Crystallographic and Spectroscopic Studies of Low-Symmetry Nickel(II) Complexes Possessing Long Nickel-Nitrogen Bonds

A. B.P. Lever, I. M. Walker, K. B. Mertes, A. Jircitano, R. Sheldon, P. J. Mccarthy

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Abstract

The X-ray structure of bis(isothiocyanato)bis(N,N-diethylethylenedi_amine)nickel(II), Ni[NH2C2H4N(C2H5)2]2(NCS)2, is reported. The complex crystallizes in the triclinic space group P1 with unit cell parameters a = 10.438 (10) A, b = 8.073 (8) Å, c = 14.876 (14) Å, α = 87.2 (8), β - 109.6 (7), γ = 112.8 (8), and 2 = 1. The nickel complexes are six-coordinate and all-trans. There is significant rhombic distortion due to bent NiNCS coordination, short NiNH2 bonds, and long NiN(C2H5)2 bonds. The single-crystal polarized spectrum of this crystal at 10 K is reported and analyzed in terms of rhombic symmetry. Single-crystal spectroscopic data for [Ni[NH2CH2CH2N(C2H5)2]2(H2O)2]2+Cl-2 and Ni-[(CH3)2NCH2CH2N(CH3)2]2(NCS)2 at 10 K are also reported. The data are compared with a range of other nickel complexes of low symmetry where both X-ray and spectroscopic data are available. The angular overlap model (AOM) is used, and it is demonstrated that AOM parameters in this low symmetry parallel those previously encountered for higher symmetries. In particular the use of sterically hindered amines provides a data set in which the Ni-N bond varies from about 208 to 233 pm. The σ-N AOM parameter is shown to correlate with the nickel-nitrogen bond length.

Original languageEnglish (US)
Pages (from-to)2252-2258
Number of pages7
JournalInorganic chemistry
Volume22
Issue number16
DOIs
StatePublished - Aug 1983

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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