Chemistry of cobalt acetate.: 7.: Electrochemical oxidation of μ3-oxo-centered cobalt(III) acetate trimers

被引：16

作者：

Beattie, JK ^{[1
]}

Beck, CU ^{[1
]}

Lay, PA ^{[1
]}

Masters, AF ^{[1
]}

机构：

[1] Univ Sydney, Sch Chem, Ctr Heavy Met Res, Sydney, NSW 2006, Australia

来源：

INORGANIC CHEMISTRY | 2003年 / 42卷 / 25期

关键词：

D O I：

10.1021/ic0345525

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Electrochemical and spectroelectrochemical properties of five cobalt(III) acetate complexes [CoIII3(mu(3)-O)(CH3-CO2)(5)(OR)(py)(3)][PF6] are described, where py = pyridine and R = OCCH3 (A), H (B), CH3 (C), CH2CH=CH2 (D), and CH2C6H5 (E). Each is reduced irreversibly as observed by cyclic voltammetry at room temperature and at -40 degreesC in acetonitrile at scan rates up to 20 V s(-1), but oxidized reversibly to a mixed-valence Co(III)(2)Co(IV) species at similar to1.23 V vs the ferrocenium/ferrocene couple. Controlled potential coulometry confirmed a one-electron-oxidation process. Spectroelectrochemical oxidation of A at 5 degreesC showed isosbestic points in the electronic absorption spectrum that showed the oxidized complex to be stable in solution for at least 1 h.

引用

页码：8366 / 8370

页数：5

共 12 条

[1] The chemistry of cobalt acetate -: IV.: The isolation and crystal structure of the symmetric cubane, tetrakis[(μ-acetato)(μ3-oxo)(pyridine)cobalt(III)]•chloroform solvate, [Co4(μ3-O)4(μ-CH3CO2)4(C5H5N)4]•5CHCl3 and of the dicationic partial cubane, trimeric, [(μ-acetato)(acetato)tris(μ-hydroxy)(μ3-oxo)hexakispyridinetricobalt(III)]hexafluorophosphate•water solvate, [Co3(μ3-O)(μOH)3(μ-CH3CO2)(CH3CO2)(C5H5N)6][PF6]2•2H2O [J].

Beattie, JK ;

Hambley, TW ;

Klepetko, JA ;

Masters, AF ;

Turner, P .

POLYHEDRON, 1998, 17 (08) :1343-1354

[2] The chemistry of cobalt acetate.: VIII.: New members of the family of oxo-centred trimers, [Co3(μ3-O)(μ-O2CCH3)5-p(μ-OR)pL5]2+ (R = H, alkyl, L = ligand, p=0-4).: The preparation and characterisation of the trimeric tetrakis(μ-acetato)-(μ-hydroxo)-μ3-oxo-pentakis(pyridine)-tri-cobalt(III) hexafluorophosphate, [Co3(μ3-O)(μ-O2CCH3)4(μ-OH)(C5H5N)5][PF6]2, and the preparation and crystal structure of the trimeric tris(μ-acetato)-(μ-hydroxo)-(μ-methoxo)-μ3-oxo-pentakis(pyridine)-tri-cobalt(III) hexafluorophosphate •methanol•water solvate [Co3(μ3-O)(μ-O2CCH3)3(μ-OH)(μ-OCH3)(C5H5N)5][Pf6]2•CH3OH•0.25H2O [J].

Beattie, JK ;

Klepetko, JA ;

Masters, AF ;

Turner, P .

POLYHEDRON, 2003, 22 (07) :947-965

[3]

Bond AM, 1998, J CHEM SOC DALTON, P1845

[4] CHEMICAL AND PHYSICAL-PROPERTIES OF TRIANGULAR BRIDGED METAL-COMPLEXES [J].

CANNON, RD ;

WHITE, RP .

PROGRESS IN INORGANIC CHEMISTRY, 1988, 36 :195-298

[5] NEW TRINUCLEAR, OXO-CENTERED, BASIC CARBOXYLATE COMPOUNDS OF TRANSITION-METALS .2. SYNTHESIS AND X-RAY STRUCTURE OF V3(O)3(THF)(C6H5CO2)6, A COMPOUND WITH A DEVIANT STRUCTURE [J].

COTTON, FA ;

LEWIS, GE ;

MOTT, GN .

INORGANIC CHEMISTRY, 1982, 21 (08) :3127-3130

[6] Mixed-valence, tetranuclear cobalt(III, IV) complexes:: preparation and properties of [Co4O4(O2CR)2(bpy) 4]3+ salts [J].

Dimitrou, K ;

Brown, AD ;

Concolino, TE ;

Rheingold, AL ;

Christou, G .

CHEMICAL COMMUNICATIONS, 2001, (14) :1284-1285

[7] Kinetics of manganese(III) acetate in acetic acid: Generation of Mn(III) with Co(III), Ce(IV), and dibromide radicals; Reactions of Mn(III) with Mn(II), Co(II), hydrogen bromide, and alkali bromides [J].

Jiao, XD ;

Espenson, JH .

INORGANIC CHEMISTRY, 2000, 39 (07) :1549-1554

[8]

PARTENHEIMER W, 1993, ACS SYM SER, V523, P81

[9] SYNTHESIS AND REACTIVITY OF ALKOXIDE-BRIDGED COBALTIC ACETATES [J].

SUMNER, CE ;

STEINMETZ, GR .

INORGANIC CHEMISTRY, 1989, 28 (23) :4290-4294

[10] ISOLATION OF OXO-CENTERED COBALT(III) CLUSTERS AND THEIR ROLE IN THE COBALT BROMIDE CATALYZED AUTOXIDATION OF AROMATIC-HYDROCARBONS [J].

SUMNER, CE ;

STEINMETZ, GR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (21) :6124-6126

← 1 2 →