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

DOI: 10.1039/DT9850000685

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 685 - 692 (1985)

Update date:2022-08-04

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Authors:

Salt, Julian E.

Girolami, Gregory S.

Wilkinson, Geoffrey

Motevalli, Majid

Thornton-Pett, Mark

Hursthouse Michael B.

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Article abstract of DOI:10.1039/DT9850000685

The reduction of trans-CrCl2(dmpe)2 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 Bu^tNC to trans-Cr(CNBu^t)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(PhCCPh)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) Angstroem, respectively.The N-N bond lenght, 1.122(3) Angstroem, is normal.The cis-dicarbonyl complex is also octahedral with a Cr-C distance of 1.812(6) Angstroem; the Cr-P distances are different at 2.343(3) Angstroem trans to CO and 2.278(3) Angstroem trans to P, reflecting large differences in thrans influence between CO and phosphine.The diphenylacetylene complex has ?-bonded acetylene groups with Cr-C distances in the range 1.886(5)-1.980(5) Angstroem and a chelating dmpe ligand, with Cr-P distances of 2.280(3), 2.298(3) Angstroem.The chromium(IV) hydride has a dodecahedral structure with phosphines occupying the B sites and the hydrogen atoms the A sites .

Full text of DOI:10.1039/DT9850000685

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