SYNTHESIS, CHARACTERIZATION, AND PROTONATION OF AN AMIDE-CONTAINING THIOLATE COMPLEX OF A RUTHENIUM NITROSYL PORPHYRIN

1-(Acetylamino)-2-methylpropane-2-thionitrite reacts with (OEP)Ru(CO) or [(OEP)Ru]2 at room temperature to give the nitrosyl thiolate derivative, namely (OEP)Ru(NO)(SC(Me)2CH2NHC(O)Me), in high yield. This nitrosyl thiolate complex is moderately air stable and has IR νNO and νCO bands at 1789 and 1673 cm-1, respectively. Protonation of this complex with tetrafluoroboric acid and subsequent workup result in the formation of the amide complex, [(OEP)Ru(NO)(OC(Me)NHCH2C(Me)2SH)]BF4, in 92% yield. The crystal structures of the neutral (OEP)Ru(NO)(SC(Me)2CH2NHC(O)Me) and cationic [(OEP)Ru(NO)(OC(Me)NHCH2C(Me)2SH)]BF4 complexes have been determined by single-crystal X-ray crystallography.