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Carboxylato Molybdenum(V) Complexes: X-Ray Structures of the Dinuclear Pivalato Complexes

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Abstract

Mononuclear molybdenum(V) starting material, (PyH)5[MoOCl4(H2O)]3Cl2 (where PyH+ stands for pyridinium cation, C5H5NH+), reacted with triethylammonium or pyridinium salt of pivalic acid (dimethylpropanoic acid) to form two dinuclear molybdenum(V) compounds with the (PyH)2[Mo2O4Cl3(Py)(Piv)] (1) and (PyH)[Mo2O4Cl2(Py)2(Piv)]·CH3CN (2) (Py = pyridine, Piv− = a deprotonated form of dimethylpropanoic acid) compositions. Compound 1 crystallized in the triclinic \( P{\bar1}\) space group with a = 9.52110(10) Å, b = 10.89790(10) Å, c = 14.5665(2) Å, α = 109.6310(6)°, β = 93.2646(7)° and γ = 111.8670(7)°. Compound 2 crystallized in the orthorhombic P nam space group with a = 10.67530(10) Å, b = 12.7801(2) Å and c = 20.1379(3) Å. X-ray structural analysis confirmed that the anions of both products consist of the central {Mo2O4}2+ core with the pivalato ligands coordinated to the sites which are trans to the terminal oxides. Because of a different pyridine/chloride content in the complex anions of 1 and 2, the metal–metal bond lengths also differ.

Graphical Abstract

Reaction of mononuclear molybdenum(V) starting material with pivalate resulted in (PyH)2[Mo2O4Cl3(Py)(Piv)] (1) and (PyH)[Mo2O4Cl2(Py)2(Piv)]·CH3CN (2) with the carboxylate coordinated as a bridging ligand to a pair of metal ions of the {Mo2O4}2+ core.

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Notes

  1. The contacts are slightly longer than the sum of the van der Waals radii of carbon and chlorine, 3.45 Å [22]. The C–H···Cl contacts are C21···Cl1 = 3.444(2), C25···Cl2 = 3.527(2) and C35···Cl3 = 3.550(2) Å in compound 1 and C21···Cl1 [x–0.5, –y + 1.5, z] = 3.520(2) Å in compound 2

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Acknowledgments

This work was supported by a Grant from the Slovenian Ministry of Education, Science and Sport (Grant P1-0134).

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  1. Department of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, 1000, Ljubljana, Slovenia

    Barbara Modec

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  1. Barbara Modec
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Correspondence to Barbara Modec.

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Modec, B. Carboxylato Molybdenum(V) Complexes: X-Ray Structures of the Dinuclear Pivalato Complexes. J Chem Crystallogr 43, 377–382 (2013). https://doi.org/10.1007/s10870-013-0431-0

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