Properties and Molecular Structures of Osmium(II) 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

Jean Pierre Djukic, Daniel A. Smith, Victor G. Young, L. Keith Woo

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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 (trimethylsily)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-c = 1.79(2) Å, torsion angle ϕ= 23(1)°). A similar conformation appears in complex 2 dos-c = 1.865(5) Å, torsion angle ϕ;= 28.4(4)°). 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)°. The complex 2 carbene moiety has a CAr ─C─CAr angle of 113.0(4)°. Complex 1, C52H46N4OsSi·OC4H8, crystallizes with a transcoordinated molecule of THF as 1·THF in the monoclinic space group P21/n with a = 13.954(2) Å,b = 9.522(2) Å,c = 17.969(2) Å, β = 101.42(1)°, V = 2340.3(6) Å3, Z = 2, R1 = 0.0532, and wR2 = 0.1276. Complex 2, C63H50N4Os·OC4H8·C7H8·½OC4H8, crystallizes as a trans-THF adduct, 2·THF, in the monoclinic space group C2/c with a = 28.003(6) Å,b = 14.385(3) Å,c = 33.748(8) Å,β = 114.51(2)°, V = 12370(5) Å3, Z = 8,R1 = 0.0389, and wR2 = 0.1165. Other metrical parameters and spectroscopic properties of these complexes are discussed.

Original languageEnglish (US)
Pages (from-to)3020-3026
Number of pages7
JournalOrganometallics
Volume13
Issue number8
DOIs
StatePublished - Aug 1 1994

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