Activation of Thionitrites and Isoamyl Nitrite by Group 8 Metalloporphyrins and the Subsequent Generation of Nitrosyl Thiolates and Alkoxides of Ruthenium and Osmium Porphyrins

Ruthenium and osmium porphyrins of the form (por)M(CO) (por = octaethylporphyrinato dianion (OEP), tetratolylporphyrinato dianion (TTP)) react with thionitrites (RSNO) and isoamyl nitrite (RONO) to give the (por)M(NO)(SR) and (por)M(NO)(OR) addition products. Reaction of S-nitroso-N-acetyl-l-cysteine methyl ester with (TPP)Fe(THF)2 (TPP = tetraphenylporphyrinato dianion) gives (TPP)Fe(NO) in high yield. The related reaction of isoamyl nitrite with [(TPP)Fe(THF)2]+ gives the nitrosyl alcohol product [(TPP)Fe(NO)(HO-i-C5H11)]+. The solid state structures of (OEP)Ru(NO)(NACysMe-S) (NACysMe = N-acetyl-l-cysteinate methyl ester), (TTP)Os(NO)(S-i-C5H11), and [(TPP)Fe(NO)(HO-i-C5H11)]+ have been determined by X-ray diffraction.