Formation of N–C bonds via alkylation of transition metal nitrosyls. Reaction of ruthenium and other transition metal nitrosyls with benzyl bromide

Abstract

[Ru(NO)2(PPh3)2] reacts with benzyl bromide in refluxing toluene under CO to give [RuBr(CO)(NO)(PPh3)2], [RuBr2(CO)2(PPh3)2], PhCHNOH, PhCN, PhCONH2, PhCHO, and PhCH2OH. In the absence of CO, [Ru(NO)2(PPh3)2] reacts with benzyl bromide to give [RuBr2(NCPh)2(PPh3)2], [RuBr3(NO)(PPh3)2], PhCN, PhCONH2, (PhCH2)2, and PhCHO, but in amounts smaller than those obtained under CO. In the absence of a metal, NO gas reacts with benzyl bromide in refluxing toluene to give PhCH2NO2(major product, 45%) and small amounts of PhCN, PhCHO, and PhCH2OH. Reaction of [Ru(NO)2(PPh3)2] with PhCH2Cl and other alkyl bromides, and of [Ru(NO)2(Ph2PCH2CH2PPh2)], [Ru(NO)2{P(OPh)3}2], [Co(NO){P(OEt)3}3], [Rh(NO)(PPh3)3], and [RhCl2(NO)(PPh3)2] with PhCH2Br are briefly discussed.