Solid-state 31P CP/MAS and static 65Cu NMR characterization of polycrystalline copper(I) dialkyldithiophosphate clusters.

Luleå University of Technology, Division of Chemistry, SE 971 87 Luleå, Sweden.
Journal of Magnetic Resonance (Impact Factor: 2.3). 04/2006; 179(1):140-5. DOI: 10.1016/j.jmr.2005.10.013
Source: PubMed

ABSTRACT Polycrystalline tetra-nuclear Cu4[S2P(O-i-C3H7)2]4, hexa-nuclear Cu6[S2P(OC2H5)2]6, and octa-nuclear Cu8[S2P(O-i-C4H9)2]6(S) complexes were synthesized and analyzed by means of solid-state 31P CP/MAS and 65Cu static NMR spectroscopy. The symmetries of the electronic environments around each P-site were estimated from the 31P chemical shift anisotropy (CSA) parameters, Deltaaniso and eta. The 65Cu chemical shift and quadrupolar splitting parameters obtained from the experimental 65Cu NMR spectra of the polycrystalline Cu(I)-complexes are presented. A solid-state NMR approach for the elucidation of the stereochemistry of poly-nuclear Cu(I) dithiophosphate complexes, when the structural analysis of the systems by single-crystal X-ray diffraction is not readily available, is proposed.

  • [Show abstract] [Hide abstract]
    ABSTRACT: Deprotonation of the N-thiophosphorylated thioureas RC(S)NHP(S)(OiPr)(2) (R = Me(2)N, HL(I); iPrNH, HL(II); 2,6-Me(2)C(6)H(3)NH, HL(III), 2,4,6-Me(3)C(6)H(2)NH, HL(IV), aza-15-crown-5, HL(V)) and reaction with CuI or Cu(NO(3))(2) in aqueous EtOH leads to the polynuclear complexes [Cu(4)(L(I)-S,S')(4)], [Cu(8)(L(II)-S,S')(8)], and [Cu(3)(L(III-V)-S,S')(3)]. The structures of these compounds were investigated by IR, (1)H, (31)P{(1)H} NMR, UV-vis spectroscopy and elemental analyses. The crystal structures of [Cu(4)L(I)(4)], [Cu(8)L(II)(8)], [Cu(3)L(III,IV)(3)] were determined by single-crystal X-ray diffraction. Reaction of the deprotonated ligands (L(I-V))(-) with a mixture of CuI and 1,10-phenanthroline (phen) or PPh(3) leads to the mixed-ligand mononuclear complexes [Cu(phen)L(I-V)], [Cu(PPh(3))L(I-V)] or [Cu(PPh(3))(2)L(I-V)]. The same mixed-ligand complexes were obtained from the reaction of [Cu(4)L(I)(4)], [Cu(8)L(II)(8)], [Cu(3)L(III-V)(3)] with phen or PPh(3).
    Dalton Transactions 11/2010; 39(48):11577-86. · 4.10 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Reaction of Cu(BF4)2 salt with the polymer [NP(OC6H4C(O)C–OC6H5)2]n (1) in THF affords three new polymers gels containing varied copper (II) ions contents, (2), (3), and (4). The nature of the copper (II) ions in the gel (2)–(4) was examined by IR spectroscopy, solid state 31P, 13C and 63Cu NMR spectroscopy and EPR spectroscopy. Despite the copper content, the gels were insulators as measured by complex impedance spectroscopy. SEM images show a uniform distribution of the Cu (II) ions and a most porous morphology than those without copper polymer. TEM images show the formation of small aggregates being smallest for, gel (2) of about 200 nm. All the data suggest the Cu2? centers behave as a solid dilute into the polyphosphazenes.
    Journal of Inorganic and Organometallic Polymers and Materials 01/2010; · 1.17 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: NMR spectroscopy continues to evolve, with publications in 2009 providing an eclectic collection of applications, advances and incremental improvements. This article covers rapid acquisition methods, DNP, SQUID, new liquid-state methods, “easy” and “difficult” solid-state methods, and computational aspects of NMR spectroscopy. A significant landmark was achieved in 2009, with the commercial release of the 1000 MHz (1 GHz, 23.4 T) NMR magnet. Also, despite the headline grabbing 1 GHz magnet, there remains significant interest in Earth-field (54 μT) NMR. I am indebted to the great and the good whose work has been reported here, all credit is theirs; errors, omissions and blame are all mine.
    Annual Reports Section B"" (Organic Chemistry)""" 01/2012;