Vanadium(IV) Complexes with Mixed O,S Donor Ligands. Syntheses, Structures, and Properties of the Anions Tris(2-mercapto-4-methylphenolato)vanadate(IV) and Bis(2-mercaptophenolato)oxovanadate(IV)
- 1 January 1996
- journal article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 35 (2) , 347-356
- https://doi.org/10.1021/ic950792b
Abstract
Reaction of VO(acac)2 with 2-mercaptophenol (mpH2) in the presence of triethylamine gives the mononuclear tris complex (Et3NH)2[V(mp)3] (1), in which the vanadyl oxygen has been displaced. An analogous reaction using 2-mercapto-4-methylphenol (mmpH2) afforded (Et3NH)(PNP)[V(mmp)3] (2), which was structurally characterized. 2 crystallizes in the orthorhombic space group Pna21 with unit cell parameters (at −163 °C) a = 23.974(7) Å, b = 9.569(4) Å, c = 25.101(6) Å, and Z = 4. The coordination geometry around the vanadium is between octahedral and trigonal prismatic. Reaction of VO(acac)2 with the sodium salt of 2-mercaptophenol produces the vanadyl(IV) complex Na(Ph4P)[VO(mp)2]·Et2O (3), which crystallizes in the triclinic space group P1̄ with unit cell parameters (at −135 °C) a = 12.185(4) Å, b = 12.658(4) Å, c = 14.244(4) Å, α = 103.19(2)°, β = 100.84(2)°, and γ = 114.17(2)°. The unit cell of 3 contains a pair of symmetry-related [VO(mp)2]2- units bridged through vanadyl and ligand oxygen atoms by a pair of sodium ions, in addition to two PPh4+ ions. The coordination geometry around the vanadium is square pyramidal, with a VO bond length of 1.611(5) Å. 1, 2, and 3 are characterized by IR and UV−vis spectroscopies, magnetic susceptibility, EPR spectroscopy, and cyclic voltammetry. 1 and 2 can be oxidized by I2, Cp2Fe+, or O2 to [V(mp)3]- and [V(mmp)3]-, respectively, which in turn can be reduced back to the dianions by oxalate ion. These reversible redox processes can be followed by UV−vis spectroscopy.Keywords
This publication has 48 references indexed in Scilit:
- Sensitive flotation-spectrophotometric determination of niobium with use of oxalate, 3,5-dinitrocatechol and rhodamine BAnalytica Chimica Acta, 1989
- Ligand substitution reactions of dirhodium(II) tetraacetate with water-soluble phosphinesInorganic Chemistry, 1988
- Isolation and structure of bis(ethane-1,2-dithiolato)(trimethylsilyloxy)vanadate(1-), an intermediate in the conversion of [VO(edt)2]2- to [VS(edt)2]2- (edt2 = ethane-1,2-dithiolate) with (Me3Si)2S. EPR characterization of the series [VE(LL)2]z- (E = O, S, OSiMe3, LL = edt; E = O, LL = propane-1,3-dithiolatoInorganic Chemistry, 1986
- Isolation of a new vanadium-containing nitrogenase from Azotobacter vinelandiiBiochemistry, 1986
- Induced redox reactivity of tetrathiovanadate(V): synthesis of the vanadium(IV) dimer V2(.mu.-S2)2(iso-Bu2NCS2)4 and its structural relationship to the V/S mineral patroniteJournal of the American Chemical Society, 1986
- Angle-resolved ultraviolet photoelectron spectroscopic studies of carbon monoxide binding to three chemically different surfaces of zinc oxide. Confirmation of step-binding sites on (000.hivin.1)Journal of the American Chemical Society, 1982
- Bifunctional activation of carbon dioxide. Synthesis and structure of a reversible carbon dioxide carrierJournal of the American Chemical Society, 1978
- A study of vanadium(IV)-3-methylcatechol-quaternary ammonium systemsAnalytica Chimica Acta, 1975
- Crystal and molecular structures of bis(tetraphenylarsonium) tris(1,2-dicyanoethylenedithiolato)molybdenate(IV), [(C6H5)4As]2[Mo(mnt)3], and its tungsten analog [(C6H5)4As]2[W(mnt)3]Inorganic Chemistry, 1973
- Octahedral vs. trigonal-prismatic coordination. Structure of (Me4N)2[V(mnt)3]Journal of the American Chemical Society, 1967