Magnetochemical properties and reactions of vanadium(III) thiolate complexes: Preparation of (NEt{sub 4}){sub 3}[V{sub 3}Cl{sub 6}(edt){sub 3}] and mixed-valence (NEt{sub 4})[V{sub 2}(edt){sub 4}] (edt = ethane-1,2-dithiolate)

Journal Article · Wed Nov 06 04:00:00 EST 1996 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic9606901· OSTI ID:420977

Rambo, J R; Castro, S L; Folting, K ^[1]

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1. Indiana Univ., Bloomington, IN (United States); and others

Reactions of the previously reported dinuclear vanadium(III) thiolate anion [V{sub 2}(edt){sub 4}]{sup 2{minus}} (edtH{sub 2} = ethane-1,2-dithiol) are described. Treatment of (NEt{sub 4}){sub 2}[V{sub 2}(edt){sub 4}] (1) in MeCN with equimolar (C{sub 12}H{sub 8}S{sub 2})BF{sub 4} (C{sub 12}H{sub 8}S{sub 2}{sup +} = the thianthrenium radical cation) results in a one-electron oxidation and isolation of the V{sup III}, V{sup IV} complex (NEt{sub 4})-[V{sub 2}(edt){sub 4}] (2). The same product can also be obtained by controlled-potential electrolysis of 1 at {minus}0.20 V vs Ag/AgCl. Treatment of 1 in CH{sub 2}Cl{sub 2} with py gives no reaction, but addition of MNe{sub 3}SiCl leads to formation of the known V{sub 2}OCl{sub 4}(py){sub 6} (3). The latter is also formed by the reduction of a 1:1 mixture of VOCl{sub 3} and VCl{sub 3}(THF){sub 3} in CH{sub 2}Cl{sub 2}/py and by the reaction in CH{sub 2}Cl{sub 2} of VCl{sub 3}(THF){sub 3} and py with edt{sup 2{minus}}. Treatment of 1 in MeCN with bpy (2,2{prime}-bipyridine) gives no reaction, but addition of Me{sub 3}SiCl results in formation and isolation of [V{sub 2}OCl{sub 2}-(bpy){sub 4}]Cl{sub 2} (4) identified by spectroscopic comparison with literature data. The reaction of 1 in MeCN with equimolar VCl{sub 3}(THF){sub 3} and NEt{sub 4}Cl gives (NEt{sub 4}){sub 3}[V{sub 3}Cl{sub 6}(edt){sub 3}] (5). A more convenient procedure to 5 is the reaction in MeCN of VCl{sub 3}(THF){sub 3}, Na{sub 2}edt, and NEt{sub 4}Cl in a 1:1:1 molar ratio. Complex 5{center_dot}MeCN crystallizes in triclinic space group P1 with (at -154{degrees}C) a = 14.918(3) {angstrom}, b = 17.142(5) {angstrom}, c = 11.276(3) {angstrom}, c = 11.276(3) {angstrom}, {alpha} = 106.78(1){degrees}, {beta} = 95.03(1){degrees}, {gamma} = 106.18(1){degrees}, and Z = 2. The effective magnetic moment of these compounds was measured from 5 to 300 K. Results of calculations were compared with the empirical data.

• OSTI ID: 420977
• Journal Information: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 23 Vol. 35; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
CHEMICAL PREPARATION
MAGNETIC PROPERTIES
OXIDATION
RADICALS
REDUCTION
SULFUR COMPOUNDS
TRICLINIC LATTICES
VANADIUM COMPLEXES
X-RAY DIFFRACTION