Phenoxo and Diphenoxo Complexes of Titanium(III) and Vanadium(III): Synthesis and X-Ray Structure

Article abstract of DOI:10.1039/DT9890001793

Reaction of and (thf = tetrahydrofuran) with 2,6-Bu^t2C3H3ONa, and 2,6-Me2C6H3ONa respectively, led to the monomeric five-co-ordinate complexes t2C6H3O)(thf)2>, (1), and , (2).Both metal atoms have a trigonal bipyramidal co-ordination, the equatorial plane being defined by the two chloride and the phenoxo ligands.The axial positions are filled by two thf molecules.Phenoxo parameters are: Ti-O 1.807(8) and V-O 1.803(5) Angstroem; Ti-O-C 174.2(9) and V-O-C 135.9(5) deg.Reaction of the sodium salt of benzene-1,2-diol (H2cat) with led to the isolation of a binuclear complex , (3), while the reaction with the sodium salt of bis(2-hydroxy-5-methyl-3-t-butylphenyl)methane (H2bhm) gave the mononuclear complex (4).Complex (3) has a planar V2(μ-cat)2Cl2 skeleton with molecules of thf above and below the plane, and vanadium(III) achieves six-co-ordination by sharing the oxygens of the catecholato dianion.Complex (4) has a monomeric structure with the diphenolato anion (bhm) forming an eight-membered ring and vanadium(III) having a pseudo-trigonal-bipyramidal co-ordinaton.Compounds (1)-(4) (all monoclinic) were characterized by single-crystal X-ray analysis: (1), space group P2₁/c, a = 10.483(1), b = 10.771(1), c = 24.847(2) Angstroem, β = 95.61(1) deg, Z = 4, R 0.064 for 1 051 observed reflections; (2), space group P2₁/n, a = 7.329(1), b = 13.195(1), c = 19.687(2) Angstroem, β = 94.58(1) deg, Z = 4, R 0.057 for 1 226 observed reflections; (3), space group P2₁/n, a = 17.743(2), b = 9.238(1), c = 9.522(1) Angstroem, β = 97.35(1) deg, Z = 2, R 0.043 (R' 0.047) for 1 264 observed reflections; (4), space group P2₁/c, a = 9.327(1), b = 13.814(2), c = 24.577(2) Angstroem, β = 93.54(1) deg, Z = 4, R 0.059 (R' 0.065) for 2 390 observed reflections.

Full text of DOI:10.1039/DT9890001793

View Article Online / Journal Homepage / Table of Contents for this issue

View Article Online

View Article Online

View Article Online

View Article Online

View Article Online