The hydrated and dimethyl sulfoxide and N,N'-dimethylpropyleneurea solvated silver(I) ions have been characterized structurally in solution by means of extended X-ray absorption fine structure (EXAFS) and large-angle X-ray scattering (LAXS). The coordination chemistry of the hydrated and dimethyl sulfoxide solvated silver(I) ions has been reevaluated because of different results from the EXAFS and LAXS methods reported previously. Consistent results are obtained with a linearly distorted tetrahedral model with two short and approximately two long Ag-O bond distances: mean Ag-O bond lengths of 2.32(1) and 2.54(1) A for the hydrate, 2.31(1) and 2.48(2) A for the dimethyl sulfoxide solvate, and 2.31(1) and 2.54(2) A for the N,N'-dimethylpropyleneurea solvate, in solution.

The coordination chemistry of the solvate complexes of the relatively soft electron-pair acceptor copper(I) has been studied in solution and solid state in seven solvents with strong electron-pair donor properties, liquid ammonia, trimethyl, triethyl, triisopropyl, tri-n-butyl and triphenyl phosphite, and tri-n-butylphosphine. The solvate complexes have been characterised by means of EXAFS and 63Cu NMR spectroscopy, and in some cases also by 65Cu NMR spectroscopy. The copper(I) ion is three-coordinated, most probably in a coplanar trigonal fashion, in liquid ammonia with a mean Cu-N bond distance of 2.00(1) Angstroms. No 63Cu NMR signal has been detected from the ammonia solvated copper(I) ion in liquid ammonia, which supports a three-coordination. The phosphite and phosphine solvated copper(I) ions are tetrahedral with Cu-P bond distances in the range 2.24-2.28 Angstrom in both solution and solid state as determined by EXAFS spectroscopy. The tetrahedral configuration of these complexes has been confirmed by 63Cu and 65Cu NMR spectroscopy through the J(63Cu-31P) and J(65Cu-31P) couplings. The fact that two of the investigated complexes, [Cu(P(OC6H5)3)4]+ and [Cu(P(C4H9)3)4]+, are 63Cu and 65Cu NMR silent is probably caused by a significantly angular distorted tetrahedral configuration.

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 Ag(I) ions have been characterized in solution by means of extended X-ray absorption fine structure (EXAFS), Raman, and (107)Ag NMR spectroscopy and the solid solvates by means of thermogravimetry and EXAFS and Raman spectroscopy. The Ag(I) 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) A, respectively. The crystal structure of [Ag(NH3)3]ClO4.0.47 NH3 (1) reveals a regular trigonal-coplanar coordination around the Ag(I) ion with Ag-N bond distances of 2.263(6) A and a Ag...Ag distance of 3.278(2) A 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...Ag distance is 3.01(1) A. 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) A, 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 A. The Au(I) 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) A, respectively.

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