Syntheses of Mo(PMe{sub 3}){sub 6} and trans-Mo(PMe{sub 3}){sub 4}(E){sub 2} = S, Se, Te. The first series of terminal sulfido, selenido, and tellurido complexes of molybdenum

Journal Article · Wed Mar 29 04:00:00 EST 1995 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja00117a021· OSTI ID:41650

Murphy, V J; Parkin, G ^[1]

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1. Columbia Univ., New York, NY (United States)

Mo(PMe{sub 3}){sub 6} has been synthesized by the reduction of MoCl{sub 5} with Na(K) alloy using PMe{sub 3} as a reactive solvent. In solution, Mo(PMe{sub 3}){sub 6} exists in equilibrium with Mo(PMe{sub 3}){sub 4}{eta}{sup 2}-CH{sub 2}PMe{sub 2}H and PMe{sub 3}. At 30{degree}C, the equilibrium constant is a factor of ca. 2 {mu} 10{sup 3} less than that for the analogous tungsten system. The reactions of Mo(PMe{sub 3}){sub 6} and Mo(PMe{sub 3}){sub 4}({eta}{sup 2}-CH{sub 2}PMe{sub 2})H with H{sub 2}S, H{sub 2}He, Se, and Te/PMe{sub 3} have provided convenient syntheses of Mo(PMe{sub 3}){sub 4}(E){sub 2} (E = S, Se, Te), the first series of terminal sulfido, selenido, and tellurido derivatives of molybdenum. Mo(PMe{sub 3}){sub 4}(S){sub 2} is monoclinic, P2/n (No. 13), a = 15.947(6) A, b = 9.704(2) A, c = 15.980(3) A,{beta} = 112.24(2){degree}, V = 2289(1) A{sup 3}, Z = 4, Mo(PMe{sub 3}){sub 4}(Se){sub 2} is monoclinic, P2/n (No. 13), a = 16.105(3) A, b = 9.777(3) A, c = 16.136(4) A,{beta} = 113.34(2){degree}, V = 2332(1) A{sup 3}, Z = 4. Mo(PMe{sub 3}){sub 4}(Te){sub 2} is tetragonal, I42m (No. 121), a = b = 9.738(1) A, c = 12.373(2) A, V = 1171.2(6) A{sup 3}, Z = 2. 35 refs., 5 figs., 10 tabs.

• Sponsoring Organization: USDOE
• DOE Contract Number: FG02-93ER14339
• OSTI ID: 41650
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 12 Vol. 117; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
66 PHYSICS
BOND ANGLE
BOND LENGTHS
CHEMICAL BONDS
CHEMICAL PREPARATION
COMPILED DATA
EXPERIMENTAL DATA
MOLECULAR STRUCTURE
MOLYBDENUM COMPLEXES
MOLYBDENUM COMPOUNDS
NUMERICAL DATA
REDUCTION
SODIUM ALLOYS
SOLVENTS
THERMODYNAMICS
X-RAY DIFFRACTION