Characterization of methyl(tri-n-butylphosphine)silver{I} (1), lithium{dimethyl(tri-n-butylphosphine)silver{I}} (2), and dilithium{trimethyl(tri-n-butylphosphine)silver{I}} (3) by ('1)H, ('7)Li, ('13)C, and ('31)P NMR spectroscopy has been already reported from our group. However, there are several factors that could affect the solution structures of these complexes which were not examined. These factors (solvent, halide ions, and concentration) are examined by various NMR spectroscopy. In various solvents such as in diethyl ether-benzene-d(,6), in diethyl ether only, and in toluene, there was no difference in NMR spectra (('13)C and ('31)P) of these methylsilver{I} complexes except for slight chemical shift changes. The presence of halide ions did not change the NMR spectra (('13)C and ('31)P) from those of the corresponding halide-free samples. Variable concentrations ranging from 0.1 M to 1.0 M for 1 and 0.1 M to 0.6 M for 2 did not influence the NMR spectra (('13)C and ('31)P) of these complexes except for slight changes in chemical shifts. Molecular weight measurements of 2 were carried out at -15(DEGREES)C by means of the vapor depression method. Although several equilibria involving 2 complicated the molecular weight measurements of 2, monomeric or dimeric structures were found to be most reasonable for 2. Kinetic studies of thermal decomposition of 1 were performed by means of ('31)P NMR spectroscopy. The results indicated that the thermal decomposition of 1 was a first order reaction and that the dissociation of a phosphine ligand was the rate-determining step. The mechanism of the thermal decomposition of 2 and 3 were also deduced based on the products and the mechanism proposed to 1. ('1)H, ('13)C, and ('31)P NMR studies of the mixtures of 1 and methyl(tri-n-butylphosphine)copper{I} (7) indicated the formation of methyl(tri-n-butylphosphine)silver{I}-copper{I} mixed complexes in ether solution. Possible structures for the mixed complexes are discussed. In addition, results of the preliminary ('199)Hg, ('31)P, and ('7)Li NMR studies of various mixtures of tetrakis{iodo(tri-n-butylphosphine)silver{I}} (4), methylmercuric bromide (18), and methyllithium are described.
