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By treating [(CO)(3)Re(Hpz)(2)(pz)] (Hpz = pyrazole) with [Cu(CH3CN)(4)]BF4, AgNO3, or [Au(tht)Cl] (tht = tetrahydrothiophene) in acetonitrile in the presence of Et3N, the corresponding trinuclear complexes {(CO)(3)Re(pz)(3)[M-(CH3CN)](2)} (1a-c) have been obtained. Treatment of complexes 1a-e with cyclohexyl isocyanide (c-CBH,INC) afforded the derivatives {(CO)(3)Re(pz)(3)[M(c-C6H11NC)](2)} (2a-c). Complexes 2a-c have been characterized in solution by H-1-NMR spectroscopy and in the solid state by single-crystal X-ray diffraction analysis.

The thermally induced solid state transformation of the [Ag(pymo)](n). 2nH(2)O 1D-polymer, 1 (Hpymo = 2-hydroxypyrimidine), followed by DSC, TGA I.r. and XRPD shows separate dehydration (with amorphization, 2) and devitrification processes into the cyclic [Ag(pymo)](6) oligomer, 3, which has been characterized by ab-initio XRPD. Monoclinic crystals, I2/m, a = 9.0149(4), b = 18.808(1), c = 8.9114(3) Angstrom, beta = 95.776(3)degrees, V = 1503.3(2) Angstrom(3), Z = 2; RP = 0.061, R-wp = 0.080, R-F = 0.043 for 4301 data points (1820 reflections) collected in the 17<2 theta<104 degrees range. This transformation is reversible, 3 double right arrow 1 being a rare case of ring opening polymerization.

The reaction of [Cu(CH3CN)(4)](BF4) with 3,5-dimethyl-4-nitropyrazole (Hdmnpz) in the presence of triethylamine yields the new copper(I) complexes [Cu(dmnpz)](3) (1) and (Et3NH)(2)[Cu-4(dmnpz)(6)] (2), depending on the experimental conditions. The reactivity of 1 and 2 toward neutral ligands such as triphenylphosphine, cyclohexyl isocyanide (RNC), and carbon monoxide has been investigated. In particular, both complexes readily react with RNC, giving the dinuclear complexes [Cu(dmnpz)(RNC)](2) (4) and [Cu(dmnpz)(RNC)(2)](2) (5), depending on the copper/RNC ratio, and with PPh3, affording the dimeric derivative [Cu(dmnpz)(PPh3)](2) (6). The crystal and molecular structure of 1 has been determined ab initio using X-ray powder diffraction data from conventional laboratory equipment. Crystals of 1 are monoclinic, C2/c, a = 20.057(2) Angstrom, b = 13.816(2) Angstrom, c = 7.883(1) Angstrom, beta = 95.912(4)degrees; R-F and R-wp 0.067 and 0.039, respectively, for Rietveld refinement on 3900 data points collected in the range 17 < 2 theta < 95 degrees (Cu K alpha radiation). Crystals of 1 contain planar trimers, with the copper atoms bridged by exo-bidentate ligands and short intermolecular Cu ... Cu contacts (3.329(7) Angstrom). For complexes 2 and 4-6, single-crystal X-ray diffraction studies have been performed. Crystals of 2 are monoclinic, P2(1)/c, a = 11.026(1) Angstrom, b = 13.456(2) Angstrom, c = 18.668(5) Angstrom, beta = 92.91(2)degrees, Z = 2. The ionic packing of 2 contains tetranuclear complexes, with the copper atoms connected by six dmnpz ligands. Crystals of 4 are triclinic, P (1) over bar, a = 7.418(1) Angstrom, b = 9.780(1) Angstrom, c = 11.177(3) Angstrom, alpha = 109.61(2); beta = 101.34(3)degrees, gamma = 105.82(1)degrees, Z = 2. Crystals of 5 are triclinic, P (1) over bar, a = 9.506(4) Angstrom, b = 9.957(2) Angstrom, c = 11.658(4) Angstrom, alpha = 86.73(2)degrees, beta = 79.54(2)degrees, gamma = 82.47(4)degrees, Z = 1. Crystals of 6 are triclinic, P (