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DOI: 10.1039/A902139F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 1867-1876

A new synthetic route to ligands of the general composition R2PCH2ER′2 (E = P, As) and some rhodium complexes derived thereof

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Justin Wolf, Matthias Manger, Ulrich Schmidt, Guido Fries, Dietmar Barth, Birgit Weberndörfer, David A. Vicic, William D. Jones and Helmut Werner

Abstract

Symmetrical and unsymmetrical bis(phosphino)methanes R2PCH2PR′2 (8–16) as well as the arsino(phosphino) analogues R′2AsCH2PR2 (21–25) with bulky alkyl, cycloalkyl or aryl groups R and R′ were prepared from the stannylated phosphines R2PCH2SnR″3 (3–5, 6, 7) via metalation with MeLi or PhLi in the presence of tetramethylethylenediamine and subsequent treatment with R′2PCl or R′2AsCl, respectively. Compound 25 [R′ = Cy, R = (R)-menthyl] is the first arsino(phosphino)methane which has been structurally characterized. The bis(phosphino)methanes R2PCH2PR2 (R = Pri 17, Cy 18) and R2PCH2PR′2 (12, 19, 20) were also obtained by thermal reaction of R2PCH2SnPh3 and the corresponding chlorophosphine R2PCl or R′2PCl in the absence of solvent. The bis(cyclooctene) derivative [RhCl(C8H14)2]2 26 reacted with excess Pri2PCH2PPri2 to give [Rh(κ2P,P′-Pri2PCH2PPri2)2]Cl 27, while treatment of 26 with Ph2PCH2PPri2 yielded the chloro-bridged dimer [RhCl(κ2P,P′-Ph2PCH2PPri2)]2 28. The reaction of the cationic species [Rh(C8H14)2(OCMe2)2]PF6 29 with Cy2PCH2PPri2 in benzene or toluene afforded the half-sandwich-type complexes [(η6-C6H6)Rh(κ2P,P′-Cy2PCH2PPri2)]PF6 30, [(η6-C6H5CH3)Rh(κ2P,P′-Cy2PCH2PPri2)]PF6 31, of which the latter was characterized by X-ray crystallography.

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