SYNTHESIS AND CHARACTERIZATION OF COPPER AND MANGANESE COMPLEXES OF MONODENTATE FUNCTIONALIZED ISOCYANIDE - TRIMETHYLSILYLMETHYLISOCYANIDE AND P-TOLYLSULFONYLMETHYLISOCYANIDE

Reaction of excess CNCH2SiMe3(L) with CuX2.nH2O (X=NO3-, n=3; ClO4-, n=6) in THF gives the Cu(I) complexes [CuL4]NO3 (1) and [CuL4]ClO4 (2). When CuCN is used as starting material, complex 3, Cu(L3)CN, C4H10O.3H2O, is obtained. Immediate reduction occurs with AgNO3 precipitating metallic Ag. Reactions with MnCl2.6H2O and Mn(NO3)2.6H2O in THF produce two new compounds which analyze as MnL4Cl2.4H2O (6) and MnL2(NO3)2.H2O (7). When excess p-tolylsulfonylmethylisocyanide (L') is reacted with Cu(NO3)2, the mixed-valence Cu(I)-Cu(II) complex Cu2L6'(NO3)3 (5) is Precipitated, while using CuCN gives the Cu(I) dimer Cu2L'4(CN)2 (4). In analogous conditions the manganese complex MnL'2(NO3)2.C3H6O.3H2O (8) is precipitated. All these complexes have been isolated, characterized by IR, NMR for diamagnetic species, magnetic susceptibilities, EPR measurements and electrochemical analyses. Influence of the two substituents is discussed.