CATIONIC SILVER COMPOUNDS WITH METAL (CO, RH, IR) TRIS(DITHIOCARBAMATE) AND TRIS(DISELENOCARBAMATE) COMPLEXES AS LIGANDS - SYNTHETIC, ELECTROCHEMICAL, NMR, ELECTROSPRAY MASS SPECTROMETRIC AND X-RAY CRYSTALLOGRAPHIC STUDIES

摘要

The interaction of metal tris(dithiocarbamate) (M=Co, Rh, Ir; dithiocarbamate=dtc=[R2NCS2](-)) and tris(diselenocarbamate) (dsc=[R2NCSe2](-)) complexes with AgBF4 in dichloromethane/toluene solution led to the formation of [Ag{M(R(2)dtc)(3))(2)]BF4 and [Ag{M(R(2)dsc)(3)}(2)]BF4 compounds which were isolated as stable solids. Extensive voltammetric and electrospray mass spectrometric studies showed that the cations retained their identities in solution. Electrochemical measurements and, for the cobalt complexes Co-59 NMR studies, showed the cations to be thermodynamically very stable but kinetically labile in solution. [Ag{Co(i-Pr(2)dtc)(3)}(2)]BF4 . 0.5C(6)H(14) was isolated in the form of crystals suitable for X-ray analysis. Crystal data for [Ag{Co(i-Pr(2)dtc)(3)}(2)]BF4 . 0.5C(6)H(14):M-r=1413.5, monoclinic space group P2(1) (No. 14), a=15.625(5), b=19.29(1), c=25.41 (1) Angstrom, beta=103.88(3)degrees, Z=4, Mo K alpha radiation, R=0.082, R-w=0.079 for 2979 independent reflections. The crystal structure consists of discrete [Ag(Co(i-Pr(2)dtc)(3)}(2)](+) cations and [BF4](-) anions together with hexane of crystallisation. The Co(i-Pr(2)dtc)(3) units are coordinated to silver through two sulfur atoms of different dithiocarbamate ligands to generate approximately tetrahedral geometry about silver. There is no direct Ag-Co bonding. [References: 37]