Synthesis and characterisation of 1,2-bis(dimethylphosphino)ethane (dmpe) complexes of chromium-(0) and -(IV): X-ray crystal structures of trans-Cr(N2)2(dmpe)2, cis-Cr(CO)2(dmpe)2, Cr(C2Ph2)2(dmpe), and CrH4(dmpe)2

Julian E. Salt, Gregory S Girolami, Geoffrey Wilkinson, Majid Motevalli, Mark Thornton-Pett, Michael B. Hursthouse

Research output: Contribution to journalArticlepeer-review

Abstract

The reduction of trans-CrCl2(dmpe)2[dmpe = 1,2-bis(dimethylphosphino)ethane] in tetrahydrofuran by sodium amalgam under dinitrogen leads to the complex trans-Cr(N2)2(dmpe)2, under carbon monoxide to the known cis-Cr(CO)2(dmpe)2, and in presence of ButNC to trans-Cr(CNBut)2(dmpe)2. Interaction of trans-Cr(N2)2(dmpe)2 with ethylene, buta-1,3-diene, diphenylacetylene, and hydrogen (under irradiation) gives, respectively, trans-Cr(C2H4)2(dmpe)2, cis-Cr(η4-C4H6)(dmpe)2, Cr(PhC=CPh)2(dmpe), and CrH4(dmpe)2. Infrared and nuclear magnetic resonance spectra are reported together with X-ray crystal structures of four of the complexes. The trans-bis(dinitrogen) complex is centrosymmetric with octahedral geometry and Cr-N and Cr-P distances of 1.874(3) and 2.296(1) Å, respectively. The N-N bond length, 1.122(3) Å, is normal. The cis-dicarbonyl complex is also octahedral with a Cr-C distance of 1.812(6) Å; the Cr-P distances are different at 2.343(3) Å trans to CO and 2.278(3) Å trans to P, reflecting large differences in trans influence between CO and phosphine. The diphenylacetylene complex has π-bonded acetylene groups with Cr-C distances in the range 1.886(5)-l.980(5) Å and a chelating dmpe ligand, with Cr-P distances of 2.280(3), 2.298(3) Å. The chromium(IV) hydride has a dodecahedral structure with phosphines occupying the B sites [Cr-P 2.255(3) Å] and the hydrogen atoms the A sites [Cr-H 1.57(3) Å].

Original languageEnglish (US)
Pages (from-to)685-692
Number of pages8
JournalJournal of the Chemical Society, Dalton Transactions
Issue number4
DOIs
StatePublished - Jan 1 1985
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

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