Chiral ruthenium (Ⅱ) and manganese(Ⅲ) porphyrins catalyse the asymmetric amidation of saturated C-H bonds of ethylbenzene and ethylnaphthalenes to form the corresponding amides in up to 85% yield with 45-58% ee.

Amidation of a variety of hydrocarbons with PhIdNTs catalyzed by ruthenium and manganese meso-tetrakis(pentafluorophenyl)porphyrins 1 and 2 afforded N-substituted amides in up to 92% yields with good to excellent substrate conversions. By employing catalyst 2, exceptionally high turnovers (up to 2600) were achieved, and the amidations can be effected by directly using PhI(OAc)2/NH2R as amidating reagents; in the case of R) COCF3 a direct amination was realized in up to 90% yield.

The reaction of [{m-h2-C(R1) CHR2}(m-CO)Fe2(CO)6] with (m-S2)Fe2(CO)6 forms (m3-S)2Fe3(CO)9 (1) and:or anionic intermediates [{m-h2-C(R1) CHR2}(m-S){Fe2(CO)6}2(m4-S)] (2) depending on the substituents R1 and R2. The actions of the anionic complexes 2 with alkyl halides, PhN2BF4 and acid chlorides give [m-h2-C(R1) CHR2](m-RS)[Fe2(CO)6]2(m4-S) (R alkyl, Ph or acyl). The structures of (m-h2-CH CHPh](m-CH2 CHCH2S)[Fe2(CO)6]2(m4-S)