Oxovanadium(V) 1,3-propanediolate chloride complexes: Tetrameric clusters

Journal Article · Wed Nov 25 04:00:00 EST 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00050a009· OSTI ID:7001145

Crans, D C; Marshman, R W; Gottlieb, M S; Anderson, O P; Miller, M M ^[1]

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1. Colorado State Univ., Fort Collins (United States)

Structural, spectroscopic, and catalytic studies of oxovanadium-(V) alkoxide chlorides have shown that these compounds are monomeric and exhibit activities as oxidation catalysts and Lewis acids. The structure of the reaction product of VOCl[sub 3] and various 1,3-propanediol derivatives was characterized in solution at various temperatures using multinuclear NMR spectroscopy. Although oxovanadium dialkoxide chlorides tend to be monomeric, 1,3-propanediol derivatives induce cluster formation generating tetrameric complexes with a molecular formula of (VOC1L)[sub 4] (where L is bidentate). The 1,3-propanediol derivatives preferred to bridge over two (or three) vanadium atoms rather than form a cyclic six-membered ring on one vanadium atom as found with the corresponding phosphorus compounds. When the 1,3-propanediol ligand was asymmetric, several complexes were observed in solution. A hydrolysis product was characterized by X-ray crystallography. The compound crystallizes in the triclinic space group P[bar 1] with a = 10.003 (2) [Angstrom], b = 11.462 (3) [Angstrom], c = 11.699 (2) [Angstrom], [alpha] = 65.72 (2)[degrees], [beta] = 79.81 (2)[degrees], [gamma] = 81.89 (2) [degrees], V = 1199.7 (4) [Angstrom][sup 3], and Z = 1. The correlation between solution and solid-state structure was determined, and a possible pathway to the hydrolysis product was suggested. Vanadium is used as a reagent in organic synthesis; however, these studies suggest that altered reactivities may surface in the presence of 1,3-propanediol ligands or substrates. The studies show that the analogy between phosphorus and vanadium breaks down in complexes containing 1,3-propanediol derivatives, reducing the prospects of chemically preparing vanadium analogs of cAMP.

• OSTI ID: 7001145
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:24; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKOXIDES
CATALYSIS
CHEMICAL PREPARATION
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
EXPERIMENTAL DATA
INFORMATION
LATTICE PARAMETERS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
RESONANCE
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VANADIUM COMPLEXES
X-RAY DIFFRACTION