The reaction of [Et4N]2[Mo2(SC6H11)2(CO)8] and I2 in MeCN affords a new dinu- clear molybdenum(I) complex [Mo2(SC6H11)2(CO)6(CH3CN)2] 1 (Mr = 672.46). The crystal and molecular structures have been determined by X-r...The reaction of [Et4N]2[Mo2(SC6H11)2(CO)8] and I2 in MeCN affords a new dinu- clear molybdenum(I) complex [Mo2(SC6H11)2(CO)6(CH3CN)2] 1 (Mr = 672.46). The crystal and molecular structures have been determined by X-ray single-crystal diffraction. 1 crystallizes in monoclinic, space group P21/c with a = 9.302(1), b = 15.514(2), c = 9.307(1) ?, β = 92.979(2)o, V = 1341.4(3) ?3, Z = 2, Dc = 1.665 g/cm3, μ = 11.28 cm-1, F(000) = 676, R = 0.0461 and wR = 0.1274 for 1702 observed reflections with I > 2σ(I). 1 possesses a rhombic bimetallic core MoS2Mo with the Mo–Mo bond length of 2.9712(4) ? and Mo–S of 2.4821(5) ?.展开更多
The reaction of W（CO）6 with pyOSNa （C5H4NOSNa） and Et4NCl in MeCN affords a new tungsten（0）complex [Et4N][W（pyS）（CO）4] 1 （Mr = 536.29）. The crystal and molecular structures have been determined by X-ray si...The reaction of W（CO）6 with pyOSNa （C5H4NOSNa） and Et4NCl in MeCN affords a new tungsten（0）complex [Et4N][W（pyS）（CO）4] 1 （Mr = 536.29）. The crystal and molecular structures have been determined by X-ray single-crystal diffraction. Complex 1 crystallizes in the orthorhombic system, space group P212121 with α= 8.2429（5）, b = 9.1045（4）, c = 26.8851（14） A, β= 90.00°, V=2017.66（18） A3^, Z = 4, Dc = 1.765 g/cm^3, μ= 58.51 cm^-1, F（000） = 1048, the final R = 0.0204 and wR = 0.0400 for 4432 observed reflections with I 〉 2σ（I）. X-ray structure analysis revealed that the molecule is acentric and has large first=order hyperpolarizability （7.2 × 10^-30 esu）, so it could be an IR second=order nonlinear optical candidate material.展开更多
The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo（0） compound [Et4N]3[Mo2（CO）6（μ-OC6H4OCH2C6H5）3] 1. 1 crystallizes in monoclinic, space group ...The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo（0） compound [Et4N]3[Mo2（CO）6（μ-OC6H4OCH2C6H5）3] 1. 1 crystallizes in monoclinic, space group P21/c with a = 15.359（2）, b = 18.378（3）, c = 24.952（2） A, β = 102.268（4）°, V = 6882.3（1 6） A^3, Mr = 1348.34, Z = 4, Dc = 1.301 g/cm^3, F（000） = 2832 and μ= 0.424 mm^-1 The final R = 0.0606 and wR = 0.1552 for 9396 observed reflections （I 〉 2σ（I））. I contains a [Mo2O3]^3 core in triangular bi-pyralnidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three ,μ-O atoms from C6H5CH2OC6H4O^- bridging ligands. The Mo…Mo distance is 3.30（8） A, indicating no metalmetal bonding. A formation pathway via forming a di-molybdenum（0） di-bridging OR compound [Mo2（μ-OR）2（CO）8]2 has been figured out and the reaction of Mo（CO）6 with alkoxide has also been discussed.展开更多
A di-molybdenum carbonyl compound containing thiolate and dithiocarbamate ligands, [Bu4N][（CO）4Mo（μ-SC6H5）2Mo（C5H10dtc）（CO）2] 1 （CsH10dtc = S2CNC5H10）, has been prepared by reaction of [Mo2（SC6H5）2（CO）8...A di-molybdenum carbonyl compound containing thiolate and dithiocarbamate ligands, [Bu4N][（CO）4Mo（μ-SC6H5）2Mo（C5H10dtc）（CO）2] 1 （CsH10dtc = S2CNC5H10）, has been prepared by reaction of [Mo2（SC6H5）2（CO）8] with C5H10dtcNa and [NBu4]Br in acetone. It crystallizes in monoclinic, space group P21/n with a = 13.162（3）, b = 17.466（2）, c = 20.453（4） A,β= 100.77（1）°, Z = 4, V= 4619（2）A^3, C40H56Mo2N2O6S4, Mr = 980.95, De= 1.389 g/cm^3,μ = 7.66 cm^-1, F（000） = 1988 and R = 0.0746 for 5161 observed reflections with I 〉 2σ（I）. The complex contains a [Mo2S2]^2- planar core in which one Mo atom is chelated by a C5H10dtc ligand, leading to different coordination environments of the two Mo atoms. 95Mo NMR measurement indicates that the two Mo atoms are in different oxidation states.展开更多
Mixed-valence dinuclear molybdenum complex [Et4N][Mo2(PyS)3(CO)5] (1) (PyS=C5H4NS) has been synthe-sized and characterized by crystallography. 1 crystallizes in monoclinic system with space group P21/c with a=1.5769(1...Mixed-valence dinuclear molybdenum complex [Et4N][Mo2(PyS)3(CO)5] (1) (PyS=C5H4NS) has been synthe-sized and characterized by crystallography. 1 crystallizes in monoclinic system with space group P21/c with a=1.5769(11) nm, b=1.3144(5) nm, c=1.6935(10) nm; b=111.20(4); V=3.2724 nm3; Z=4, Dc=1.61 g/cm3, =9.7 cm-1 and F(000)=1600. The final R=0.054 and wR=0.073, for 1811 observed reflection with I>3s(I). In compound 1, one chelating PyS ligand and two bridging PyS ligands are 3-electron and 5-electron donors, respec-tively, and two molybdenum atoms are located in different coordination environments resulting in mixed-valence state. The reaction mechanism of Mo(CO)6 with PySH and PySO (C5H5SNO) was investigated and two reac-tion pathways were proposed.展开更多
文摘The reaction of [Et4N]2[Mo2(SC6H11)2(CO)8] and I2 in MeCN affords a new dinu- clear molybdenum(I) complex [Mo2(SC6H11)2(CO)6(CH3CN)2] 1 (Mr = 672.46). The crystal and molecular structures have been determined by X-ray single-crystal diffraction. 1 crystallizes in monoclinic, space group P21/c with a = 9.302(1), b = 15.514(2), c = 9.307(1) ?, β = 92.979(2)o, V = 1341.4(3) ?3, Z = 2, Dc = 1.665 g/cm3, μ = 11.28 cm-1, F(000) = 676, R = 0.0461 and wR = 0.1274 for 1702 observed reflections with I > 2σ(I). 1 possesses a rhombic bimetallic core MoS2Mo with the Mo–Mo bond length of 2.9712(4) ? and Mo–S of 2.4821(5) ?.
基金This research was supported by NNSFC (No. 01008) and SKLSC (No. 980148-2)
文摘The reaction of W（CO）6 with pyOSNa （C5H4NOSNa） and Et4NCl in MeCN affords a new tungsten（0）complex [Et4N][W（pyS）（CO）4] 1 （Mr = 536.29）. The crystal and molecular structures have been determined by X-ray single-crystal diffraction. Complex 1 crystallizes in the orthorhombic system, space group P212121 with α= 8.2429（5）, b = 9.1045（4）, c = 26.8851（14） A, β= 90.00°, V=2017.66（18） A3^, Z = 4, Dc = 1.765 g/cm^3, μ= 58.51 cm^-1, F（000） = 1048, the final R = 0.0204 and wR = 0.0400 for 4432 observed reflections with I 〉 2σ（I）. X-ray structure analysis revealed that the molecule is acentric and has large first=order hyperpolarizability （7.2 × 10^-30 esu）, so it could be an IR second=order nonlinear optical candidate material.
基金This research was supported by NNSFC (No. 90203017 29733090), NBRP (2004CB7201005) and SKLSC
文摘The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo（0） compound [Et4N]3[Mo2（CO）6（μ-OC6H4OCH2C6H5）3] 1. 1 crystallizes in monoclinic, space group P21/c with a = 15.359（2）, b = 18.378（3）, c = 24.952（2） A, β = 102.268（4）°, V = 6882.3（1 6） A^3, Mr = 1348.34, Z = 4, Dc = 1.301 g/cm^3, F（000） = 2832 and μ= 0.424 mm^-1 The final R = 0.0606 and wR = 0.1552 for 9396 observed reflections （I 〉 2σ（I））. I contains a [Mo2O3]^3 core in triangular bi-pyralnidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three ,μ-O atoms from C6H5CH2OC6H4O^- bridging ligands. The Mo…Mo distance is 3.30（8） A, indicating no metalmetal bonding. A formation pathway via forming a di-molybdenum（0） di-bridging OR compound [Mo2（μ-OR）2（CO）8]2 has been figured out and the reaction of Mo（CO）6 with alkoxide has also been discussed.
文摘A di-molybdenum carbonyl compound containing thiolate and dithiocarbamate ligands, [Bu4N][（CO）4Mo（μ-SC6H5）2Mo（C5H10dtc）（CO）2] 1 （CsH10dtc = S2CNC5H10）, has been prepared by reaction of [Mo2（SC6H5）2（CO）8] with C5H10dtcNa and [NBu4]Br in acetone. It crystallizes in monoclinic, space group P21/n with a = 13.162（3）, b = 17.466（2）, c = 20.453（4） A,β= 100.77（1）°, Z = 4, V= 4619（2）A^3, C40H56Mo2N2O6S4, Mr = 980.95, De= 1.389 g/cm^3,μ = 7.66 cm^-1, F（000） = 1988 and R = 0.0746 for 5161 observed reflections with I 〉 2σ（I）. The complex contains a [Mo2S2]^2- planar core in which one Mo atom is chelated by a C5H10dtc ligand, leading to different coordination environments of the two Mo atoms. 95Mo NMR measurement indicates that the two Mo atoms are in different oxidation states.
基金Project supported by the National Natural Science Foundation of China (No. 29733090-3) and State Key Laboratory of Structural Chemistry.
文摘Mixed-valence dinuclear molybdenum complex [Et4N][Mo2(PyS)3(CO)5] (1) (PyS=C5H4NS) has been synthe-sized and characterized by crystallography. 1 crystallizes in monoclinic system with space group P21/c with a=1.5769(11) nm, b=1.3144(5) nm, c=1.6935(10) nm; b=111.20(4); V=3.2724 nm3; Z=4, Dc=1.61 g/cm3, =9.7 cm-1 and F(000)=1600. The final R=0.054 and wR=0.073, for 1811 observed reflection with I>3s(I). In compound 1, one chelating PyS ligand and two bridging PyS ligands are 3-electron and 5-electron donors, respec-tively, and two molybdenum atoms are located in different coordination environments resulting in mixed-valence state. The reaction mechanism of Mo(CO)6 with PySH and PySO (C5H5SNO) was investigated and two reac-tion pathways were proposed.
