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Properties and Molecular Structures of Osmium(ll) Porphyrin Carbene Complexes: (5,10,15,20-Tetra-p-tolylporphyrinato )osmium Di-p-tolylmethylidene and (5,10,15,20-Tetra-p-tolylporphyrinato)osmium (Trimethylsilyl)methylidene
Organometallics
  • Jean-Pierre Djukic, Iowa State University
  • Daniel A. Smith, Iowa State University
  • Victor G. Young, Jr., Iowa State University
  • L. Keith Woo, Iowa State University
Document Type
Article
Disciplines
Publication Version
Published Version
Publication Date
8-1-1994
DOI
10.1021/om00020a018
Abstract
The first molecular structures of two (porphyrinato)osmium(II) alkylidene complexes are described. The carbene fragments of (5,10,15,20-tetra-p-tolylporphyrinato)osmium (trimethylsilyl) methylidene (1) and (5,10,15,20-tetra-p-tolylporphyrinato)osmium di-p-tolylmethylidene (2) adopt different conformations in the solid state. With respect to the porphyrin ring nitrogen atoms, a staggered conformation is found for the complex 1 carbene moiety (dos-e = 1. 79(2) A, torsion angle ¢ = 23(1)0 ). A similar conformation appears in complex 2 (dos-e= 1.865(5) A, torsion angle¢= 28.4(4)0 ). The carbene fragments in the two molecular structures are distorted and do not possess ideal sp2 geometries. Complex 1 displays a large distortion with an Os-C-Si angle of 142(2)0 • The complex 2 carbene moiety has a CAr-C-CAr angle of 113.0(4)0 • Complex 1, C52H46N40sSioOCJia, crystallizes with a transcoordinated molecule ofTHF as 1·111F in the monoclinic space group P21/n with a = 13.954- (2) A, b = 9.522(2) A, c = 17.969(2) A, f3 = 101.42(1)0 , v = 2340.3(6) A3, z = 2, Rl = 0.0532, and wR2 = 0.1276. Complex 2, CsaH5oN40soOC4HaoC7Ha·1/20CJia, crystallizes as a transTHF adduct, 2·THF, in the monoclinic space group C2/c with a = 28.003(6) A, b = 14.385(3) A, c = 33.748(8) A, f3 = 114.51(2)0 , V = 12370(5) A3, Z = 8, Rl = 0.0389, and wR2 = 0.1165. Other metrical parameters and spectroscopic properties of these complexes are discussed.
Comments

Reprinted (adapted) with permission from Organometallics 13 (1994): 3020, doi:10.1021/om00020a018. Copyright 1994 American Chemical Society.

Copyright Owner
American Chemical Society
Language
en
File Format
application/pdf
Citation Information
Jean-Pierre Djukic, Daniel A. Smith, Victor G. Young and L. Keith Woo. "Properties and Molecular Structures of Osmium(ll) Porphyrin Carbene Complexes: (5,10,15,20-Tetra-p-tolylporphyrinato )osmium Di-p-tolylmethylidene and (5,10,15,20-Tetra-p-tolylporphyrinato)osmium (Trimethylsilyl)methylidene" Organometallics Vol. 13 Iss. 8 (1994) p. 3020 - 3026
Available at: http://works.bepress.com/l-woo/106/