Reactions of acetylenes with nobile-metal carbonyl halides .14. chemical characterization and X-ray structural-analysis of PT(-C(C3H7)=C(H)C(=NC6H4ME)C2H5)(CO)CL

The mixture of[H3O]2[Pt(CO)2]3n with[H3O][Pt(CO)Cl3], prepared by reduction of Pt(CO)2Cl2 with carbon monoxide and water, reacts with C3H7C=CC(O)C2H5 to give Pt{-C(C3H7)=C(H)C(=O)C2H5}(CO)Cl, 1. This compound reacts with aromatic amines to give the ketimine derivatives Pt{-C(C3H7)=C(H)C(=NR C2H5}(CO)Cl (2a R = C6H4Me; 2b R = C6H5). The solution structures of compounds 1, 2a and 2b have been determined by a multinuclear NMR study (H-1, C-13, N-15, and Pt-195) and an unambiguous assignment of the different resonances is given. The crystal structure of complex 2a has been determined by X-ray diffraction methods. Crystals of 2a are triclinic, space group P1BAR, a = 10.375(2), b = 9.850(2), c = 8.563(3) angstrom, alpha = 88.66(4); beta = 84.80(4); gamma = 81.03(6)-degrees, and Z = 2; R = 0.0708 and R(W) = 0.0737 for 1203 observed reflections. The crystal contains discrete molecules of 2a with a square-planar coordination around the Pt atom showing large deviations from ideality due to the five-membered ring.