Reduction and deoxygenation of MoO3+(aq) by pyrrole-N-carbodithioate (L) to yield eight-coordinate MoL4: Crystal and molecular structure of tetrakis(pyrrole-N-carbodithioato)molybdenum-Hemi(methylene chloride)

Robert D. Bereman, Donald M. Baird, Charles T. Vance, John Hutchinson, Jon A Zubieta

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Abstract

The reaction between MoCl5 and potassium pyrrole-N-carbodithioate (K(pdc)) in an aqueous solution led to a surprising product with the stoichiometry Mo(pdc)4. Optical spectra and infrared spectra suggested an eight-coordinate, nonoxygenated molybdenum product. A single-crystal structural study on this material recrystallized from CH2Cl2 was carried out, and the eight-coordinate geometry was confirmed. The crystal Mo(pdc)4·1/2CH2Cl2 crystallizes in the centrosymmetric space group P1 with a = 11.197 (6) Å, b = 11.220 (5) Å, c = 13.165 (7) Å, α = 73.36 (4)°, β = 67.07 (4)°, γ = 66.75 (4)°, V = 1382 (1) Å3, and ρ(calcd) = 1.700 g cm-3 for mol wt 707.3 and Z = 2. A unique set of data (h,±k,±l; 3° < 2θ < 45°; Mo Kα) were collected with a Nicolet R3m automated diffractometer using graphite-monochromatized radiation. The structure was solved via a combination of Patterson, Fourier, and least-squares techniques. The final discrepancy indices were RF = 3.17% and RwF = 3.26% for the 2822 unique data with F > 6σ(F). The molecule has approximate D2d symmetry with the sulfurs located at the vertices of a D2d dodecahedron. The average Mo-S bond lengths are 2.541 and 2.507 Å for the dodecahedral a and b sites, respectively.

Original languageEnglish (US)
Pages (from-to)2316-2318
Number of pages3
JournalInorganic Chemistry
Volume22
Issue number16
StatePublished - 1983
Externally publishedYes

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ASJC Scopus subject areas

  • Inorganic Chemistry

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