Preparation and structure of mono- and binuclear complexes of (diphenylarsino)(diphenylphosphino)methane including the x-ray crystal structure of trans-Rh(CO)Cl(μ-Ph2AsCH2PPh2) 2-cis-PtCl2

Alan L. Balch, Rosalvina R. Guimerans, John Linehan, Fred E. Wood

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The reactions of (diphenylarsino)(diphenylphosphino)methane with (1,5-COD)PtX2 (1,5-COD = 1,5-cyclooctadiene; X = Cl, Br, I) or with Rh2(CO)4(μ-Cl)2 to yield Pt(dapm)X2 (chelating dapm), Pt(dapm)2X2, or trans-Rh(dapm)2(CO)Cl (monodentate dapm) are reported. In solution Pt(dapm)2X2 can ionize to form [Pt(damp)2X]X or [Pt(dapm)2]X2. The degree of ionization depends on X and on the solvent. trans-Rh(dapm)2(CO)Cl reacts with Rh2(CO)4(μ-Cl)2 to yield the face-to-face dimer Rh2(μ-dapm)2(CO)2Cl2 as a mixture of head-to-head (P trans to P) and head-to-tail (P trans to As) isomers. Pt(dapm)2Cl2 reacts with Pt(dibenzylideneacetone)2 to form head-to-head and head-to-tail isomers of Pt2(μ-dapm)2Cl2. These react with carbon monoxide to form Pt2(μ-dapm)2(μ-CO)Cl2. Rh2(CO)4(μ-Cl)2 reacts with Pt(dapm)2Cl2 to form trans-Rh(CO)Cl(μ-dapm)2-cis-PtCl2. This orange complex crystallizes in the space group P21/c (No. 14) with a = 18.760 (3) Å, b = 11.610 (3) Å, c = 22.954 (6) Å, β = 92.81 (2)°, and Z = 4 at 140 K. The structure was refined to a conventional R value of 0.038 by using 6415 significant reflections and 572 parameters. The structure consists of face-to-face planar Rh(CO)ClAs2 and PtP2Cl2 units. The nonbonded Pt⋯Rh distance is 3.043 (1) Å.

Original languageEnglish
Pages (from-to)2021-2026
Number of pages6
JournalInorganic Chemistry
Issue number13
Publication statusPublished - 1985


ASJC Scopus subject areas

  • Inorganic Chemistry

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