Coordination chemistry of the solvated AgI and AuI ions in liquid and aqueous ammonia, trialkyl and triphenyl phosphite, and tri-n-butylphosphine solutions

The coordination chemistry of solvated Ag-I and Au-I ions has been studied in some of the most strong electron-pair donor solvents, liquid and aqueous ammonia, and the P donor solvents triethyl, tri-n-butyl, and triphenyl phosphite and tri-n-butylphosphine. The solvated AgI ions have been characterized in solution by means of extended X-ray absorption fine structure (EXAFS), Raman, and Ag-107 NMR spectroscopy and the solid solvates by means of thermogravimetry and EXAFS and Raman spectroscopy. The AgI ion is two- and three- coordinated in aqueous and liquid ammonia solutions with mean Ag - N bond distances of 2.15(1) and 2.26(1) angstrom, respectively. The crystal structure of [Ag(NH3)(3)] ClO4, 0.47 NH3 (1) reveals a regular trigonal-coplanar coordination around the AgI ion with Ag - N bond distances of 2.263(6) angstrom and a Ag center dot center dot center dot Ag distance of 3.278(2) angstrom separating the complexes. The decomposition products of 1 have been analyzed, and one of them, [Ag( NH3) 2] ClO4, has been structurally characterized by means of EXAFS, showing [ Ag( NH3) 2] units connected into chains by double O bridges from perchlorate ions; the Ag center dot center dot center dot Ag distance is 3.01( 1) angstrom. The linear bisamminegold(I) complex, [Au(NH3)(2)](+), is predominant in both liquid and aqueous ammonia solutions, as well as in solid [Au(NH3)(2)]BF4, with Au - N bond distances of 2.022(5), 2.025- 5), and 2.026(7) angstrom, respectively. The solvated Ag-I ions are three- coordinated, most probably in triangular fashion, in the P donor solvents with mean Ag-P bond distances of 2.48 - 2.53 angstrom. The AuI ions are three- coordinated in triethyl phosphite and tri-n-butylphosphine solutions with mean Au - P bond distances of 2.37(1) and 2.40(1) angstrom, respectively.