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Trimethylphosphine Complexes of Niobium(IV) and Tantalum(IV). Crystal, Molecular, and Electronic Structures of (M = Nb or Ta)

DOI: 10.1039/DT9870000307

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 307 - 314 (1987)

Update date:2022-08-02

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Authors:

Boyd, Peter D. W.Boyd, Peter D. W.

Nielsen, Alastair J.Nielsen, Alastair J.

Rickard, Clifton E. F.Rickard, Clifton E. F.

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Article abstract of DOI:10.1039/DT9870000307

Reaction of or (thf = tetrahydrofuran) with three equivalents of PMe3 gives the seven-co-ordinate complex .In refluxing benzene this complex converts to which is obtained in good yield by reacting with two equivalents of PMe3. reacts with one equivalent of PMe3 in acetonitrile to give <n>. was obtained by reacting dilithium t-butyl-phosphide and PMe3 with TaCl5.Reduction of TaCl5 with Na-Hg amalgam in the presence of Cl gave 2.X-ray structure determinations show the complexes (M = Ta or Nb) are isostructural (space group Im3), containing four symmetrical chlorine bridges across two metal centres each of which have co-ordinated two terminal chlorines and two terminal phosphine ligands .Scattered wave Xα calculations on the electronic structure of the dinuclear complexes (M = Nb or Ta) indicate the formation of a metal-metal single ? bond between the metal atom dz2 orbitals.THe ?-?* energy separation suggests greater metal-metal interaction for the tantalum complex.

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