Synthesis and Structure of Vanadium Halide Complexes Containing Diphosphine Ligands with Pendant Amines

Egbert, Jonathan D.; Labios, Liezel A.; Darmon, Jonathan M.; Piro, Nicholas A.; Scott Kassel, W.; Mock, Michael T.

doi:10.1002/ejic.201501477

Title: Synthesis and Structure of Vanadium Halide Complexes Containing Diphosphine Ligands with Pendant Amines

Journal Article · Thu Feb 18 00:00:00 EST 2016 · European Journal of Inorganic Chemistry

DOI:https://doi.org/10.1002/ejic.201501477· OSTI ID:1337225

Egbert, Jonathan D.; Labios, Liezel A.; Darmon, Jonathan M.; Piro, Nicholas A.; Scott Kassel, W.; Mock, Michael T.

A series of vanadium(III) diiodide complexes of the formula CpV(P^RN^R'P^R)I₂ (Cp = 5-C₅H₅; P^RN^R'P^R = (R₂PCH₂)₂N(R)), where R = Et, R = Me (1a), R = Ph (1b); R = Ph, R = Me (1c)) is reported. The corresponding vanadium(II) monoiodide complexes of the formula CpV(P^RN^R'^PR)I, where R = Et, R = Me (2a), R = Ph (2b); R = Ph, R = Me (2c)) were prepared in THF by reduction of 1a-c with Zn powder. The paramagnetic complexes 1a-c and 2a-c are characterized by elemental analysis, 1H NMR spectroscopy, and by cyclic voltammetry for complexes 2b and 4b. Complexes 1c and 2a-c were also characterized in the single crystal by X-ray crystallography. We report the preparation of the vanadium(II) complexes CpV(P^Ph₂N^Ph₂)I (3) (P^Ph₂N^Ph₂ = 1,5-diphenyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) and trans-[VCl₂(PEtNMePEt)2] (4a) and trans-[VCl₂(PEtNPhPEt)₂] (4b). These complexes represent initial coordination chemistry of vanadium complexes with P^RN^R'P^R and P^Ph₂N^Ph₂ diphosphine ligands, which contain a pendant amine in the second coordination sphere. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1337225

Report Number(s):: PNNL-SA-115098; KC0307010

Journal Information:: European Journal of Inorganic Chemistry, Vol. 2016, Issue 8; ISSN 1434-1948

Publisher:: ChemPubSoc Europe

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
vanadium
phosphines
pendant amines

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