Remarkably Stable Iron Porphyrins Bearing Nonheteroatom-Stabilized Carbene or (Alkoxycarbonyl)carbenes:  Isolation, X-ray Crystal Structures, and Carbon Atom Transfer Reactions with Hydrocarbons

Reactions of [Fe(TPFPP)] (TPFPP = meso-tetrakis(pentafluorophenyl)porphyrinato dianion) with diazo compounds N(2)C(Ph)R (R = Ph, CO(2)Et, CO(2)CH(2)CH=CH(2)) afforded [Fe(TPFPP)(C(Ph)R)] (R = Ph (1), CO(2)Et (2), CO(2)CH(2)CH=CH(2) (3)) in 65-70% yields. Treatment of 1 with N-methylimidazole (MeIm) gave the adduct [Fe(TPFPP)(CPh(2))(MeIm)] (4) in 65% yield. These new iron porphyrin carbene complexes were characterized by NMR and UV-vis spectroscopy, mass spectrometry, and elemental analyses. X-ray crystal structure determinations of 1.0.5C(6)H(6).0.5CH(2)Cl(2) and 4 reveal Fe=CPh(2) bond lengths of 1.767(3) (1) and 1.827(5) A (4), together with large ruffling distortions of the TPFPP macrocycle. Complexes 2 and 4 are reactive toward styrene, affording the corresponding cyclopropanes in 82 and 53% yields, respectively. Complex 1 is an active catalyst for both intermolecular cyclopropanation of styrenes with ethyl diazoacetate and intramolecular cyclopropanation of allylic diazoacetates. Reactions of 2 and 4 with cyclohexene or cumene produced allylic or benzylic C-H insertion products in up to 83% yield.