3056 Organometallics, Vol. 28, No. 10, 2009
Willms et al.
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1
Hz, CCH3), 96.2 (d, JPC ) 7.0 Hz, CCH3), 104.1 (d, JPC ) 60.0
Hz, R-CHCOH), 120.2 (s, HCdCH), 126.6 (s, HCdCH), 145.9
(s, NCN) ppm. Minor diastereomer: 31P{1H} NMR (81 MHz,
2078, 1956. Anal. Calcd for C20H17FeMoN2O5P: C, 43.83; H, 3.13;
N, 5.11. Found: C, 43.88; H, 3.74; N, 5.40.
Synthesis of 10b and 11b. Ligand 3b (401 mg, 1.23 mmol) and
[Mo(CO)6] (327 mg, 1.23 mmol) were dissolved in THF (10 mL) and
heated at 60 °C for 36 h. The solution was then evaporated to dryness,
and the residue was subjected to column chromatography on neutral
alumina. 11b was eluted with hexane/diethyl ether 3:1); 10b with pure
diethyl ether. Removal of the solvents afforded 11b (244 mg, 35%)
and 10b (170 mg, 32%) as yellow solids. 10b: 31P{1H} NMR (81
1
CDCl3, 298 K): δ -83.5 (s) ppm. H NMR (200 MHz, CDCl3,
298 K): δ 2.17 (s, 3H, CCH3), 2.31 (s, 3H, CCH3), 3.07 (m, 2H,
CH2), 3.64 (s, 3H, NCH3), 3.79 (d, JPH ) 36.6 Hz, 1H, R-CH),
2
4.15 (s, 5H, Cp), 4.97 (m, 1H, HCOH), 6.84 (br s, 1H, HCdCH),
6.94 (br s, 1 H, HCdCH) ppm. The signal of the hydroxyl proton
cannot be assigned. 13C{1H} NMR (50 MHz, CDCl3, 298 K): δ
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13.7 (s, CCH3), 16.6 (s, CCH3), 32.5 (s, NCH3), 33.5 (d, JPC
15.1 Hz, CH2), 69.0 (d, JPC ) 16.7 Hz, HCOH), 71.8 (s, Cp),
)
MHz, CDCl3, 298 K): δ -22.6 (s), -22.5 (s) ppm. H NMR (200
2
MHz, CDCl3, 298 K): δ 2.01 (s, 6H, CCH3), 2.02 (s, 6H, CCH3),
2.16 (s, 12H, CCH3), 2.70 (m, 8H, PfcCH2CH2), 3.59 (d, 2JPH ) 32.6
Hz, 4H, R-CH), 4.06 (m, 8H, PfcCH2CH2), 4.19 (s, 10H, Cp), 4.23
(s, 10H, Cp), 6.19 (br s, 4H, CHCHCH), 7.19 (d, 3JHH ) 2.2 Hz, 2H,
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76.0 (d, JPC ) 57.4 Hz, R-CH), 94.2 (d, JPC ) 5.1 Hz, CCH3),
96.8 (d, 2JPC ) 6.8 Hz, CCH3), 99.7 (d, 1JPC ) 60.8 Hz, R-CHCOH),
120.2 (s, HCdCH), 126.5 (s, HCdCH), 146.7 (s, NCN) ppm. MS
(EI): m/z 356 (M+, 61%), 273 ([M - Cp - H2O]+, 100%), 121
([CpFe]+, 42%). Anal. Calcd for C17H21FeN2OP: C, 57.33; H, 5.94;
N, 7.86. Found: C, 57.19; H, 6.18; N, 7.63.
Synthesis of 9b. A solution of ligand 3b (65 mg, 0.20 mmol) in
THF (10 mL) was slowly added to a solution of [Mo(nbd)(CO)4] (60
mg, 0.20 mmol) in THF (5 mL). The reaction mixture was stirred for
4 h at ambient temperature. After evaporation of the solvent the NMR
spectra in CDCl3 showed the desired chelate complex 9b and the bis-
ligand complex 10b in a 2:1 ratio. 31P{1H} NMR (81 MHz, CDCl3,
CHCHCH), 7.22 (d, 3JHH ) 2.1 Hz, 2H, CHCHCH), 7.51 (d, 3JHH
)
1.8 Hz, 4H, CHCHCH) ppm. 13C{1H} NMR (50 MHz, CDCl3, 298
K): δ 13.1 (br s, CCH3), 16.6 (br s, CCH3), 30.6 (d, 2JPC ) 16.8 Hz,
PfcCH2CH2), 30.7 (d, 2JPC ) 15.0 Hz, PfcCH2CH2), 53.4 (d, 3JPC
)
)
5.0 Hz, PfcCH2CH2), 71.2 (br s, R-CH), 73.7 (s, Cp), 88.3 (d, 2JPC
2
4.8 Hz, CCH3), 88.4 (d, JPC ) 4.9 Hz, CCH3), 92.4 (br s, CCH3),
93.8 (s, R-CCH2), 105.3 (s, CHCHCH), 129.1 (s, CHCHCH), 139.3
(s, CHCHCH), 207.1 (m, CO), 212.6 (m, CO) ppm. MS (FAB): m/z
778 ([M - 3CO]+, 22%), 508 ([M - 3b - CO]+, 56%), 424 ([M -
3b - 4CO]+, 100%), 326 ([3b]+, 75%). IR νCO (ATR, cm-1): 2027,
1921, 1894. 11b: 31P{1H} NMR (81 MHz, CDCl3, 298 K): δ -27.5
(s) ppm. 1H NMR (200 MHz, CDCl3, 298 K): δ 1.99 (s, 3H, CCH3),
2.18 (s, 3H, CCH3), 2.68 (m, 2H, PfcCH2CH2), 3.69 (d, 2JPH ) 33.7
Hz, 1H, R-CH), 4.05 (m, 2H, PfcCH2CH2), 4.23 (s, 5H, Cp), 6.20 (vt,
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298 K): δ -24.7 (s) ppm. H NMR (200 MHz, CDCl3, 298 K): δ
2.11 (s, 3H, CCH3), 2.18 (s, 3H, CCH3), 2.67 (m, 2H, PfcCH2CH2),
3.71 (d, 2JPH ) 34.3 Hz, 1H, R-CH), 4.11 (s, 5 H, Cp), 4.79 (m, 2H,
PfcCH2CH2), 6.33 (vt, 3JHH ) 2.4 Hz, 1H, CHCHCH), 7.52 (d, 3JHH
) 2.6 Hz, 4JHH ) 0.8 Hz, 1H, CHCHCH), 7.81 (dd, 3JHH ) 2.4 Hz,
4JHH ) 0.8 Hz, 1H, CHCHCH) ppm.
3
3JHH ) 2.1 Hz, 1H, CHCHCH), 7.22 (d, JHH ) 2.1 Hz, 1H,
3
Synthesis of 10a and 11a. Ligand 3a (241 mg, 0.77 mmol) and
[Mo(CO)6] (205 mg, 0.77 mmol) were dissolved in THF (10 mL)
and heated at 60 °C overnight. The solution was then evaporated
to dryness, and the residue was subjected to column chromatography
on neutral alumina. 11a was eluted with hexane/diethyl ether (3:1)
to 1:1; 10a with pure diethyl ether. Removal of the solvents afforded
11a as a yellow powder (169 mg, 40%) and 10a as an orange solid
(36 mg, 11%). 10a: 31P{1H} NMR (81 MHz, CDCl3, 298 K): δ
-18.0 (s), -17.9 (s) ppm. 1H NMR (200 MHz, CDCl3, 298 K): δ
2.12 (s, 6H, CCH3), 2.14 (s, 12H, CCH3), 2.15 (s, 6H, CCH3), 3.56
(d, 2JPH ) 33.0 Hz, 2H, R-CH), 3.57 (d, 2JPH ) 33.0 Hz, 2H, R-CH),
4.25 (s, 20H, Cp), 4.79 (m, 8H, CH2), 6.05 (vt, 2JHH ) 2.1 Hz, 2H,
CHCHCH), 6.09 (vt, 2JHH ) 2.1 Hz, 2H, CHCHCH), 7.09 (d, 3JHH
) 2.2 Hz, 2H, CHCHCH), 7.15 (d, 3JHH ) 2.2 Hz, 2H, CHCHCH),
7.38 (d, JHH ) 2.1 Hz, 2H, CHCHCH), 7.39 (d, JHH ) 2.1 Hz,
2H, CHCHCH) ppm. 13C{1H} NMR (50 MHz, CDCl3, 298 K): δ
13.7 (s, CCH3), 16.6 (s, CCH3), 16.6 (s, CCH3), 50.3 (br s, CH2),
72.5 (br s, R-CH), 73.9 (s, Cp), 84.7 (br s, CCH3), 93.1 (br s,
R-CCH2), 94.6 (d, 2JPC ) 4.6 Hz, CCH3), 107.0 (br s, CHCHCH),
128.8 (br s, CHCHCH), 139.6 (br s, CHCHCH), 206.5 (m, CO)
212.2 (m, CO) ppm. MS (FAB): m/z 750 ([M - 3CO]+, 23%),
494 ([M - 3a - CO]+, 50%), 410 ([M - 3a - 4CO]+, 100%),
312 ([3a]+, 64%), 245 ([PfcCH2]+, 38%), 121 ([CpFe]+, 70%), 56
(Fe+, 41%). IR νCO (ATR, cm-1): 2028, 1933, 1906, 1897. 11a:
31P{1H} NMR (81 MHz, CDCl3, 298 K): δ -21.4 (s) ppm. 1H NMR
(200 MHz, CDCl3, 298 K): δ 2.21 (s, 3H, CCH3), 2.22 (s, 3H,
CHCHCH), 7.52 (d, JHH ) 2.1 Hz, 1H, CHCHCH) ppm. 13C{1H}
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NMR (50 MHz, CDCl3, 298 K): δ 13.0 (d, JPC ) 3.4 Hz, CCH3),
16.5 (d, 3JPC ) 4.7 Hz, CCH3), 30.4 (d, 2JPC ) 17.0 Hz, PfcCH2CH2),
53.4 (d, 3JPC ) 2.2 Hz, PfcCH2CH2), 70.9 (d, 1JPC ) 3.4 Hz, R-CH),
73.8 (s, Cp), 88.0 (d, 2JPC ) 7.5 Hz, CCH3), 92.6 (d, 2JPC ) 5.5 Hz,
CCH3), 94.3 (s, R-CCH2), 105.4 (s, CHCHCH), 129.1 (s, CHCHCH),
2
139.5 (s, CHCHCH), 204.3 (d, JPC ) 10.9 Hz, cis-CO), 208.1 (d,
2JPC ) 30.9 Hz, trans-CO) ppm. MS (FAB): m/z 564 (M+, 15%), 508
([M - 2CO]+, 57%), 480 ([M - 3CO]+, 34%), 452 ([M - 4CO]+,
17%), 424 ([M - 5CO]+, 74%), 326 ([3b]+, 92%), 258 ([PfcCH2CH]+,
100%), 245 ([PfcCH2]+, 29%). IR νCO (ATR, cm-1): 2075, 1949.
Synthesis of 12a. [Cp*RuCl]4 (137 mg, 0.13 mmol, 1 equiv) was
dissolved in THF (5 mL) and treated with a solution of 3a (157 mg,
0.50 mmol, 4 equiv) in THF (5 mL). The solution was stirred for a
few minutes and then evaporated to dryness, affording a brownish
powder in quantitative yield according to the NMR spectra (294 mg,
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100%). 31P{1H} NMR (81 MHz, CDCl3, 223 K): δ 5.8 (s) ppm. H
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NMR (200 MHz, CDCl3, 223 K): δ 1.60 (d, JPH ) 2.6 Hz, 15H,
Cp*), 2.18 (s, 3H, CCH3), 2.21 (s, 3H, CCH3), 3.87 (d, 2JPH ) 34.1
Hz, 1H, R-CH), 3.94 (s, 5H, Cp), 4.50 (m, 2H, CH2), 6.32 (br s, 1H,
CHCHCH), 7.41 (br s, 1H, CHCHCH), 8.13 (br s, 1H, CHCHCH)
ppm. MS (MALDI): m/z 549 ([M - Cl]+, 100%).
Synthesis of 12b. [Cp*RuCl]4 (101 mg, 0.09 mmol, 1 equiv)
was dissolved in THF (5 mL) and treated with a solution of 3b
(121 mg, 0.37 mmol, 4 equiv) in THF (5 mL). The solution was
stirred for a few minutes and then evaporated to dryness, affording
a red powder in quantitative yield according to the NMR spectra
(222 mg, 100%). 31P{1H} NMR (81 MHz, CDCl3, 298 K): δ 16.4
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CCH3), 3.81 (d, JPH ) 33.7 Hz, 1H, R-CH), 4.31 (s, 5H, Cp),
4.65-4.98 (m, 2H, CH2), 6.21 (br s, 1H, CHCHCH), 7.30 (br s,
1H, CHCHCH), 7.47 (br s, 1H, CHCHCH) ppm. 13C{1H} NMR
(s) ppm. H NMR (200 MHz, CDCl3, 298 K): δ 1.62 (d, JPH
)
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(50 MHz, CDCl3, 298 K): δ 13.6 (d, JPC ) 2.9 Hz, CCH3), 16.6
2.7 Hz, 15H, Cp*), 2.11 (s, 3H, CCH3), 2.17 (s, 3H, CCH3),
(d, 3JPC ) 4.6 Hz, CCH3), 49.6 (d, 2JPC ) 19.1 Hz, CH2), 72.3 (d,
1JPC ) 3.2 Hz, R-CH), 73.9 (s, Cp), 84.6 (d, 2JPC ) 6.0 Hz, CCH3),
2.39-2.85 (m, 2H, PfcCH2CH2), 3.56 (d, JPH ) 33.6 Hz, 1H,
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R-CH), 3.86 (s, 5H, Cp), 4.23 (m, 1H, PfcCH2CH2), 4.99 (vt, 2JHH
) 13.3 Hz, 3JHH ) 13.3 Hz, 1H, PfcCH2CH2), 6.39 (vt, 3JHH ) 2.4
Hz, 1H, CHCHCH), 7.55 (d, 3JHH ) 2.4 Hz, 1H, CHCHCH), 8.41
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93.4 (d, JPC ) 5.4 Hz, CCH3), 95.2 (s, R-CCH2), 105.7 (br s,
CHCHCH), 128.0, 139.2 (2 br s, CHCHCH), 204.0 (d, 2JPC ) 10.9
2
3
Hz, cis-CO), 208.0 (d, JPC ) 31.9 Hz, trans-CO) ppm. MS (EI):
(d, JHH ) 2.4 Hz, 1H, CHCHCH) ppm. MS (MALDI): m/z 563
m/z 410 ([M - 5CO]+, 24%), 312 ([3a]+, 48%), 244 ([PfcCH]+,
8%), 121 ([CpFe]+, 70%), 56 (Fe+, 41%). IR νCO (ATR, cm-1):
([M - Cl]+, 100%). Anal. Calcd for C26H34ClFeN2PRu: C, 52.23;
H, 5.73; N, 4.69. Found: C, 51.56; H, 4.97; N, 4.40.