SYNTHESES AND SPECTROSCOPIC AND STRUCTURAL CHARACTERIZATION OF SILVER(I) COMPLEXES CONTAINING TERTIARY PHOSPHINES AND HYDROTRIS(PYRAZOL-1-YL)BORATES, HYDROTRIS(4-BROMOPYRAZOL-1-YL)BORATES, HYDROTRIS(3,5-DIMETHYPYRAZOL-1-YL)BORATES, AND HYDROTRIS(3-METHYL-2-THIOXO-1-IMIDAZOLYL)BORATES

(Trialkyl- and (triarylphosphine)silver(I) derivatives containing anio nic tris(1H-pyrazol-1-yl)borates were prepared from AgX (X = CF3SO3 or NO3), PR3 (R = phenyl, benzyl, cyclohexyl, 2,4,6-trimethylphenyl, or o-, m-, and p-tolyl) or PMePh2, and M[HB(pz)(3)] [M = K or Na; pzH pyr azole in general; in detail, pyrazole (PzH), 3,5-dimethylypyrazole (3, 5-Me(2)PzH), or 4-bromopyrazole (4-BrPzH)] and characterized through a nalytical and spectral (IR;H-1, C-13, and P-31 NMR) measurements. Thes e air stable, light-sensitive complexes are not electrolytes in CH2Cl2 and acetone. In these solvents they decompose even with strict exclus ion of oxygen and light. The solid-state structures show that the silv er atom adopts a distorted tetrahedral geometry. Crystal data with Mo K alpha (lambda = 0.710 70 Angstrom) at 293 K: [HB(Pz)(3)]Ag(PPh3), C5 4H50Ag2B2N12P2, a = 15.081(2) Angstrom, b = 19.728(2) Angstrom, c = 9. 432(1) Angstrom, alpha = 94.8(1)degrees, beta = 107.4(1)degrees, gamma = 87.8(1)degrees, triclinic, P (1) over bar, Z = 2; [HB(Pz)(3)]Ag[P(o -tolyl)(3)], C30H31- AgBN6P, a = 14.461(2) Angstrom, b = 14.461(2) Ang strom, c = 30.473(2) Angstrom, alpha = 90 degrees, beta = 90 degrees, gamma = 120 degrees, trigonal, R (3) over bar, Z = 6; [HB(Pz)(3)]AgP(B z)(3), C30H31AgBN6P, a = 12.183(2) Angstrom, b = 18.596(2) Angstrom, c = 13.804(2) Angstrom, beta = 100.8(1)degrees, monoclinic. P2(1)/n, Z = 4; [HB(3,5-Me(2)Pz)(3)]Ag[P(p-tolyl)(3)], C36H41AgBN6P, a = 33.839(3 ) Angstrom, b = 10.375(2) Angstrom, c = 10.203(2) Angstrom, beta = 90. 8(1)degrees, monoclinic: P2(1)/n, Z = 4. Crystal data with Cu K alpha (lambda = 1.5318 Angstrom) [HB(4-BrPz)(3)]AgPPh3, C27H22AgBBr3N6P2, a = 10.306(2) Angstrom, b = 11.425(2) Angstrom, c = 13.571(2) Angstrom, alpha = 90.3(1)degrees, beta = 107.0(1)degrees, gamma = 91.4(1)degrees , triclinic, P (1) over bar, Z = 2. The anionic soft S-3-donor hydrotr is(3-methyl-2-thioxo-1-imidazolyl)-borate (Tm) was synthesized as its potassium salt from the corresponding imidazole and KBH4 in high yield . The potassium complex KTm was used as ligand transfer agent in the p reparation of the silver(I) derivatives [(Tm)Ag](n) and (Tm)Ag(PPh3). The S-donor 1-methylimidazolyl-2-thione (Hmimt) reacts with [HB(3,5-Me -2-Pz)(3)]Ag(PPh3), yielding the derivative [HB(3,5-Me(2)Pz)(3)](Hmimt )AgPPh3 in which the [HB(3,5-Me(2)Pz)(3)](-) acts likely as bidentate N-2-donor.