182012-99-3Relevant articles and documents
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 [ (Cy3P)2(pzH)Cu]ClO4·CH3OH (Cy = cyclohexyl, pzH = pyrazole)
Pettinari, Claudio,Marchetti, Fabio,Polimante, Roberta,Cingolani, Augusto,Portalone, Gustavo,Colapietro, Marcello
, p. 215 - 229 (2008/10/08)
The reaction of (PPh3)4CuClO4, (PPh3)2CuCl, (Cy3P)2CuNO3 and (Cy3P)2CuClO4 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 [(PPh3)2(QH)2Cu]ClO4 (QH = ImH, 1-MeimH, 2-MeimH, 4-PhimH, BimH, pzH) and [(PCy3)2(QH)2Cu]NO3 (QH = 4-PhimH, BimH), 1:3:1 [(PPh3)(1-BzimH)3Cu]ClO4, [(PCy3)(I-MeimH)3Cu]ClO4 and [(PCy3)(QH)3Cu]NO3 (QH = ImH, 1-MeimH, pzH), 2:1:1 [(PPh3)2(QH)CuCl] (QH = ImH, 2-MeimH, 4-PhimH, BimH, 1-BzimH), [(PCy3)2(QH)Cu]NO3 (QH= 1-BzimH, pz′H) and [(PCy3)2(QH)Cu]ClO4 (QH = 2-MeimH, 4-PhimH, BimH, 1-BzimH, pzH, pz′H), 1:2:1 [(PCy3) (2-MeimH)2Cu]NO3 and [(PCy3)(ImH)2Cu]ClO4 and 1:1:1 [(PPh3)(1-MeimH)CuCl] adducts. With the bidentate donors bis(pyrazol-1-yl)methane (L1), bis(3,5-dimethylpyrazol-l-yl)methane (L2) and bis(4-methylpyrazol-l-yl)methane (L4), 2:1:1 [ (PPh3)2(L) Cu]ClO4 and 1:1:1 [(PCy3)(L)Cu]ClO4 complexes were obtained, whereas the exopolydentate bis(1,2,4-triazol-1-yl) methane (L3) in similar conditions yielded 1:1:1 [(PPh3)(L3)Cu]ClO4 and [(PCy3)(L3)Cu]NO3, and 1:2:1 [(PCy3)(L3)2Cu]ClO4 derivatives. Breaking of the bridging C(sp3)-N bond in the bidentate bis (pyrazol-1-yl) methane occurred when the reaction between L1 and (PCy3)2CuNO3 was carried out in diethyl ether under aerobic conditions, the derivative [ (PCy3) (pzH)3Cu]NO3 being formed. In methanol in the presence of base, ImH, 2-MeimH, 4-PhimH and BimH react with (PPh3)2CuCl giving the sparingly soluble complexes [(PPh3)2(Im)Cu] · 1/2H2O, [(PPh3)2(2-Meim)Cu] · H2O, [(PPh3)(4-PhJm)Cu] and [ (PPh3) (Bim)Cu], respectively. Reaction of [(PPh3)2(ImH)2Cu]ClO4 with PCy3, PBz3 (Bz = benzyl), P(p-tolyl)3 and (Ph2PCH2)2 (abbreviated Diphos) resulted in the formation of compounds [(PPh3)(PCy3)(ImH)2Cu]ClO4, [(PPh3)(PBz3)(ImH)Cu]ClO4, [(PPh3)P(p-tolyl)3(ImH)2Cu]ClO4 and [(Diphos)2Cu]ClO4, respectively, whereas reaction with 1,10-phenanthroline (Phen) and 2,2′-bipyridyl (Bipy) produced [ (PPh3)2(ImH) (Phen)Cu]ClO4 and [(PPh3)2(ImH) (Bipy)Cu]ClO4, respectively. While PCy3, PBz3 and P(p-tolyl)3 were not able to displace the triphenylphosphine from [(PPh3)2(L1)Cu]ClO4, Phen and Bipy in the same conditions formed the derivatives [ (PPh3)2(Phen)Cu]ClO4 and [ (PPh3)2(Bipy)Cu]ClO4. All of the complexes were characterized by IR and far-IR data, conductivity, 1H NMR and in some cases also with UV, 13C and 31P NMR and molecular weight measurements. The structure of [ (Cy3P)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) A, β=91.15(7)°. The copper atom exhibited a distorted ideal trigonal planar geometry involving two phosphine groups (Cu-P: 2.262(9) and 2.272(6) A;P-Cu-P: 132.3(7)°) and one pyrazole ligand (Cu-N: 2.047(18) A) 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.
