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Norberto Masciocchi

Publications and source records attributed to Norberto Masciocchi.

7 recordsLinked to original sources
PubMed2002

Synthesis, structure and magnetism of homologous series of polycrystalline cobalt alkane mono- and dicarboxylate soaps.

Carboxylate-bridged chain complexes of Co(II) (the diaquacobalt(II) mono- and ,-dialkanoates) form two homologous series of layered compounds which have been fully characterised both structurally and magnetically. The crystal structures of two selected members, [Co[CH3(CH2)10COO]2(H2O)2] and [Co[CH3(CH2)18COO]2(H2O)2], have been solved by X-ray powder diffraction and selected-area electron diffraction methods, and refined by the Rietveld technique. Crystal data: monoclinic, P 2(1)/a; a=9.688(1), b=7.5495(9), c=37.281(5) A, =96.70(3) primary, Z=4; and monoclinic, P 2(1)/a; a=9.7260(7), b=7.5477(7), c=57.53(1) A, =94.66(4) primary, Z=4, respectively. Their isomorphous structures contain layers of octahedral diaquacobalt(II) ions bonded to two chemically inequivalent alkanoates, one chelating and one bridging two Co atoms about 6.3 A apart, thus confirming the rare anti-anti conformation mode of the -RCOO groups recently proposed for diaquacobalt(II) ,-dodecanedioate. Extensive magnetic characterisation allowed estimation of the feeble antiferromagnetic coupling, which is weaker in the mono- than in the dialkanoate series.

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PubMed1999

Metal Pyrazolato Complexes. Synthesis, Characterization, and X-ray Powder Diffraction Studies of Group 12 Coordination Polymers.

A number of polymeric pyrazolato complexes have been prepared and characterized by spectroscopy, thermal analyses (DSC and TGA), and X-ray powder diffraction (XRPD) methods. Ab initio XRPD studies showed that the (isomorphous) [Zn(pz)(2)](n)() and [Cd(pz)(2)](n)() species (Hpz = pyrazole) are 1-D polymers containing tetrahedrally coordinated metals and M(&mgr;-pz)(2)M (M = Zn, Cd) bridges, much alike [Cu(pz)(2)](n)() [orthorhombic, Ibam, a = 7.4829(4), b = 14.3844(6), c = 7.3831(3) Å (Zn) and a = 7.8591(6), b = 13.652(1), c = 7.9165(4) Å (Cd)]; differently, Hg(pz)(2) [triclinic, P&onemacr;, a = 7.4097(3), b = 9.4474(3), c = 5.8345(3) Å, alpha = 96.310(2), beta = 96.752(3), and gamma = 73.694(2) degrees ] is best described as a mononuclear complex, containing two monodentate pyrazolato ligands loosely interacting, through long(er) Hg.N contacts with neighboring molecules. During the synthesis of the latter, an intermediate phase was obtained, and characterized as Hg(pz)NO(3), which contains a polymeric polycation, [Hg(pz)](n)()(n)()(+), based on Hg(&mgr;-pz)Hg bridges, and uncoordinated NO(3)(-) groups (orthorhombic, Pcmn, a = 17.2985(9), b = 5.2538(3), c = 7.3912(4) Å). All structures were ultimately refined by the Rietveld method.

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PubMed1998

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).

The reaction of [Cu(CH(3)CN)(4)](BF(4)) with 3,5-dimethyl-4-nitropyrazole (Hdmnpz) in the presence of triethylamine yields the new copper(I) complexes [Cu(dmnpz)](3) (1) and (Et(3)NH)(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 PPh(3), affording the dimeric derivative [Cu(dmnpz)(PPh(3))](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) Å, b = 13.816(2) Å, c = 7.883(1) Å, 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 < 2theta < 95 degrees (Cu Kalpha 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) Å). 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) Å, b = 13.456(2) Å, c = 18.668(5) Å, 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&onemacr;, a = 7.418(1) Å, b = 9.780(1) Å, c = 11.177(3) Å, alpha = 109.61(2); beta = 101.34(3) degrees, gamma = 105.82(1) degrees, Z = 2. Crystals of 5 are triclinic, P&onemacr;, a = 9.506(4) Å, b = 9.957(2) Å, c = 11.658(4) Å, alpha = 86.73(2) degrees, beta = 79.54(2) degrees, gamma = 82.47(4) degrees, Z = 1. Crystals of 6 are triclinic, P&onemacr;, a = 11.379(2) Å, b = 13.592(2) Å, c = 14.409(3) Å, 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 PPh(3), forces the inner [Cu(2)(dmnpz)(2)] core of the three complexes into markedly different conformations.

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PubMed1997

Silver(I) Pyrazolates. Synthesis and X-ray and (31)P-NMR Characterization of Triphenylphosphine Complexes and Their Reactivity toward Heterocumulenes.

Silver(I) pyrazolate was reacted with triphenylphosphine, leading to the dinuclear [Ag(2)(pz)(2)(PPh(3))(2)] and [Ag(2)(pz)(2) (PPh(3))(3)] complexes (Hpz = pyrazole), which were extensively characterized by (31)P-NMR methods and single-crystal X-ray analyses. Crystals of [Ag(2)(pz)(2)(PPh(3))(2)] are triclinic, space group P&onemacr;, with a = 9.567(2) Å, b = 11.440(2) Å, c = 10.073(2) Å, alpha = 93.59(2) degrees, beta = 64.01(2) degrees, gamma = 107.24(2) degrees, Z = 1, and D(calc) = 1.539 g.cm(-)(3); final R = 0.028 for 2532 independent reflections having F > 4sigma(F). They contain centrosymmetric dimers with trigonally coordinated silver atoms, which are 3.870(1) Å apart. Crystals of [Ag(2)(pz)(2) (PPh(3))(3)] are triclinic, space group P&onemacr;, with a = 9.752(2) Å, b = 14.163(2) Å, c = 20.450(2) Å, alpha = 101.84(1) degrees, beta = 99.83(2) degrees, gamma = 100.68(2) degrees, Z = 2, and D(calc) = 1.424 g.cm(-)(3); final R = 0.025 for 7075 independent reflections having F > 4sigma(F). Each molecule contains two inequivalent silver ions, bearing one and two phosphines, respectively, and a Ag(&mgr;-pz)(2)Ag ring with a rare twisted conformation. Both complexes readily react with heterocumulenes such as CS(2), COS, CO(2), and RNCO, affording new derivatives, the nature of which is dependent on the experimental conditions. Single-crystal X-ray analysis of [Ag(pz-CS(2))(PPh(3))(2)] has shown the unexpected S,S coordination of the pyrazolecarbodithioate fragment. Its crystals are triclinic, space group P&onemacr;, with a = 10.329(4) Å, b = 13.082(2) Å, c = 14.284(3) Å, alpha = 86.71(2) degrees, beta = 75.14(2) degrees, gamma = 74.79(2) degrees, Z = 2, and D(calc) = 1.431 g.cm(-)(3); final R = 0.028 for 5179 independent reflections having F > 4sigma(F).

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