Insertion of unsaturated hydrocarbons into the platinum–nitrogen bond of [Pt(PPh3)2(PhNO)]

Abstract

[Pt(PPh₃)₂(PhNO)](1) reacts with unsaturated hydrocarbons such as dimethyl acetylenedicarboxylate, tetracyanoethylene, and β,β-dicyanostyrene to give the corresponding 1:1 adducts [[graphic omitted](CO₂Me)}(PPh₃)₂](2) and [[graphic omitted](CN)₂}(PPh₃)₂][R¹= R²= CN (3); R¹= H, R²= Ph (4)] respectively. Fumaronitrile (NCCHCHCN) reacts with (1) to give a mixture of the 1:1 adduct and of the substitution product, [Pt(PPh₃)₂(NCCHCHCN)], while p-benzoquinone gave only [Pt(PPh₃)₂(OC₆H₄O-p)]. X-Ray studies on compound (2) have confirmed that the entering molecule is inserted into the platinum–nitrogen bond of the η²-bonded nitroso-ligand of compound (1). The reactions of (2) with mineral acids have been studied, I.r., ¹H n.m.r., and ³¹P n.m.r. spectra of the new compounds are reported and discussed.