Aryldiazo Complexes. Structure of an Iron-Aryldiazo Complex, [Fe(CO)2(N2C6H5)(P(C6H5)3)2][BF4]

Barry L. Haymore, James A. Ibers

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Abstract

The structure of [Fe(CO)2(N2C6H5)(P(C6H5)3)2] [BF4] has been determined crystallographically. The compound crystallizes from acetone as solvent-free crystals in space group C2h5-P21/c with a = 13.447 (4) Å, b = 14.260 (4) Å, c = 22.755 (16) Å, β = 113.29 (2)°, Z = 4, pexptl = 1.37(1) g/cm3, and pealed = 1.373 g/cm3. Based on 3159 unique reflections with Fo2 > 3σ (Fo2), the structure was solved and refined by full-matrix, least-squares methods to R = 0.064 and Rw= 0.088. The structure consists of discrete cations and anions; the BF4 anions are partially disordered. The iron cation is five-coordinate with a coordination geometry close to trigonal bipyramidal. Apparently for steric reasons, the two carbonyl groups are nonequivalent. The phenyldiazo ligand in this complex is singly bent with Fe-N = 1.702 (6) Å, N-N = 1.201 (7) Å, N-C = 1.404 (8) Å, Fe-N-N = 179.2 (5)°, and N-N-C = 124.2 (6)°. The short Fe-N and N-N distances, as well as the general ligand geometry, suggest that multiple metal-nitrogen and nitrogen-nitrogen bonding is present and that the complex is best described as a PhN2+ complex of Fe(0). Structural and spectroscopic data suggest that the aryldiazo ligand is a good π acceptor but a poor σ donor.

Original languageEnglish (US)
Pages (from-to)1369-1376
Number of pages8
JournalInorganic chemistry
Volume14
Issue number6
DOIs
StatePublished - Jun 1 1975

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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