eq),
ꢀ2.7 (SiCH3ax); 195Pt NMR (107 MHz, CDCl3):
d = ꢀ5306 ppm. IR (film, cmꢀ1): 2923 s, 1234 m, 1178 m,
992 m. MS (APCI): m/z = 531–530–529 [MH ꢀ dvtms]+,
337 [IAd ꢀ H]+.
4.2.5. IMes–Pt(dvtms) (5)
1
4.2.2. ICy–Pt(dvtms) (2)
Yield: 90%. 1H NMR (200 MHz, CDCl3): d = 7.24 (s, 2H,
Yield: 85%. H NMR (300 MHz, CDCl3): d = 7.12 (s,
4
2H, JPt–H = 9.2 Hz, HImi), 6.86 (s, 4H, Mes), 2.25 (s, 6H,
4JPt–H = 12.6 Hz, HImi), 4.30 (tt, 1H, Jtrans = 12.6 Hz,
p-Me), 2.12 (s, 12H, o-Me), 1.93 (d, 2H, 3J = 11.3 Hz,
3
3Jcis = 7.7 Hz, N–CH), 4.19 (tt, 1H, Jtrans = 12.6 Hz,
JPt–H ¼ 55:0 Hz, C@CH2eq), 1.73-1.20 (m, 4H,
3
2
Å
3Jcis = 3.5 Hz, N–CH), 2.17 (d, 2H, 3J = 10.1 Hz,
SiACH@ + @CH2 aq), 0.16 (s, 6H, SiCH3eq), ꢀ0.77 (s,
6H, SiCH3ax); NMR 13C (75 MHz, CDCl3): d = 184.2
(Pt–Ccar), 138.6 (Carom.), 136.9 (Carom.), 135.4 (Carom.),
129.1 (Carom.), 128.9 (Carom.), 123.0 (3JPt–C = 41.8 Hz,
2
Å
JPt–H ¼ 53:1 Hz, C@CH2eq), 2.17–1.07 (m, 4H,
Si–CH@ + @CH2ax), 0.31 (s, 6H, SiCH3eq), ꢀ0.29 (s, 6H, Si-
CH3ax); NMR 13C (50 MHz, CDCl3): d = 180.0 (1JPt–C
=
1350 Hz, Pt–Ccar), 118.0 (C@CAN), 59.4 (3JPt–C = 15 Hz,
NCH), 59.2 (3JPt–C = 15 Hz, NCH), 41.2 (1JPt–C
C =
Im), 41.3 (1JPt–C = 165.7 Hz, C–Si), 35.3 (1JPt–C
=
117.7 Hz, C=CHSi), 21.1 (p-CH3), 18.1 (o-CH3), 1.6 (Si-
CH3eq), ꢀ2.5 (SiCH3ax); 195Pt NMR (107 MHz, CDCl3):
d = ꢀ5339 ppm. IR (film, cmꢀ1): 3134 m, 2964 s, 1488 m,
1322 m, 1246 m, 1179 m, 838 s, 784 s. MS (APCI): m/z =
659–658–658 [MH ꢀ CH@CH2]+, 305 [IMes ꢀ H]+. Anal.
Calc. for C29H42N2OPtSi2: C, 50.78; H, 6.17; N, 4.08.
Found: C, 50.86; H, 6.14; N, 4.04.
157.9 Hz, C–Si), 34.6 (Ccyclohexyl), 34.5 (1JPt–C = 119.0 Hz,
C@CHSi), 25.4 (Ccyclohexyl), 25.3 s (Ccyclohexyl), 1.4 (Si-
CH3eq), ꢀ1.9 (SiCH3ax); 195Pt NMR (107 MHz, CDCl3):
d = ꢀ5343 ppm. IR (film, cmꢀ1): 3008 w, 2933 s, 1450 m,
1422 m, 1295 m, 1236 m, 1170 m, 992 s, 779 s. MS (APCI):
m/z = 587–586–585 [MH ꢀ vinyl]+, 233 (100) [ICy ꢀ H]+.
Anal. Calc. for C23H42N2OPtSi2: C, 45.00; H, 6.90; N,
4.56. Found: C, 44.95; H, 6.82; N, 4.47.
4.2.6. IPr–Pt(dvtms) (6)
1
Yield: 70%. H NMR (300 MHz, CDCl3): d = 7.35 (t,
4.2.3. ItBu–Pt(dvtms) (3)
2H, 3J = 7.7 Hz, p-HPh), 7.20 (s, 2H, JPt–H = 7.8 Hz,
4
Yield: 65%. 1H NMR (200 MHz, CDCl3): d = 7.31 (s, 1H,
3J = 2.2 Hz, 4JPt–H = 12.0 Hz, HImi), 7.30 (s, 1H,
H
Imi), 7.17 (d, 4H, J = 7.7 Hz, m-HPh), 2.97 (h, 4H,3J =
3
6.7 Hz, CH(CH3)2), 1.51 (d, 2H, 3J = 11.0 Hz, JPt–H
¼
2
Å
4
3
3J = 2.2 Hz, JPt–H = 12.0 Hz, CHImi), 2.26 (d, 2H, J =
54:1 Hz, C@CH2eq), 1.39–1.27 (m, 4H, Si–CH), 1.23 (d,
2H, 3J = 13.2 Hz, C@CH2ax), 1.24 (d, 12H,3J = 6.7 Hz,
CH(CH3)2), 1.13 (d, 12H, 3J = 6.7 Hz, CH(CH3)2), 0.13
(s, 6H, SiCH3eq), ꢀ0.76 (s, 6H, SiCH3ax); NMR 13C
(75 MHz, CDCl3): d = 186.4 (Pt–Ccar), 146.0 (Carom.),
11.0 Hz, JPt–H ¼ 54 Hz, C@CH2eq), 1.88 (dd, 2H, 3J =
2
Å
3
3
11.4 Hz, J = 13.6 Hz, SiACH@), 1.74 (d, 2H, J = 13.6 Hz,
2JPt–H = 52.2 Hz, =CH2ax), 1.60 (s, 9H, tBu), 0.31 (s, 6H, Si-
CH3eq), ꢀ0.28 (s, 6H, SiCH3ax); NMR 13C (50 MHz,
CDCl3): d = 181.2 (1JPt–C = 1360.8 Hz, Pt–Ccar), 118.2
(3JPt–C = 23.3 Hz, C@CÆN), 117.4 (3JPt–C = 23.3 Hz,
136.9 (4JPt–C = 9.8 Hz, Carom.), 129.5 (Carom.), 124.1 (3JPt–C
=
42.0 Hz, CIm), 123.8 (Carom.), 42.1 (1JPt–C = 166.5 Hz, C–
Si), 35.9 (1JPt–C = 120.9 Hz, C@CHSi), 28.6 (CH(CH3)2),
26.0 (CH(CH3)2), 22.6 (CH(CH3)2), 1.8 (SiCH3eq), ꢀ2.1
(SiCH3ax); 195Pt NMR (107 MHz, CDCl3): ꢀ5340 ppm.
IR (film, cmꢀ1): 3135 m, 2962 s, 1463 s, 1401 s, 1385 s,
1322 s, 1246 s, 1179 s, 1059 s, 977 s, 781 s. MS (APCI):
m/z = 744–743–742 [MH ꢀ CH@CH2]+, 579–578–577
[IPrNHC ꢀ Pt ꢀ 2H2]+, 390 [IPr ꢀ H]+, 385 [IPr ꢀ
H ꢀ 2H2]+. Anal. Calc. for C35H54N2OPtSi2: C, 54.59; H,
7.07; N, 3.64. Found: C, 54.44; H, 7.10; N, 3.50.
C@CÆN), 58.8 (3JPt–C = 11.5 Hz, C(CH3)), 58.5 (3JPt–C
=
11.5 Hz, C(CH3)3), 46.7 (1JPt–C = 184.2 Hz, C–Si), 32.0
(1JPt–C = 123.2 Hz, C=CHSi), 31.0 (C(CH3)3), 30,6
(C(CH3)3), 1.6 (SiCH3eq), ꢀ2.7 (SiCH3ax); 195Pt NMR
(107 MHz, CDCl3): d = ꢀ5333 ppm. IR (film, cmꢀ1): 1915
w, 1540 w, 1476 m, 1397 m, 1368 m, 1340 s, 1299 s, 1245 s,
1219 s, 1175 s, 1010 s, 977 s, 908 m, 845 s, 838 s, 778 s. MS
(EI): m/z = 562.1–561–560 ([M]+Å), 318–317–316 (100)
([M ꢀ dvtms]+Å), 181 ([ItBu ꢀ H]+Å); m.p. = 189–191 ꢁC.
4.2.4. IAd–Pt(dvtms) (4)
1
4.3. General procedure for the synthesis of
SNHC–Pt(dvtms) complexes
Yield: 66%. H NMR (300 MHz, CDCl3): d = 7.30 (d,
1H, 3J = 2.3 Hz, JPt–H ¼ 11:8 Hz, HImi), 7.28 (s, 1H,
4
Å
3
3
2
Å
J = 2.3 Hz, JPt–H ¼ 11:8 Hz, CHImi), 2.35 (d, 2H, J =
The 4,5-dihydroimidazol-2-ylidene platinum(0)(dvtms)
complexes were synthesized and purified in an analogous
2
Å
11.2 Hz, JPt–H ¼ 53:2 Hz, C@CH2eq). 2.30–1.21 (m, 30H,