Synthesis and properties of the divalent 1,2-bis(dimethylphosphino)ethane (dmpe) complexes MCl2(dmpe)2 and MMe2(dmpe)2 (M = Ti, V, Cr, Mn, or Fe). X-Ray crystal structures of MCl2(dmpe)2 (M = Ti, V, or Cr), MnBr2(dmpe)2...

Gregory S. Girolami, Geoffrey Wilkinson, Anita M.R. Galas, Mark Thornton-Pett, Michael B. Hursthouse

Research output: Contribution to journalArticlepeer-review

Abstract

full title:Synthesis and properties of the divalent 1,2-bis(dimethylphosphino)ethane (dmpe) complexes MCl2(dmpe)2 and MMe2(dmpe)2 (M = Ti, V, Cr, Mn, or Fe). X-Ray crystal structures of MCl2(dmpe)2 (M = Ti, V, or Cr), MnBr2(dmpe)2, TiMe1.3Cl0.7(dmpe)2, and CrMe2(dmpe)2 The reaction of transition-metal dichlorides with 1,2-bis(dimethylphosphino)ethane (dmpe) leads to the brightly coloured, highly-crystalline octahedral complexes trans-MCl2(dmpe)2 (M = Ti, V, Cr, or Fe). Although the Mn analogue could not be prepared, both trans-MnBr2(dmpe)2 and trans-Mnl2(dmpe)2 can be obtained from the respective dihalides. Alkylation of the MX2(dmpe)2 (X = halide) compounds with either LiMe or MgMe2 leads to the dimethyl complexes trans-MMe2(dmpe)2 (M = V, Cr, or Mn); the titanium complex isolated under these conditions is a mixture of trans-TiMeCl(dmpe)2 and trans-TiMe2(dmpe)2, while the iron species obtained is cis-FeMe2(dmpe)2. Magnetic susceptibility and e.s.r. measurements indicate a low-spin state for all the complexes except the manganese halide derivatives, and metal-ligand bond lengths observed in those complexes structurally characterised by X-ray crystallographic methods are consistent with the proposed ground-state configurations. There is a similarity between the electronic structures of the MCl2(dmpe)2 species and the metallocenes M(η5-C5H5)2, while the MMe2(dmpe)2 compounds resemble M(η5-C5Me5)2. Our studies indicate a progressive change in the nature of the M-Me groups upon lowering the electron count from 18 (Fe) to 14 (Ti). Thus, the titanium complex trans-TiMe1.3Cl0.7(dmpe)2 appears to contain a distorted methyl group involving a Ti ⋯ H-C interaction due to donation of C-H bond electrons into an empty orbital on the metal.

Original languageEnglish (US)
Pages (from-to)1339-1348
Number of pages10
JournalJournal of the Chemical Society, Dalton Transactions
Issue number7
DOIs
StatePublished - Dec 1 1985
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

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