Synthesis and molecular structures of N,N-dialkyl-4-nitrosoaniline adductsof formally d(6) metalloporphyrins of ruthenium and cobalt

Para-aminosubstituted nitrosoarenes react with Ru(CO)(OEP) or [Co(TPP)(THF) (2)]SbF6 (OEP2- 2,3,7,8,12,13,17,18-octaethylporphyrinato dianion, TPP2- = 5,10,15,20-tetraphenylporphyrinato dianion) to generate Ru(OEP)(ONC6H4NMe2) (2) and [Co(TPP)(ONC6H4NR2)(2)]SbF6 (R =Me, Et), respectively, in fair to h igh yields. These N-bound nitrosoarene complexes have been characterized by spectroscopic methods. The complexes Ru(OEP)(ONC6H4NMe2)(2) and [Co(TPP)(O NC6H4NMe2)(2)]ClO4 have also been characterized by single-crystal X-ray cry stallography. Their structures represent the first reported solid-state str uctures of Ru and Co porphyrins containing C-nitroso ligands. Copyright (C) 2001 John Wiley & Sons, Ltd.