Insertion reaction of isocyanide into the Pt-C bonds of 2,5-thienylene-bridged diplatinum complexes and 2-thienyl platinum complexes: molecular structure of Cl(Et3P)2PtC(=NC6H4OMe-p)C4H2SC(=NC6H4OMe-p)Pt(PEt3)2Cl*CH2Cl2

Article abstract of DOI:10.1016/0022-328X(94)05193-F

Treatments of 2,5-thienylene-bridged diplatinum complexes Cl(R3P)2PtC4H2SPt(PR3)2Cl (1) with two equivalents of isocyanide cause the insertion of isocyanide into each of the two Pt-C bonds to produce Cl(R3P)2PtC(=NAr)C4H2SC(=NAr)Pt(PR3)2Cl (2). 2-Thienyl platinum complexes C4H3SPt(PR3)2Cl (4) also react with isocyanide to give iminoacyl complexes C4H3SC(=NAr)Pt(PR3)2Cl (5).Further insertion of isocyanide into Pt-C bonds of 2 and 5 was not observed even in the reaction with excess isocyanide.When 1a was treated with an equimolar amount of p-tolyl isocyanide, a single-insertion product Cl(Et3P)2PtC(=NC6H4Me-p)C4H2SPt(PEt3)2Cl (3b) was obtained altogether with the mixture of 1a and 2a.The molecular structure of Cl(Et3P)2PtC(=NC6H4OMe-p)C4H2SC(=NC6H4OMe-p)Pt(PEt3)2Cl*CH2Cl2 (2b) was determined by an X-ray crystallographic analysis and the crystallographic data are as follows: space group, P2₁/n; a = 11.044(2), b = 28.086(3) and c = 18.396(3) Angstroem; β = 93.96 deg, V = 5692(2) Angstroem³; Z = 4. Keywords: Platinum; Isocyanide; Crystal structure