Arene displacement, C-H activation and acetonitrile insertion reactions enabled by coordination of a functionalized iminophosphorane to a RuII-p-cymene scaffold.

Reaction of a sterically demanding iminophosphorano-phosphine, Ph2PCH2Ph2PNAr* (here onwards referred to as PCPNAr*; Ar* = 2,6-dibenzhydryl-4-methylphenyl), (1) with [Ru(η6-p-cymene)Cl2]2 yielded three different types of complex, [RuCl2{(η6-p-cymene)(PCPNAr*)-κ1-P}] (2), [RuCl{(P(O)CPNAr*)(κ2-N,C)(C-η6-arene)}] (3) and [RuCl{(POCPNAr*)(κ2-N,C-o)(C-η6-arene)}] (4), depending on the reaction conditions via CH activation, tethered η6-arene coordination, ortho-metallation or PN bond cleavage/rearrangement reactions. Interestingly, a similar reaction in CH3CN in the presence of AgBF4 resulted in the insertion of CH3CN into the PN bond to form a novel metallacycle [Ru(NCMe)3{(PC2PN(CH3)CNAr*)-κ3-N,N,P}][BF4]2 (5) containing 4- and 5-membered rings via an aza-Wittig type reaction. Complex 4 showed very good catalytic activity in the transfer hydrogenation of carbonyl compounds.