Synthesis and Redox-Induced Structural Isomerization of the Pentagonal Bipyramidal Complexes [W(CN)5(CO)2]3- and [W(CN)5(CO)2]2-

被引：10

作者：

Karunadasa, Hemamala I. ^{[1
]}

Long, Jeffrey R. ^{[1
]}

机构：

[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2009年 / 48卷 / 04期

关键词：

carbonyl ligands; cyanides; isomerization; oxidation; tungsten; SINGLE-MOLECULE MAGNETS; ORDERING TEMPERATURE; MN-II; EXCHANGE INTERACTIONS; SPIN REORIENTATION; CRYSTAL-STRUCTURE; BUILDING-BLOCKS; CYANIDE CLUSTER; MO-V; TRANSITION;

D O I：

10.1002/anie.200804199

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Figure Presented) Mixed company: The use of a mixed carbonyl/cyanide ligand set enables stabilization of two new heptacoordinate complexes: [W(CN)5(CO)2]3- and [W(CN)5(CO) 2]2-. In the trianionic complex the two carbonyl ligands occupy the axial positions. Remarkably, one-electron oxidation causes loss of this axial symmetry, as shown by X-ray crystallography (see picture, orange W, gray C, blue N, red O), IR, and EPR spectroscopy. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：738 / 741

页数：4

共 45 条

[1] THE SYNTHESIS AND SPECTRAL PROPERTIES OF SOME HIGHLY REACTIVE NEW 7-COORDINATE MOLYBDENUM(II) AND TUNGSTEN(II) BISACETONITRILE DIHALOGENOTRICARBONYL COMPLEXES [J].

BAKER, PK ;

FRASER, SG ;

KEYS, EM .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1986, 309 (03) :319-321

[2] Cyanide-limited complexation of molybdenum(III):: Synthesis of octahedral [Mo(CN)6]3- and cyano-bridged [Mo2(CN)11]5- [J].

Beauvais, LG ;

Long, JR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (10) :2110-2111

[3] CO3[Co(CN)5]2:: a microporous magnet with an ordering temperature of 38 K [J].

Beauvais, LG ;

Long, JR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (41) :12096-12097

[4] Directed assembly of metal-cyanide cluster magnets [J].

Beltran, LMC ;

Long, JR .

ACCOUNTS OF CHEMICAL RESEARCH, 2005, 38 (04) :325-334

[5] New cyanometalate building units:: Synthesis and characterization of [Re(CN)7]3- and [Re(CN)8]3- [J].

Bennett, MV ;

Long, JR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (09) :2394-2395

[6]

Berlinguette C.P., 2003, ANGEW CHEM-GER EDIT, V115, P1561

[7] A trigonal-bipyramidal cyanide cluster with single-molecule-magnet behavior:: Synthesis, structure, and magnetic properties of {[MnII(tmphen)2]3[MnIII(CN)6]2} [J].

Berlinguette, CP ;

Vaughn, D ;

Cañada-Vilalta, C ;

Galán-Mascarós, JR ;

Dunbar, KR .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (13) :1523-1526

[8] Magnetic anisotropy of [Mo(CN)7]4- anions and fragments of cyano-bridged magnetic networks [J].

Chibotaru, LF ;

Hendrickx, MFA ;

Clima, S ;

Larionova, J ;

Ceulemans, A .

JOURNAL OF PHYSICAL CHEMISTRY A, 2005, 109 (32) :7251-7257

[9] Exchange coupling in metal complexes of the second transition series: A theoretical exploration [J].

Desplanches, C ;

Ruiz, E ;

Alvarez, S .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2003, (09) :1756-1760

[10] PREPARATION AND PROPERTIES OF HEPTACYANOMOLYBDATE(II) ANION AND CRYSTAL AND MOLECULAR-STRUCTURES OF ITS SODIUM AND POTASSIUM-SALTS [J].

DREW, MGB ;

MITCHELL, PCH ;

PYGALL, CF .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1977, (11) :1071-1077

← 1 2 3 4 5 →