Aryldiazo Complexes. Synthesis and Structure of a Five-Coordinate Complex Possessing a “Half Doubly Bent” Aryldiazo Ligand and an Intermediate Coordination Geometry[IrCl(N2C6H5)P(CH3(C6H5)2)3][PF6]

Martin Cowie, James A. Ibers*, Barry L. Haymore

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

36 Scopus citations

Abstract

The complex [IrCl(N2C6H5)(P(CH3)(C6H5)2)] [PF6] has been prepared with the specific intent of inducing the aryldiazo ligand into a geometry intermediate between the previously observed singly and doubly bent geometries. This has been accomplished by employing ligands of intermediate bulk (P(CH3)(C6H5)2) to distort the coordination geometry of the Ir atom from its electronically favored geometry. The structure of this iridium-aryldiazo complex has been determined crystallographically and consists of discrete cations and anions. The cation is five-coordinate with a highly distorted geometry about the metal which cannot be adequately described by any idealized geometry. The intermediate coordination geometry about the iridium atom is mirrored by the geometry of the aryldiazo ligand which is intermediate between singly and doubly bent. Some relevant metrical parameters are: Ir-N(1), 1.835 (8)Å; N(1)-N(2), 1.241 (11) Å; N(2)-C(11), 1.421 (11) Å; Ir-N(1)-N(2), 155.2 (7)°; N(1)-N(2)-C(111), 118.8 (8)°. The hexafluorophosphate anion is disordered. The compound crystallizes from acetone in space group C22-P21 with a = 15.767 (7) Å,b= 15.583 (7) Å, c = 9.002 (4) Å, β = 91.67 (2)°, and Z = 2. The pseudo-mirror-symmetry of the cation caused great difficulty in the solution of the structure, as it was very difficult to differentiate the correct atomic positions from the mirror-related images. The correct solution was obtained by excluding those solutions which resulted in highly irregular bond angles and distances and in unreasonably short nonbonded contacts. Based on 7134 reflections with Fo2≥ 3σ{Fo2), the structural data were refined by full-matrix, least-squares methods to R indices of R = 0.046 and Rw= 0.072. The synthesis, spectra, and reaction chemistry of the complex are discussed.

Original languageEnglish (US)
Pages (from-to)7608-7617
Number of pages10
JournalJournal of the American Chemical Society
Volume98
Issue number24
DOIs
StatePublished - Nov 1 1976

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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