Issue 7, 1985

Preparation and properties of cis-[W(N2)2(Ph2PCH2PPh2)2] and trans-[M(N2)2(Ph2PCH[double bond, length half m-dash]CHPPh2)2](M = Mo or W), and the crystal structure of cis-[W(N2)2(PMe2Ph)4]

Abstract

The complexes cis-[W(N2)2(Ph2PCH2PPh2)2](A) and trans-[W(N2)2(Ph2PCH[double bond, length half m-dash]CHPPh2)2](B) have been prepared by reduction of WCl6 or [WCl4(Ph2PCH[double bond, length half m-dash]CHPPh2)] with Mg in tetrahydrofuran (thf) under N2 in the presence of the appropriate phosphine. Dinitrogen is displaced from (A) by CO to give cis-[W(CO)2(Ph2PCH2PPh2)2]. Compound (B) reacts with I2, FeCl3, and CuCl2 to give [W(N2)2(Ph2PCH[double bond, length half m-dash]CHPPh2)2]Y (Y = I3, FeCl4, or CuCl2) and with HCl to give the cation [WCl(NNH2)(Ph2PCH[double bond, length half m-dash]CHPPh2)2]+. Both complexes (A) and (B) undergo reversible one-electron oxidation in thf. The complex trans-[Mo(N2)2(Ph2PCH[double bond, length half m-dash]CHPPh2)2] gives tans-[Mo(N2)(RCN)(Ph2PCH[double bond, length half m-dash]CHPPh2)2](R = Me or Et) on treatment with RCN. X-Ray analysis of the related complex, cis-[W(N2)2(PMe2Ph)4], shows a well defined octahedral structure in which the dinitrogen ligands have different environments and the W–N distances are 1.983 and 2.015(3)Å.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1985, 1523-1526

Preparation and properties of cis-[W(N2)2(Ph2PCH2PPh2)2] and trans-[M(N2)2(Ph2PCH[double bond, length half m-dash]CHPPh2)2](M = Mo or W), and the crystal structure of cis-[W(N2)2(PMe2Ph)4]

H. Dadkhah, J. R. Dilworth, K. Fairman, C. T. Kan, R. L. Richards and D. L. Hughes, J. Chem. Soc., Dalton Trans., 1985, 1523 DOI: 10.1039/DT9850001523

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