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(ET(3)P)(2)PTC(=NC(6)H(4)OME-P)C4H2SC (=NC(6)H(4)OME-P)PT(PET(3))(2)CL-CENTER-DOT-CH2CL2

Treatments of 2,5-thienylene-bridged diplatinum complexes Cl(R(3)P)(2) PtC4H2SPt(PR(3))(2)Cl (1) with two equivalents of isocyanide cause the insertion of isocyanide into each of the two Pt-C bonds to produce Cl (R(3)P)(2)PtC(=NAr)C4H2SC(=NAr)-Pt(PR(3))(2)Cl (2). 2-Thienyl platinum complexes C4H3SPt(PR(3))(2)Cl (4) also react with isocyanide to give iminoacyl complexes C4H3SC(=NAr)Pt(PR(3))(2)Cl (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 (Et(3)P)(2)P tC(=NC(6)H(4)Me-p)C4H2SPt(PEt(3))(2)Cl (3b) was obtained altogether wi th the mixture of 1a and 2a. The molecular structure of 6)H(4)OMe-p)C4 H2SC(=NC(6)H(4)OMe-p)Pt(PEt(3))(2)Cl . CH2Cl2 (2b) was determined by a n X-ray crystallographic analysis and the crystallographic data are as follows: space group, P2(1)/n; a = 11.044(2), b = 28.086(3) and c = 1 8.396(3) Angstrom; beta = 93.96 degrees; V = 5692(2) Angstrom(3); Z = 4.