Synthesis, Characterization, and Reactivity of Iron Carbonyl Clusters Containing Bismuth or Antimony. Crystal Structures of Isomorphous [Et4N][BiFe3Cr(CO)17] and [Et4N][SbFe3Cr(CO)17] and the Ring Complex Bi2Fe2(CO)8Me2

Kenton H. Whitmire, Minghuey Shieh, Juanita Cassidy

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Abstract

The reaction of [Et4N]2[Fe2(CO)8] with BiCl3 or SbCl3 forms compounds (la, E = Bi; lb, E = Sb) that are proposed to be the previously characterized [Et4N][EClFe3(CO)12] based on elemental analyses and spectroscopic data. Treatment of la or lb with Cr(CO)5(THF) produces [Et4N][EFe3Cr(CO)17] (IIa and IIb, respectively), while the methylation of la affords Bi2Fe2(CO)8Me2(III). Refluxing la and lb in acetonitrile gives the previously known [Et4N]2[Bi2Fe4(CO)13] and [Et4N]2[Sb2Fe5(CO)17], respectively. Ila, Ilb, and III have been characterized by X-ray crystallography. Ila crystallizes in the centrosymmetric triclinic space group P1 (no. 2) with a = 12.297 (3) A, b = 15.154 (3) A,c = 9.791 (1) A, a = 107.60 (1)°,β = 95.24 (2)°, ϒ = 92.02 (2)°, V = 1727.9 (6) A3 and Z = 2, The structure was refined to R - 4,5% and Rw= 5.3% for those 5114 reflections with 1 > 3σ(I). The core framework of Ila consists of a distorted tetrahedral BiFe3Cr cluster in which a central bismuth atom is bonded to isolated Fe(CO)4 and Cr(CO)5 groups and a metal-metal-bonded Fe2(CO)8 fragment. The Fe-Fe bond distance is 2.608 (2) A, and the Fel-Bil-Fe2 angle is 56.91 (4)°. lib is isomorphous with Ila: centrosymmetric triclinic space group P1 (no. 2), a = 12.233 (1) A, b = 15.108 (5) A, c = 9.742 (3) A,a- 107.23 (3)°, β= 94.61 (2)°, y = 92.37 (1)°, V= 1710.0 (9) A3, and Z = 2. Diffraction data were refined to R= 4.2% and Rw= 5.7% for those 6100 reflections with I > 3σ(I). The Fe-Fe bond distance in lib is 2.598 (1) A. Ill crystallizes in the centrosymmetric triclinic space group P1 (no. 2) with a = 7.571 (4) A, b = 8.734 (4) A, c = 7.136 (3) A, a = 107.02 (4)°, β= 108.41 (4)°, ϒ = 79.89 (4)°, V= 426.3 (4) A3, and Z = 1. Refinement converged at R = 4.1% and Rw= 5.3% for those 1355 reflections with I> 3σ(I). Ill consists of a Bi2Fe2 parallelogram situated about a crystallographic inversion center. There is one Me group bonded to each bismuth atom. The Fe(CO)4 groups are pseudooctahedral with an average Bi-Fe distance of 2.786 A. The Bi-C distance is 2.28 (1) A.

Original languageEnglish
Pages (from-to)3164-3170
Number of pages7
JournalInorganic Chemistry
Volume28
Issue number16
DOIs
Publication statusPublished - 1989 Aug 1

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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