Synthesis and reactivity toward nucleophiles of bis(isocyanide)(porphyrinato)rhodium(III) complexes. Crystal and molecular structure of a novel carbene complex: {(TPP)Rh(PhCH2NC)[:C(NHCH2Ph)2]PF6}

Article abstract of DOI:10.1021/om00104a010

Bis(isocyanide)(octaethylporphyrinato)- and bis(isocyanide)(tetraphenylporphyrinato)rhodium(III) hexafluorophosphates undergo nucleophilic attack leading to the formation of cationic carbene derivatives or neutral carboxymethyl, amido, and alkyl complexes. The formation of the various products is related tq the strength of the nucleophile. The crystal and molecular structure of the title compound has been determined by X-ray diffraction methods. The crystals are triclinic, space group P1, with unit cell dimensions a = 16.427 (7) ?, b = 14.386 (7) ?, c = 13.268 (5) ?, α = 107.83 (4)°, β = 99.51 (4)°, γ = 77.31 (3)°, and Z = 2. The structure was solved by the heavy-atom technique and refined to R = 0.0773 for 3991 independent reflections. The rhodium atom is at the center of a slightly distorted octahedral environment.