Structural studies of the 1:1 addition complexes of niobium and tantalum pentachlorides with o-phenylenebis(dimethylarsine)

John C. Dewan, David L. Kepert, Colin L. Raston, Allan H. White

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34 Citations (Scopus)

Abstract

The addition of o-phenylenebis(dimethylarsine), 'diars.' in equimolar ratio to the pentachlorides of tantalum and niobium has yielded addition complexes shown by X-ray crystallographic structure determination to have the probable stoicheiometries [TaCl4(diars)2]+[TaCl5(OEt)] - (I), [NbCl4(diars)2]+2[NbCl 3O2]2- (II), and [NbCl4-(diars)2]+ [NbOCl4]- (III). Crystals of (I) are triclinic, space group P1, a = 12.983(4), b = 14.484(6), c = 12.359(6) Å, α = 108.04(3), β = 102.17(5), γ = 110.35(5)°, Z = 2, 2 448 observed reflections being refined to R 0.09. Crystals of (II) are monoclinic, space group C2/c or Cc, a = 20.877(4), b = 16.086(3), c = 19.458(2) Å, β = 106.25(1)°, Z = 4, 1 183 observed reflections refined to R 0.08. Crystals of (III) are triclinic, space group P1 a = 14.815(3), b = 12.273(2), c = 10.397(2) Å, α = 92.03(1), β = 103.56(2), γ = 110.80(2)°, Z = 2, 2 473 observed reflections refined to R 0.06. In all three, an eight-co-ordinate dodecahedral cation is found; mean distances: Ta-As 2.761, Ta-Cl 2.40, Nb-As 2.743, and Nb-Cl 2.426 Å. The structures were determined from diffractometer data [(I) and (III) by the heavy-atom method, (II) by direct methods].

Original languageEnglish
Pages (from-to)2031-2038
Number of pages8
JournalJournal of the Chemical Society, Dalton Transactions
Issue number20
DOIs
Publication statusPublished - 1975
Externally publishedYes

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