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

[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 [Pt{ON(Ph)C(C02Me)=C(C02Me)}(PPh3)2 (2) and [Pt{ON(Ph)CR1R2C(CN)2}(PPh3) 2] [R1 = R2 = CN (3); R1 = H, R2 = Ph (4)] respectively. Fumaronitrile (NCCH=CHCN) reacts with (1) to give a mixture of the 1:1 adduct and of the substitution product, [Pt(PPh3)2(NCCH=CHCN)], 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.