Ruthenium-Mediated Insertion of an Unsaturated C4 Unit into the P−N Bond of an Aminophosphine Ligand

The reactions of 1,6-heptadiyne and 1,7-octadiyne with [RuCp(PPh2NEt2)(CH3CN)2]+ afford the η3-phosphaallyl−η2-vinylamine complexes [RuCp(η3(P,C,C)-PPh2CHC(CH2)n2(C,C)-CCHNEt2)]+ (n = 3, 4), which cleanly rearrange to give the η1-phosphaallyl−η3-azaallyl complexes [RuCp(η1(P)-PPh2CHC(CH2)n3(C,C,N)-CCHNEt2)]+ (n = 3, 4).