SYNTHESIS AND SPECTROSCOPIC CHARACTERIZATION OF NEW CU(I) COMPLEXES CONTAINING TRIARYL-, TRICYCLOALKYLPHOSPHINES AND HETEROCYCLIC ANIONIC OR NEUTRAL N-DONOR LIGANDS - CRYSTAL AND MOLECULAR STRUCTURE OF [(CY(3)P)(2)(PZH)CU]CLO4-CENTER-DOT-CH3OH (CY EQ

摘要

The reaction of (PPh(3))(4)CuClO4, (PPh(3))(2)CuCl, (Cy(3)P)(2)CuNO3 and (Cy(3)P)(2)CuClO4 with an excess of monodentate heterocyclic N-donor ligand (QH in general, in detail: ImH = imidazole, 1-MeimH = 1-methylimidazole, 2-MeimH = 2-methylimidazole, 4-PhimH = 4-phenylimidazole, BimH = benzimidazole, 1-BzimH = 1-benzylimidazole, pzH = pyrazole, pz'H = 3,5-dimethylpyrazole) in diethyl ether or benzene resulted in the formation of new 2:2:1 [(PPh(3))(2)(QH)(2)Cu]ClO4 (QH = ImH, 1-MeimH, 2-MeimH, 4-PhimH, BimH, pzH) and [(PCy(3))(2)(QH)(2)Cu]NO3 (QH = 4-PhimH, BimH), 1:3:1 [(PPh(3))(1-BzimH)(3)Cu]ClO4, [(PCy(3))(1-MeimH)(3)Cu]ClO4 and [(PCy(3))(3)(QH)(2)Cu]NO3 (QH = ImH, 1-MeimH, pzH), 2:1:1 [(PPh(3))(2)(QH)CuCl] (QH = ImH, 2-MeImH, 4-PhimH, BimH, 1-BzimH), [PCy(3))(2)(QH)Cu]NO3 (QH = 1-BzimH, pz'H) and [(PCy(3))(2)(QH)Cu]ClO4(QH = 2-MeimH, 4-PhimH, BimH, 1-BzimH, pzh, pz'H), 1:2:1 [PCy(3))(2-MeimH)(2)Cu]NO3 and [(PCy(3)O(ImH)(2)Cu]ClO4 and 1:1:1 [(PPh(3))(1-MeimH)CuCl] adducts. With the bidentate donors bis(pyrazol-1-yl)methane (L(1)), bis(2,5-dimethylpyrazol-1-yl)methane (L(2)) and bis (4-methylpyrazol-1-yl)methane (L(4)), 2:1:1 [(PPH3)(2)(L)Cu]ClO4 and 1:1:1 [(PCy(3)(L)Cu]ClO4 complexes were obtained, whereas the exopolydentate bis(1,2,4-triazol-1-yl)methane (L(3)) in similar conditions yielded 1:1:1 [(PPh(3)(L(3))Cu]ClO4 and [(PCy(3)(L(3))Cu]NO3, and 1:2:1 [(PCy(3))(L(3))(2)Cu]ClO4 derivatives. Breaking of the bridging C(sp(3))-N bond in the bidentate bis(pyrazol-1-yl)methane occurred when the reaction between L(1) and (PCy(3))(2)CuNO3 was carried out in diethyl ether under aerobic conditions, the derivative [(PCy(3))(pzH)(3)Cu]NO3 being formed. In methanol in the presence of base, ImH, 2-MeimH, 4-PhimH and BimH react with (PPh(3))(2)CuCl giving the sparingly soluble complexes [(PPh(3))(2)(Im)Cu]. 1/2H(2)O, [(PPh(3))(2)(2-Meim)Cu]. H2O, [(PPh(3))(4-Phim)Cu] and [(PPh(3))(Bim)Cu], respectively. Reaction of [(PPh(3))(2)(Im)Cu]ClO4 with PCy(3), PBz(3) (Bz = benzyl), P(p-tolyl)(3) and (Ph(2)PCH(2))(2) (abbreviated Diphos)resulted in the formation of compounds [(PPh(3))(PCy(3))(ImH)(2)Cu]ClO4, [(PPh(3))(PBz(3))(ImH)Cu]ClO4, [PPh(3))P(p-tolyl)(3)(ImH)(2)Cu]ClO4 and [(Diphos)(2)Cu]ClO4, respectively, whereas reaction with 1,10-phenanthroline (Phen) and 2,2'-bipyridyl (Bipy) produced [(PPh(3))(2)(ImH)(Phen)Cu]ClO4 and [(PPh(3))(2)(imH(Bipy)Cu]ClO4, respectively. While PCy(3), PBz(3) and P(p-tolyl)(3) were not able to displace the triphenylphosphine from [(PPh(3))(2)(L(1))Cu]ClO4, Phen and Bipy in the same conditions formed the derivatives [(PPh(3))(2)(Phen)Cu]ClO4 and [(PPh(3))(2)(Bipy)Cu]ClO4. All of the complexes were characterized by IR and far-IR data, conductivity, H-1 NMR and in some cases also with UV, C-13 and P-31 NMR and molecular weight measurements. The structure of [(Cy(3)P)(2)(pzH)Cu]ClO4 . CH3OH was determined by single crystal X-ray diffraction: monoclinic, space group Pn, Z = 2, a= 9.949(7), b = 13.128(4), c = 16.588(8) Angstrom, beta = 91.15(7)degrees. The copper atom exhibited a distorted ideal triagonal planar geometry involving two phosphine groups (Cu-P: 2.272(9) and 2.272(6) Angstrom; P-Cu-P: 132.3(7)degrees) and one pyrazole ligand (Cu-N: 2.047(18) Angstrom) coordinating through a pyridine-like nitrogen atom. The pyrazole donor of one molecule was hydrogen bonded to a molecule of methanol, which in turn was hydrogen bonded to the ionic perchlorato group. [References: 68]