Regioselective nucleophilic addition of triphenylphosphine to the nitrosylruthenium alkynyl complexes having a hydrotris(pyrazol-1-yl)borate: formation of phosphonio-alkenyl, alkynyl, and allenyl species

A nitrosylruthenium alkynyl complex of TpRuCl(Ctriple bond]CPh)(NO)(1a) was reacted with PPh3 in the presence of HBF4.Et2O at room temperature to give a beta-phosphonio-alkenyl complex (E)-TpRuCl{CH=C(PPh3)Ph}(NO)]BF4(2.BF4). On the other hand, for gamma-hydroxyalkynyl complexes TpRuCl{Ctriple bond]CC(R)2OH}(NO)(R = Me (1b), Ph (1c), H (1d)), similar treatments with PPh3 were found to give gamma-phosphonio-alkynyl TpRuCl{Ctriple bond]CC(Me)2PPh3}(NO)]BF4(3.BF4),alpha-phosphonio-allenyl TpRuCl{C(PPh3)=C=CPh2}(NO)]BF4(4.BF4), and a novel product of gamma-hydroxy-beta-phosphonio-alkenyl (E)-TpRuCl{CH=C(PPh3)CH2OH}(NO)]BF4(5.BF4), respectively. Dominant factors for the selectivity in affording 3-5 were associated with the steric congestion and electronic properties at the gamma-carbons, along with those around the metal fragment. From the bis(alkynyl) complex TpRu(Ctriple bond]CPh)2(NO)6, a bis(beta-phosphonio-alkenyl)(E,E)-TpRu{CH=C(PPh3)Ph}2(NO)](BF4)2{7.(BF4)2} was produced at room temperature. However, similar reactions at 0 degrees C gave an alkynyl beta-phosphonio-alkenyl complex (E)-TpRu(Ctriple bondCPh){CH=C(PPh3)Ph}(NO)]BF4(8.BF4) as a sole product, of which additional hydration in the presence of HBF4.Et2O afforded a small beta]-phosphonio-alkenyl ketonyl (E)-TpRu{CH2C(O)Ph}{CH=C(PPh3)Ph}(NO)]BF(.9BF4). Five complexes, 2-5 and 7 were crystallographically characterized.