Article
Organometallics, Vol. 30, No. 5, 2011 1199
(s), 750 (m), 603 (m). EI-MS: m/z 279 [M - C5Me5 - NPh2]þ
(10%). Anal. Found (calcd for C31H42N4S2Ti): C, 63.88 (63.90);
H, 7.40 (7.27); N, 9.55 (9.62).
C6H5), 7.36 (2 H, d, 3J = 7.5 Hz, ob-C6H5), 7.21 (2H, t, 3J = 7.5
Hz, ma-C6H5), 7.12 (4 H, m, overlapping mb-C6H5 and m-
C6H4Me), 6.97 (2 H, d, 3J = 8.4 Hz, o-C6H4Me), 6.89 (1 H, t,
3J = 7.5 Hz, pa-C6H5), 6.79 (1 H, t, 3J = 7.5 Hz, pb-C6H5), 3.25
(1 H, app sept, app 3J = 6.6 Hz, NCHaMeMe), 2.98 (1 H, app
NMR Tube Scale Reaction of Cp*Ti{MeC(NiPr)2}(NNPh2)
(13) with Cp*Ti{MeC(NiPr)2}{N(NMe2)C(S)S} (21). To a solu-
tion of Cp*Ti{MeC(NiPr)2}{N(NMe2)C(S)S} (21; 0.012 g,
0.026 mmol) in C6D6 (0.3 mL) in an NMR tube equipped with
a J. Young Teflon valve was added Cp*Ti{MeC(NiPr)2}-
(NNPh2) (13; 0.013 g, 0.026 mmol) in C6D6 (0.3 mL) at room
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sept, app J = 6.6 Hz, NCHbMeMe), 2.08 (3 H, s, C6H4Me),
1.94 (15 H, s, C5Me5), 1.51 (3 H, s, MeCN2), 1.21 (6 H, over-
lapping 2 ꢀ d, 3J = 6.6 Hz, overlapping NCHaMeMe and
NCHbMeMe), 1.10 (3 H, d, 3J = 6.6 Hz, NCHaMeMe), 0.97 (3
1
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temperature. The reaction was monitored by H NMR spec-
H, d, J = 6.6 Hz, NCHbMeMe). 13C{1H} NMR (C6D6, 75.4
troscopy. [Cp*Ti{MeC(NiPr)2}(μ-S)]2 (25) and Cp*Ti{MeC-
(NiPr)2}{N(NPh2)C(NNMe2)S} (26) were formed quantita-
tively after 4 days. 26 was characterized by 1H NMR spectros-
copy. 1H NMR data (C6D6, 499.9 MHz, 293 K): δ 7.52 (1 H, d,
3J = 7.5 Hz, oa-C6H5), 7.30 (1 H, d, 3J = 7.5 Hz, ob-C6H5), 7.21
(2 H, app t, app 3J = 7.5 Hz, ma-C6H5), 7.10 (2 H, app t, app 3J =
MHz, 293 K): δ 169.1 (MeCN2), 154.7 (SC(N)N), 147.5
(overlapping ia-C6H5, ib-C6H5 and i-C6H4Me), 130.9 (p-
C6H4Me), 129.8 (C5Me5), 129.0 (o-C6H4Me), 128.5 (ma-
C6H5), 123.7 (overlapping m-C6H4Me and mb-C6H5), 121.9
(pa-C6H5), 121.4 (oa-C6H5), 119.5 (pb-C6H5), 117.7 (ob-C6H5),
51.9 (NCHaMeMe), 49.6 (NCHbMeMe), 26.3 (NCHbMeMe),
25.5 (NCHbMeMe), 24.6 (NCHaMeMe), 23.5 (NCHaMeMe),
20.9 (C6H4 Me), 14.2 (MeCN2), 13.6 (C5Me5). IR (NaCl plates,
Nujol mull, cm-1): ν 1577 (s), 1490 (s), 1412 (m), 1327 (m), 1313
(m), 1278 (m), 1204 (m), 1167 (m), 1153 (m), 1104 (m), 1042 (m),
1020 (m), 944 (w), 810 (m), 763 (w), 740 (m), 690 (m), 649 (w). EI-
MS: m/z 338 [M - TolNCS - NPh2]þ (20%). Anal. Found
(calcd for C38H49N5STi): C, 69.63 (69.60); H, 7.60 (7.53); N,
10.63 (10.68).
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7.5 Hz, mb-C6H5), 6.88 (2 H, t, J = 7.5 Hz, pa-C6H5), 6.79 (2
H, t, 3J = 7.5 Hz, pb-C6H5), 3.29 (1 H, app sept, app 3J = 6.5 Hz,
NCHaMeMe), 2.97 (1 H, app sept, app 3J = 6.5 Hz,
NCHbMeMe), 2.51 (6 H, s, NNMe2), 1.96 (15 H, s, C5Me5),
1.50 (3 H, s, MeCN2), 1.20 (6 H, overlapping 2 ꢀ d, 3J = 6.5 Hz,
overlapping NCHaMeMe and NCHbMeMe), 1.17 (3 H, d, 3J =
6.5 Hz, NCHaMeMe), 0.83 (3 H, d, 3J = 6.5 Hz, NCHbMeMe).
13C{1H} NMR (C6D6, 125.7 MHz, 293 K): δ 168.7 (MeCN2),
156.0 (SC(N)N), 147.4 (ia-C6H5) 147.4 (ib-C6H5), 129.2 (C5Me5),
128.3 (ma-C6H5), 128.1 (mb-C6H5), 121.7 (pa-C6H5), 121.3 (oa-
C6H5), 119.4 (pb-C6H5), 117.7 (ob-C6H5), 51.6 (NCHaMeMe), 49.4
(NCHbMeMe), 48.7 (NNMe2), 26.3 (NCHbMeMe), 25.5
(NCHbMeMe), 24.6 (NCHaMeMe), 23.5 (NCHaMeMe), 14.2
(MeCN2), 13.5 (C5Me5).
Cp*Ti{MeC(NiPr)2}{N(NPh2)C(NtBu)O} (30). To a solution
of Cp*Ti{MeC(NiPr)2}(NNPh2) (13; 0.300 g, 0.590 mmol) in
benzene (20 mL) was added tBuNCO (67.6 μL, 0.590 mmol), all
at room temperature. An immediate color change from dark
yellow to dark brown was observed. After 16 h, the volatiles
were removed under reduced pressure to afford 30 as a dark
brown solid. The resultant dark brown solid was washed with
cold pentane (3 ꢀ 5 mL), filtered, and dried in vacuo. Yield:
0.184 g (51%). 1H NMR (C6D6, 299.9 MHz, 293 K): δ 7.62 (2 H,
d, 3J = 6.5 Hz, oa-C6H5), 7.22 (2 H, t, 3J = 6.5 Hz, ma-C6H5),
7.09 (2 H, d, 3J = 6.5 Hz, ob-C6H5), 7.01 (2 H, t, 3J = 6.5 Hz, mb-
C6H5), 6.88 (1 H, t, 3J = 6.5 Hz, pa-C6H5), 6.71 (1 H, t, 3J = 6.5
Hz, pb-C6H5), 3.34 (1 H, app sept, app 3J = 6.5 Hz,
NCHaMeMe), 2.80 (1 H, app sept, app 3J = 6.5 Hz,
Cp*Ti{MeC(NiPr)2}{N(NPh2)C(NTol)O} (24). To a solution
of Cp*Ti{MeC(NiPr)2}(NNPh2) (13; 0.400 g, 0.790 mmol) in
benzene (20 mL) was added p-TolNCO (0.100 mL, 0.790 mmol),
all at room temperature. An immediate color change from dark
yellow to dark brown was observed. After 16 h, the volatiles
were removed under reduced pressure to afford 24 as a dark
brown solid. The resultant dark brown solid was washed with
cold pentane (3 ꢀ 5 mL), filtered, and dried in vacuo. Yield:
0.342 g (68%). 1H NMR (C6D6, 299.9 MHz, 293 K): δ 7.71 (2 H,
d, 3J = 7.5 Hz, oa-C6H5), 7.65 (2 H, d, 3J = 7.5 Hz, o-C6H4Me),
7.20 (2 H, t, 3J = 7.5 Hz, ma-C6H5), 7.10 (4 H, m, overlapping
ob-C6H5 and m-C6H4Me), 7.02 (2 H, t, 3J = 7.5 Hz, mb-C6H5),
6.90 (1 H, t, 3J = 7.5 Hz, pa-C6H5), 6.74 (1 H, t, 3J = 7.5 Hz, pb-
C6H5), 3.29 (1 H, app sept, app 3J = 6.5 Hz, NCHaMeMe), 2.82
t
NCHbMeMe), 1.96 (15 H, s, C5Me5), 1.56 (9 H, s, Bu), 1.39
(3 H, s, MeCN2), 1.17 (3 H, d, 3J = 6.5 Hz, NCHaMeMe), 1.14
(3 H, d, 3J = 6.5 Hz, NCHaMeMe), 1.09 (3 H, d, 3J = 6.5 Hz,
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NCHbMeMe), 0.92 (3 H, d, J = 6.5 Hz, NCHbMeMe). 13C-
{1H} NMR (C6D6, 75.4 MHz, 293 K): δ 168.5 (MeCN2), 152.4
(OC(N)N), 148.1 (ia-C6H5), 147.8 (ib-C6H5), 128.4 (C5Me5),
128.3 (ma-C6H5), 128.1 (mb-C6H5), 121.7 (pa-C6H5), 121.6 (oa-
C6H5), 119.3 (pb-C6H5), 117.7 (ob-C6H5), 51.90 (NCMe3), 50.4
(NCHaMeMe), 49.5 (NCHbMeMe), 32.9 (NCMe3), 26.2
(NCHbMeMe), 25.1 (NCHbMeMe), 25.0 (NCHaMeMe),
24.35 (NCHaMeMe), 13.0 (MeCN2), 12.9 (C5Me5). IR (NaCl
plates, Nujol mull, cm-1): ν 1653 (m), 1636 (w), 1589 (w), 1559
(w), 1540 (w), 1521 (w), 1506 (w), 1490 (m), 1458 (s), 1335 (w),
1313 (w), 1207 (w), 1175 (w), 1019 (w), 793 (w), 744 (w), 691 (w),
668 (m). Anal. Found (calcd for C35H51N5OTi): C, 69.52
(69.41); H, 8.42 (8.49); N, 11.48 (11.56).
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(1 H, app sept, app J = 6.5 Hz, NCHbMeMe), 2.18 (3 H, s,
C6H4Me), 1.96 (15 H, s, C5Me5), 1.40 (3 H, s, MeCN2), 1.17 (3
H, d, 3J = 6.5 Hz, NCHbMeMe), 1.11 (6 H, overlapping 2 ꢀ d,
3J = 6.5 Hz, overlapping NCHaMeMe and NCHaMeMe), 0.93
(3 H, d, 3J = 6.5 Hz, NCHbMeMe). 13C{1H} NMR (C6D6, 75.4
MHz, 293 K): δ 169.4 (MeCN2), 155.9 (OC(N)N), 147.7
(overlapping ia-C6H5 and ib-C6H5), 147.2 (i-C6H4Me), 129.7
(p-C6H4Me), 129.6 (C5Me5), 129.0 (m-C6H4Me), 128.7 (ma-
C6H5), 128.4 (mb-C6H5), 125.8 (o-C6H4Me), 122.41 (pa-C6H5),
122.2 (oa-C6H5), 119.3 (pb-C6H5), 117.2 (ob-C6H5), 50.9
(NCHaMeMe), 49.9 (NCHbMeMe), 26.3 (NCHbMeMe), 24.8
(NCHbMeMe), 24.4 (NCHaMeMe), 24.2 (NCHaMeMe), 21.0
(C6H4Me), 12.9 (C5Me5), 12.7 (MeCN2). IR (NaCl plates, Nujol
mull, cm-1): ν 1619 (m), 1587 (s), 1491 (s), 1336 (m), 1315 (m),
1206 (m), 1173 (w), 1124 (w), 1027 (w), 982 (w), 811 (w), 743 (m),
691 (w). EI-MS: m/z 506 [M - OC(NTol)]þ (20%). A satisfac-
tory elemental analysis could not be obtained.
Cp*Ti{MeC(NiPr)2}{OC(NTol)N(NPh2)C(O)O} (31). A so-
lution of Cp*Ti{MeC(NiPr)2}{N(NPh2)C(NTol)O} (24; 0.450
g, 0.700 mmol) in toluene (20 mL) was freeze-pump-thawed
three times. The solution was then exposed to CO2 at a pressure
of ca. 1.1 atm at room temperature. After 4 days, the volatiles
were removed under reduced pressure to afford 31 as a dark
brown solid. The resultant dark brown solid was washed with
cold pentane (3 ꢀ 5 mL), filtered, and dried in vacuo. Yield:
0.178 g (37%). 1H NMR (C6D6, 299.9 MHz, 293 K): δ 7.95 (2 H,
d, 3J = 6.0 Hz, oa-C6H5), 7.40 (2 H, d, 3J = 6.0 Hz, ob-C6H5),
7.29 (2H, t, 3J = 6.0 Hz, ma-C6H5), 7.10 (2 H, m, mb-C6H5), 7.00
(4 H, m, overlapping o- and m-C6H4Me), 6.98 (1 H, m, pa-C6H5),
6.82 (1 H, t, 3J = 6.0 Hz, pb-C6H5), 3.47 (1 H, app sept, app 3J =
Cp*Ti{MeC(NiPr)2}{N(NPh2)C(NTol)S} (28). To a solution
of Cp*Ti{MeC(NiPr)2}(NNPh2) (13; 0.300 g, 0.590 mmol) in
benzene (15 mL) was added p-TolNCS (88.0 mg, 0.590 mmol) in
benzene (15 mL), all at room temperature. The resulting dark
green solution was stirred for 16 h. Volatiles were then removed
under reduced pressure to afford 28 as a dark green solid. The
resultant dark green solid was washed with cold pentane (3 ꢀ 5
mL), filtered, and dried in vacuo. Yield: 0.210 g (54%). 1H NMR
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6.0 Hz, NCHaMeMe), 3.35 (1 H, app sept, app J = 6.0 Hz,
NCHbMeMe), 2.19 (3 H, s, C6H4Me), 1.83 (15 H, s, C5Me5),
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(C6D6, 299.9 MHz, 293 K): δ 7.57 (2 H, d, J = 7.5 Hz, oa-
1.44 (3 H, s, MeCN2), 1.13 (3 H, d, 3J = 6.0 Hz, NCHaMeMe),