Inorganic Chemistry
Article
7.8 Hz, 2H, pyH-m), 6.85 (d, J = 7.8 Hz, 2H, pyH-m), 2.65 (s, 6H,
CH3) ppm. 13C NMR (CD2Cl2, 75 MHz): δ 166.71 (s, 2C, pyC-o),
158.77 (s, 2C, pyC-o), 139.98 (s, 2C, pyC-p), 122.95 (s, 2C, pyC-m),
121.21 (s, 2C, pyC-m), 24.44 (s, 2C, CH3) ppm. IR (cm−1): 1585
(m), 1557 (m), 1548 (m), 1440 (s), 1372 (m), 1172 (s), 1011 (w),
928 (s, MoO), 896 (s, MoO), 876 (m), 774 (s), 727 (m), 685
(m), 555 (w), 462 (m). EI-MS (70 eV) m/z: M+ 378.1. Anal. Calcd
for C12H12N2O2S2Mo: C, 38.30; H, 3.21; N, 7.44; S, 17.04. Found: C,
38.36; H, 3.35; N, 7.49; S, 16.69.
(CD2Cl2, 75 MHz): δ 170.43 (s, 2C, Cq), 144.97 (s, 2C, pyC-o),
136.07 (s, 2C, pyC-p), 123.67 (s, 2C, pyC-m), 115.18 (s, 2C, pyC-m),
1
14.52 (t, JCP = 23.9 Hz, 6C, PCH3) ppm. 31P NMR (CD2Cl2, 121
MHz): δ −8.07 ppm. IR (cm−1): 3071 (w), 3049 (w), 3027 (w),
2970 (w), 2900 (w), 1571 (m), 1540 (m), 1438 (m), 1416 (m), 1279
(m), 1248 (m), 1139 (m), 1085 (m), 937 (s, MoO), 876 (s), 847
(m), 758 (m), 747 (s), 734 (s), 666 (m), 504 (m), 469 (m). EI-MS
(70 eV) m/z: [M − 2 PMe3]+3 34.0. Anal. Calcd for
C16H26N2OP2S2Mo: C, 39.67; H, 5.41; N, 5.78; S, 13.24. Found:
C, 39.51; H, 5.14; N, 5.76; S, 12.99.
[Mo2O3L4] (6−9). PPh3 (79 mg, 0.30 mmol) was added to a
suspension of [MoO2L2] (1−4) (0.50 mmol) in 10 mL of MeCN.
The mixture was stirred for 2 h, and the volume of the reaction
mixture was reduced by half before 5 mL of Et2O was added. The
dark precipitate was isolated by filtration, washed with 3 mL of Et2O,
and dried in vacuo.
[MoO(4-MePyS)2(PMe3)2] (12). A solution of PMe3 (0.36 mL,
3.50 mmol) in 3 mL of MeCN was added to a stirred solution of 2
(263 mg, 0.70 mmol) in 4 mL of CH2Cl2 and 2 mL of MeCN. After 3
h, the volume of the now deep green solution was reduced to
approximately 3 mL. The resulting precipitate was isolated by
filtration, washed with 3 mL of MeCN, and subsequently dried in
vacuo to give [MoO(4-MePyS)2(PMe3)2] (359 mg, 100%) as a green
microcrystalline powder. Single crystals suitable for X-ray diffraction
[Mo2O3(PymS)4] (6). Yield: 159 mg (93%). IR (cm−1): 1567 (m),
1542 (m), 1428 (m), 1366 (s), 1248 (m), 1185 (m), 1173 (m), 1162
(m), 1099 (w), 1067 (w), 947 (s, MoO), 822 (w), 810 (m), 798
(m), 762 (m), 746 (m), 662 (m), 653 (m), 468 (m), 438 (m, Mo−
O−Mo). EI-MS (70 eV) m/z: [MoO2(PymS)2]+ 351.9, [MoO-
(PymS)2]+ 335.9.
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analysis were obtained from CH2Cl2/heptane at −37 °C. H NMR
(CD2Cl2, 300 MHz): δ 8.55 (d, J = 5.7 Hz, 2H, pyH-o), 6.49 (dd, J =
5.7, 1.1 Hz, 2H, pyH-m), 6.44 (m, 2H, pyH-m), 2.24 (s, 6H, CH3),
[Mo2O3(PyS)4] (7). Yield: 154 mg (91%). IR (cm−1): 1579 (s),
1549 (m), 1439 (m), 1417 (s), 1262 (m), 1132 (m), 941 (s, Mo
O), 878 (m), 775 (vw), 752 (s), 726 (s), 651 (m), 643 (m), 539 (w),
481 (m), 457 (m), 437 (m, Mo−O−Mo). EI-MS (70 eV) m/z:
[MoO2(PyS)2]+ 349.9, [MoO(PyS)2]+ 333.9.
1.23 (t, JHP = 7.6 Hz, 18H, PCH3) ppm. 13C NMR (CD2Cl2, 75
2
MHz): δ 169.74 (s, 2C, SCq), 147.53 (s, 2C, Cq), 144.39 (s, 2C, pyC-
o), 124.17 (s, 2C, pyC-m), 117.10 (s, 2C, pyC-m), 20.98 (s, 2C,
CH3), 14.59 (t, 1JCP = 23.6 Hz, 6C, PCH3) ppm. 31P NMR (CD2Cl2,
121 MHz): δ − 7.86 ppm. IR (cm−1): 3068 (w), 3048 (w), 3012 (w),
2970 (w), 2901 (w), 1588 (m), 1530 (m), 1454 (m), 1412 (m), 1375
(m), 1279 (m), 1223 (m), 1086 (m), 1007 (m), 941 (s, MoO),
885 (s), 873 (s), 846 (m), 813 (s), 730 (m), 700 (w), 668 (m), 563
(w), 472 (m), 444 (m). EI-MS (70 eV) m/z: [M − 2 PMe3]+ 362.0.
Anal. Calcd for C18H30N2OP2S2Mo: C, 42.19; H, 5.90; N, 5.47; S,
12.51. Found: C, 42.38; H, 5.75; N, 5.40; S, 11.84.
[Mo2O3(4-MePyS)4] (8). Yield: 182 mg (99%). IR (cm−1): 1595 (s),
1539 (w), 1379 (m), 1268 (m), 1089 (m), 943 (s, MoO), 902 (w),
872 (m), 810 (m), 784 (m), 725 (m), 696 (w), 554 (m), 541 (m),
455 (m), 441 (s, Mo−O−Mo), 428 (m). EI-MS (70 eV) m/z:
[MoO2(4-MePyS)2]+ 378.0, [MoO(4-MePyS)2]+ 362.0. Anal. Calcd
for C24H24N4O3S4Mo2: C, 39.13; H, 3.28; N, 7.61; S, 17.41. Found:
C, 39.52; H, 3.17; N, 7.92; S, 15.92.
[MoO(6-MePyS)2(PMe3)] (13). A solution of PMe3 (134 μL,
1.30 mmol) in 2 mL of CH2Cl2 was added to a stirred solution of 3
(188 mg, 0.50 mmol) in 8 mL of CH2Cl2. After 1 h, the solvent was
evaporated in vacuo. The resulting green solid was first washed with
3 mL of MeCN and then recrystallized from CH2Cl2/heptane. After
filtration and drying in vacuo, [MoO(6-MePyS)21(PMe3)] (192 mg,
88%) was obtained as a deep blue-green powder. H NMR (CD2Cl2,
300 MHz): δ 7.50 (t, J = 7.8 Hz, 1H, pyH-p), 7.02−6.96 (m, 2H,
pyH), 6.77−6.74 (m, 2H, pyH), 6.51 (d, J = 7.9 Hz, 1H, pyH-m),
[Mo2O3(6-MePyS)4] (9). Yield: 184 mg (100%). IR (cm−1): 1582
(m), 1555 (m), 1447 (s), 1430 (s), 1171 (s), 930 (s, MoO), 877
(m), 777 (s), 729 (m), 692 (m), 683 (m), 563 (w), 542 (w), 464
(m), 436 (m, Mo−O−Mo). EI-MS (70 eV) m/z: [MoO2(6-
MePyS)2]+ 378.0, [MoO(6-MePyS)2]+ 362.0. Anal. Calcd for
C24H24N4O3S4Mo2: C, 39.13; H, 3.28; N, 7.61; S, 17.41. Found: C,
39.58; H, 2.95; N, 7.44; S, 17.39.
[MoO(PymS)2(PMe3)2] (10). A solution of PMe3 (0.36 mL,
3.50 mmol) in 3 mL of MeCN was added to a stirred suspension
of complex 4 (245 mg, 0.70 mmol) in 6 mL of MeCN. After 2 h, the
volume of the deep orange-brown solution was reduced to
approximately 3 mL. The resulting precipitate was isolated by
filtration, washed with MeCN (2 × 2 mL), and subsequently dried in
vacuo to give [MoO(PymS)2(PMe3)2] (280 mg, 82%) as a dark
brown crystalline powder. 1H NMR (CD2Cl2, 300 MHz): δ 8.56 (d, J
= 3.0 Hz, 4H, pymH-o), 6.66 (t, J = 5.1 Hz, 2H, pymH-m), 1.25 (t,
2JHP = 7.8 Hz, 18H, PCH3) ppm. 13C NMR (CD2Cl2, 75 MHz): δ
176.72 (m, 2C, Cq), 155.50 (bs, 4C, pymC-o), 113.40 (s, 2C, pymC-
2
2.79 (s, 3H, CH3), 2.06 (s, 3H, CH3), 1.46 (d, JHP = 9.0 Hz, 9H,
PCH3) ppm. 13C NMR (CD2Cl2, 75 MHz): δ 183.16 (d, pyC-o),
169.21 (d, pyC-o), 159.83 (s, pyC-o), 158.96 (s, pyC-o), 140.28 (s,
pyC-p), 134.35 (s, pyC-p), 125.09 (d, 4JPC = 1.7 Hz, pyC-m), 123.43
4
(s, pyC-m), 117.98 (s, pyC-m), 117.81 (d, JPC = 1.2 Hz, pyC-m),
25.14 (s, CH3), 22.66 (s, CH3), 16.14 (d, 3C, 1JPC = 27.6 Hz, PCH3).
31P NMR (CD2Cl2, 121 MHz): δ 8.23 ppm. IR (cm−1): 3057 (w),
2980 (w), 2955 (w), 2907 (w), 1585 (m), 1578 (m), 1555 (m), 1540
(m), 1438 (m), 1422 (m), 1374 (m), 1300 (w), 1280 (m), 1236 (w),
1168 (m), 1086 (w), 937 (s, MoO), 875 (w), 843 (w), 793 (m),
777 (m), 729 (m), 685 (m), 668 (m), 558 (w), 467 (w). EI-MS (70
eV) m/z: [M − PMe3]+ 362.1. Anal. Calcd for C15H21N2OPS2Mo: C,
41.29; H, 4.85; N, 6.42; S, 14.69. Found: C, 41.16; H, 4.89; N, 6.60;
S, 14.35.
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m), 14.61 (t, JCP = 24.6 Hz, 6C, PCH3) ppm. 31P NMR (CD2Cl2,
121 MHz): δ −9.00 ppm. IR (cm−1): 2971 (w), 2903 (w), 1548 (w),
1532 (m), 1415 (m), 1361 (s), 1282 (m), 1246 (m), 1160 (m), 1086
(m), 1003 (m), 940 (s, MoO), 887 (m), 871 (s), 846 (m), 803
(m), 761 (m), 732 (m), 667 (w), 653 (m), 501 (w), 472 (m). EI-MS
(70 eV) m/z: [M − 2 PMe3]+ 335.9. Anal. Calcd for
C14H24N4OP2S2Mo: C, 34.57; H, 4.97; N, 11.52; S, 13.18. Found:
C, 34.51; H, 4.68; N, 11.76; S, 13.02.
X-ray Diffraction Analysis. Single-crystal X-ray diffraction
analyses were carried out on a Bruker AXS SMART APEX-II
diffractometer equipped with a CCD detector. All measurements were
performed using monochromatized Mo Kα radiation from an
Incoatec microfocus sealed tube at 100 K. Absorption corrections
were performed semiempirically from equivalents. Molecular
structures were solved by direct methods (SHELXS-97)108 and
refined by full-matrix least-squares techniques against F2 (SHELXL-
2014/6).109 Crystallographic data, figures, and selected geometry
graphic data for this paper. These data can be obtained free of charge
[MoO(PyS)2(PMe3)2] (11). A solution of PMe3 (0.36 mL,
3.50 mmol) in 3 mL of CH2Cl2 was added to a stirred solution of
1 (244 mg, 0.70 mmol) in 6 mL of CH2Cl2. After 3 h, the solvent was
evaporated. The resulting green solid was washed with MeCN
(2 × 3 mL) and subsequently dried in vacuo to give [MoO-
(PyS)2(PMe3)2] (281 mg, 83%) as a dark green microcrystalline
powder. Single crystals suitable for X-ray diffraction analysis were
obtained from MeCN. 1H NMR (CD2Cl2, 300 MHz): δ 8.73 (ddd, J
= 5.6, 0.7 Hz, 2H, pyH-o), 7.16 (td, J = 7.7, 1.7 Hz, 2H, pyH-p), 6.63
(ddd, J = 7.1, 5.6, 1.2 Hz, 2H, pyH-m), 6.56 (dt, J = 8.0, 1.0 Hz, 2H,
Catalytic Reactions. All catalytic experiments were performed at
least three times under a nitrogen atmosphere in J. Young NMR tubes
2
pyH-m), 1.24 (t, JHP = 7.7 Hz, 18H, PCH3) ppm. 13C NMR
M
Inorg. Chem. XXXX, XXX, XXX−XXX