Five-Coordinate Nickel(III). The Crystal and Molecular Structure of NiBr3(P(C6H5)(CH3))2)2 0.5NiBr2(P(C6H5)(CH3)2)2 C6H6

Judith K. Stalick, James A. Ibers

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31 Scopus citations

Abstract

The crystal and molecular structuee of the 1:0.5:1 adduct of tribromobis(phenyldimethylphosphine)nickel(III), dibromo-bis(phenyldimethylphosphine)nickel(II), and benzene has been determined from three-dimensional X-ray data collected by counter methods. The structure has been refined by least-squares techniques to a final R factor on F of 0.054. The material crystallizes in space group Ci1-P1 of the triclinic system, with two molecules of NiBr3(P(C6H5)(CH3)2)2, one molecule of NiBr2(P(C6H5)(CH3)2)2, and two molecules of benzene in a cell of dimensions a = 9.021 (5), b = 17.951 (10), c = 11.181 (6) A; a = 98° 52 (1)′, β = 94° 29 (1)′, γ = 90° 44 (1)′. The observed and calculated densities are 1.67 ± 0.02 and 1.68 g/cm3, respectively. The four- and five-coordinate molecules are well separated. The trans-planar complex NiBr2(P-(C6H5)(CH3)2)2 is crystallographically required to possess a center of inversion; the Ni-P and Ni-Br bond lengths are 2.251 (3) and 2.297 (2) Å, respectively. The five-coordinate Ni(III) complex NiBr3(P(C6H5)(CH3)2)2 possesses a trigonal-bipyramidal geometry with axial phosphine groups. There is a slight distortion of the molecule in the plane of the Ni and three Br atoms, which could arise from Jahn-Teller effects. The Ni-P bond distances are 2.263 (3) and 2.273 (3) Å, and the Ni-Br bond distances are 2.349 (2), 2.375 (2), and 2.339 (2) Å.

Original languageEnglish (US)
Pages (from-to)453-458
Number of pages6
JournalInorganic chemistry
Volume9
Issue number3
DOIs
StatePublished - Mar 1 1970

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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