Synthesis and x-ray crystallographic characterization of new dinuclear bis(phenyldiazenido)molybdenum complexes...

Valérie Chilou, Pierre Gouzerh, Yves Jeannin, Giuseppe Olivarès, Francis Robert, T. C. Hsieh, Jon Zubieta

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27 Scopus citations

Abstract

Title full: Synthesis and x-ray crystallographic characterization of new dinuclear bis(phenyldiazenido)molybdenum complexes [{Mo(C6H5N2)2X(μ-OR)(C 6H5NHNH2)2}] (X = Cl, OR), [{Mo(C6H5N2)2(μ-OR)(C 6H5CONHO)2}] and [{Mo(C6H5N2)2Cl(μ-OEt)(Et OH)2}]. Polyoxomolybdates, monomeric chelated(O,O) oxomolybdenum(VI) and monomeric halogenooxomolybdenum(V) complexes reacted in alcohols with phenylhydrazine to yield dinuclear complexes of the following formulae noted (1), (2), (3), and (4): [{Mo(C6H5N2)2(μ-OR)(C 6H5CONHO)}2], [{Mo(C6H5N2)2(μ-OR)(OR)(C 6H5NHNH2)}2],[{Mo(C6 H5N2)2Cl(μ-OR)(C6 H5NHNH2)}2] and [{Mo(C6H5N2)2Cl(μ-OC 2H5)(C2H5OH)}2]; a : R = CH3 ; b: R = C2H5 ; c: R = C3H7. 1b crystallized in the triclinic space group P1 a = 9.728(3), b = 11.154(1),c = 12.720(2) Å, α = 97.92(1)°,β = 106.40(2)°γ = 106.56(2)°, V = 1233 Å3, Z = 1. Refinement was based on 2549 reflections and converged at R = 0.06. 2a crystallized in the monoclinic space group P21/n, a = 11.404(2), b = 11.998(1), c = 16.778(4) Å, β = 108.56(1)°, V = 2176 Å3, Z = 2. Refinement was based on 2481 reflections and converged at R = 0.024. Mixed crystals containing 2a and 3a in the same unit cell (70:30) are isomorphous with 2a, a = 11.443(3), b = 11.826(4), c = 16.785(4) Å, β = 108.45(2)°, V = 2155 Å3, Z = 2. Refinement was based on 2623 reflections and converged at R = 0.049. 3c crystallized in the triclinic space group P1, a = 9.534(3), b = 12.057(2), c = 12.751(3) Å, α = 98.90(1)°, β = 96.37(2)°, γ = 112.50(2)°, V = 1314 Å3, Z = 1. Refinement was based on 1615 reflections and converged at R = 0.053. 4 crystallized in the monoclinic space group C2/m, a = 10.495(3), b = 18.792(4), c = 11.115(3) Å, β = 101.91(1)°, V = 2145 Å3, Z = 2. Refinement was based on 1238 reflections and converged at R = 0.055. All these structures consist of discrete dinuclear units containing cis-bisdiazenido moieties [MO(C6H5N2)2]2+ bridged by two alkoxo groups. Molybdenum achieves six coordination either with a chelating bidentate ligand as in 1 or with two unidentate ligands as in 2, 3 and 4. A unique feature of 2 and 3 is the occurrence of phenylhydrazine and phenyldiazenido in the same coordination sphere.

Original languageEnglish (US)
Pages (from-to)29-38
Number of pages10
JournalPolyhedron
Volume8
Issue number1
DOIs
StatePublished - 1989
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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