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Syntheses, 95Mo NMR Spectroscopy and Structures of Distorted Cubic Mo4(μ3-O)4(μ2-O2P(CH2C6H5)2)4O4 and the Open Mixed-Valent Cluster, Mo4(μ3-O)2(μ2-O2P(CH2C6H5)2)6O6

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Abstract

The reaction of MoO2(acac)2 and dibenzylphosphinic acid in ethanol leads to a red distorted cubic tetrameric cluster, Mo4(μ3-O)4(μ2-O2P(CH2C6H5)2)4O4, and a pink open mixed-valent cluster, Mo4(μ3-O)2(μ2-O2P(CH2C6H5)2)6O6, when the reduction is carried out at 120 and 75 °C, respectively. 95Mo NMR spectroscopy revealed a singlet for Mo4(μ3-O)4(μ2-O2P(CH2C6H5)2)4O4 (1) at 584.9 ppm (Δν1/2 = 4500 Hz) and two resonances for Mo4(μ3-O)2(μ2-O2P(CH2C6H5)2)6O6 (2) at 238.8 ppm (Δν1/2 = 1250 Hz) and 6.4 ppm (Δν1/2 = 5999 Hz), which were assigned to the Mo(V) and Mo(VI) sites, respectively. DFT geometries and 95Mo DFT-GIAO chemical shifts for Mo4(μ3-O)4(μ2-O2P(CH3)2)4O4 (3) and Mo4(μ3-O)2(μ2-O2P(CH3)2)6O6 (4) are consistent with X-ray crystallography and 95Mo NMR of 1 and 2. The open complex, Mo4(μ3-O)2(μ2-O2P(CH2C6H5)2)6O6·2(CH2Cl2), exhibits a central Mo(V)–Mo(V) single bond at 2.6217(5) Å with each Mo(V) atom bonded to one oxo (trans-disposed) terminal ligand.

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Acknowledgments

The diffractometer used to solve the structures was funded by NSF Grant 0087210, by Ohio Board of Regents Grant CAP-491, and by YSU. Support by Michigan Technological University is acknowledged.

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Authors and Affiliations

  1. Department of Chemistry, Michigan Technological University, 1400 Townsend Drive, Houghton, MI, 49931, USA

    John S. Maass & Rudy L. Luck

  2. Department of Chemistry, Youngstown State University, 1 University Plaza, Youngstown, OH, 44555, USA

    Matthias Zeller

  3. Department of Chemistry, Michigan State University, East Lansing, MI, 48824, USA

    Daniel Holmes

  4. Department of Chemistry and Biochemistry, Old Dominion University, Hampton Boulevard, Norfolk, VA, 23529, USA

    Craig A. Bayse

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  1. John S. Maass
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  2. Matthias Zeller
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Correspondence to Rudy L. Luck.

Electronic supplementary material

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10876_2011_373_MOESM1_ESM.doc

Listings and comparisons of selected bond distances and angles, Tables S1–S4. Molecular representation figure of 2, Fig. S1, packing diagrams of 1a and 1b as Figs. S2 and S3 respectively. Figures of the 95Mo NMR spectra of complexes 1 and 2, and, an illustration of the deconvolution of the spectrum of complex 2 as Figs. S4–S6, respectively. CCDC 783573, 783574 and 783575 contain the supplementary crystallographic data for complexes 1a, 1b, and 2, respectively. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif (DOC 745 kb)

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Maass, J.S., Zeller, M., Holmes, D. et al. Syntheses, 95Mo NMR Spectroscopy and Structures of Distorted Cubic Mo4(μ3-O)4(μ2-O2P(CH2C6H5)2)4O4 and the Open Mixed-Valent Cluster, Mo4(μ3-O)2(μ2-O2P(CH2C6H5)2)6O6 . J Clust Sci 22, 193–210 (2011). https://doi.org/10.1007/s10876-011-0373-7

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