Syntheses, structures, and reactivity of polynuclear pyrazolato copper(I) complexes, including an ab-initio XRPD study of [Cu(dmnpz)]3 (Hdmnpz = 3,5-dimethyl-4-nitropyrazole)

被引:78
作者
Ardizzoia, GA
Cenini, S
La Monica, G
Masciocchi, N
Maspero, A
Moret, M
机构
[1] Univ Milan, Ctr CNR, Dipartimento Chim Inorgan Met Organ & Analit, I-20133 Milan, Italy
[2] Univ Milan, Ctr CNR, Dipartimento Chim Strutturale & Stereochim Inorga, I-20133 Milan, Italy
关键词
D O I
10.1021/ic970875n
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
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 (1) over bar, a = 11.379(2) Angstrom, b = 13.592(2) Angstrom, c = 14.409(3) Angstrom, alpha = 81.22(1)degrees, beta = 85.21(1)degrees, gamma = 87.55(1)degrees, Z = 2. 4, 5, and 6 are binuclear complexes bearing one RNC, two RNC, and one triphenylphosphine ligands on each copper atom, respectively. The steric requirement of the dmnpz ligands, in the presence of RNC or PPh3, forces the inner [Cu-2(dmnpz)(2)] core of the three complexes into markedly different conformations.
引用
收藏
页码:4284 / 4292
页数:9
相关论文
共 47 条
  • [1] SIR92 - a program for automatic solution of crystal structures by direct methods
    ALTOMARE, A
    CASCARANO, G
    GIACOVAZZO, G
    GUAGLIARDI, A
    BURLA, MC
    POLIDORI, G
    CAMALLI, M
    [J]. JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1994, 27 : 435 - 435
  • [2] COORDINATIVE VERSATILITY OF THE DMCPZ LIGAND (HDMCPZ = 3,5-DIMETHOXYCARBONYLPYRAZOLE) IN COPPER-COMPOUNDS - SYNTHESIS, CHARACTERIZATION AND CRYSTAL-STRUCTURES OF [CU(DMCPZ)2(PY)2] AND [CU3(DMCPZ)6] (PY = PYRIDINE)
    ANGARONI, M
    ARDIZZOIA, GA
    LAMONICA, G
    BECCALLI, EM
    MASCIOCCHI, N
    MORET, M
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1992, (18): : 2715 - 2721
  • [3] [Anonymous], 1992, INT TABLES CRYSTALLO, VC
  • [4] Silver(I) pyrazolates. Synthesis and X-ray and P-31-NMR characterization of triphenylphosphine complexes and their reactivity toward heterocumulenes
    Ardizzoia, GA
    LaMonica, G
    Maspero, A
    Moret, M
    Masciocchi, N
    [J]. INORGANIC CHEMISTRY, 1997, 36 (11) : 2321 - 2328
  • [5] SYNTHESIS, X-RAY STRUCTURE, AND CATALYTIC PROPERTIES OF THE UNPRECEDENTED TETRANUCLEAR COPPER(I) SPECIES [CU(DPPZ)]4 (HDPPZ = 3,5-DIPHENYLPYRAZOLE)
    ARDIZZOIA, GA
    CENINI, S
    LAMONICA, G
    MASCIOCCHI, N
    MORET, M
    [J]. INORGANIC CHEMISTRY, 1994, 33 (07) : 1458 - 1463
  • [6] REACTION OF DIOXYGEN WITH [CU(DMPZ)]N (HDMPZ = 3,5-DIMETHYLPYRAZOLE) - CRYSTAL-STRUCTURE, REACTIVITY, AND CATALYTIC PROPERTIES OF [CU8(DMPZ)8(OH)8]
    ARDIZZOIA, GA
    ANGARONI, MA
    LAMONICA, G
    CARIATI, F
    CENINI, S
    MORET, M
    MASCIOCCHI, N
    [J]. INORGANIC CHEMISTRY, 1991, 30 (23) : 4347 - 4353
  • [7] SYNTHESIS, X-RAY CRYSTAL-STRUCTURE, AND REACTIVITY OF THE BINUCLEAR COPPER(I) COMPLEX [(CU(3,5ME2-PZ)(CNR))2] (R = CYCLOHEXYL, 3,5ME2-PZ = 3,5-DIMETHYLPYRAZOLATE) TOWARD RNCO (R = CYCLOHEXYL), PHNCS, COS, AND CS2.N,S COORDINATION OF THE 3,5-DIMETHYLPYRAZOLECARBODITHIOATE ANION IN [CU(3,5ME2-PZ-C(S)-S)(CNR)2]
    ARDIZZOIA, GA
    ANGARONI, MA
    LAMONICA, G
    MASCIOCCHI, N
    MORET, M
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1990, (07): : 2277 - 2281
  • [8] SYNTHESIS OF [CU(DCMPZ)]N AND ITS REACTIONS WITH CARBON-MONOXIDE AND CYCLOHEXYL ISOCYANIDE - CRYSTAL-STRUCTURES OF [CU2(DCMPZ)2(PY)2(CO)] AND [CU(DCMPZ)(RNC)]2 (HDCMPZ = 3,5-DICARBOMETHOXYPYRAZOLE, R = CYCLOHEXYL)
    ARDIZZOIA, GA
    BECCALLI, EM
    LAMONICA, G
    MASCIOCCHI, N
    MORET, M
    [J]. INORGANIC CHEMISTRY, 1992, 31 (13) : 2706 - 2711
  • [9] BANDINI AL, 1984, J ORGANOMET CHEM, V269, P91, DOI 10.1016/0022-328X(84)80280-6
  • [10] SYNTHESIS OF COMPLEXES OF RHODIUM(I) AND IRIDIUM(I) WITH 3,5-PYRAZOLEDICARBOXYLIC ACID AND THEIR MIXED-VALENCE OXIDATION-PRODUCTS
    BAYON, JC
    NET, G
    ESTEBAN, P
    RASMUSSEN, PG
    BERGSTROM, DF
    [J]. INORGANIC CHEMISTRY, 1991, 30 (25) : 4771 - 4777