Synthesis and reactivity towards diiodine of palladium(II) and platinum(II) complexes with non-cyclic and cyclic ligands (C6H3{CH=NR1R2}2-2,6)-. End-on diiodine-platinum(II) bonding in macrocyclic [PtI(C6H3{CH2NMe(CH2)7MeNCH2}-2,6)(h1-I2)]

Abstract

Several new organo-platinum(II) and -palladium(II) complexes [MX(C{6}H{3}{CH{2}NR}1{R}2{}{2}-2, 6)] (X = halide, M = Pt, Pd; R}1{ = R}2{ = Et; R}2{ = Me, R}1{ = }t{Bu, M = Pt: R}2{ = Me, R}1{ = Ph) have been synthesized from [PtCl{2}(SEt{2}){2}] or [PdCl{2}(COD)] (COD = 1, 5-cyclooctadiene) by reaction with [Li(C{6}H{3}{CH{2}NR}1{R}2{}{2}-2,6]{n}. Two of the intermediate Li complexes, i.e. [Li((tBu)MeNCN)]{2} and [Li((Ph)MeNCN)]{2} were isolated. In the platinum and palladium complexes the NCN ligands are terdentate bonded through C{i}{p}{s}{o} and two trans-positioned amine donor atoms. The complexes [PtI(C{6}H{3}{CH{2}NMe(CH{2}){7}MeNCH{2}}-2,6)] (4), in which the N(Me) atoms of the terdentate ligand are connected by a short (CH{2}){7} chain, and [PtCl(C{6}H{3}{CH{2}NPh{2}}{2}-2,6)(SEt{2}){2}], in which the Ph{2}NCN ligand is chain, and [PtCl(C{6}H{3}{CH{2}NPh{2}}{2}-2,6)(SEt{2}){2}], in which the Ph{2}NCN ligand is only monodentate bonded via C{i}{p}{s}{o}, were also made. The coordination ability of the NR}1{R}2{ donor atoms in these compounds was found to decrease in the order Me{2}N ~ (}t{Bu)MeN > Et{2}N > (Ph)MeN > Ph{2}N.