Département de chimie moléculaire

{Several phosphinous acid-coordinated platinum complexes were prepd. and characterized. In the presence of secondary phosphine oxide (2 equiv), PtCl2(cod) was converted to cis/trans platinum complexes PtCl2[R1R2POH]2 featuring phosphinous acids (PAs) as ligands (20-29). A balance between the steric and electronic effects of ligands governs their coordination mode. NMR expts. and d. functional theory calcns. show that the anti conformer for trans complexes is favored by intramol. H···Cl bonding. PtCl2[R1R2POH]2 treated with NEt3 (1 equiv) gave bimetallic platinum complexes cis-[Pt2($μ$-Cl)2{\{}(R1R2PO)2H{\}}2] characterized by 31P NMR and x-ray diffraction. An unusual monometallic platinum complex, cis-[PtCl2{\{}(i-Bu)2PO{\}}2H]-[HNEt3]+ (30), was isolated and characterized as a possible intermediate in the formation of dinuclear species. Silver acetate and triethylamine both reacted with PtCl2[(t-Bu)2POH]2 to yield new bulky Pt($ąppa$2-acetato){\{}[(t-Bu)2PO]2H{\}} platinum complex 31. The structure of complexes 20d (R1 = Ph