Electronic Structure of the [Tris(dithiolene)chromium]z(z=0, 1-, 2-, 3-) Electron Transfer Series and Their Manganese(IV) Analogues. An X-ray Absorption Spectroscopic and Density Functional Theoretical Study

被引：80

作者：

Banerjee, Priyabrata ^{[1
]}

Sproules, Stephen ^{[1
]}

Weyhermueller, Thomas ^{[1
]}

George, Serena DeBeer ^{[2
]}

Wieghardt, Karl ^{[1
]}

机构：

[1] Max Planck Inst Bioanorgan Chem, D-45470 Mulheim, Germany

[2] Stanford Univ, SLAC, Stanford Synchrotron Radiat Lightsource, Stanford, CA 94309 USA

来源：

INORGANIC CHEMISTRY | 2009年 / 48卷 / 13期

关键词：

TRANSITION-METAL-COMPLEXES; TRIGONAL-PRISMATIC COORDINATION; IRON TRANSPORT COMPOUNDS; GAUSSIAN-BASIS SETS; MOLECULAR-STRUCTURE; CORRELATION-ENERGY; CRYSTAL-STRUCTURE; ATOMS LI; SEMIQUINONE; APPROXIMATION;

D O I：

10.1021/ic900154v

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Three members of the electron transfer series [Cr-III(dithiolene)(3)](z) (z = 1-, 2-, 3-) along with [Mn-IV(dithiolene)(3)](2-) analogues are shown to possess Cr(III) and Mn(IV) ions, respectively, by X-ray absorption spectroscopy (Cr and Mn K-edges). S K-edge spectra show the Cr series to be linked by ligand-based redox processes. All complexes are octahedral with DFT calculations reproducing the molecular structures and spectroscopic parameters such that [Cr(dithiolene)(3)](0) is predicted to be and octahedral with three S,S'-coordinated radical ligands.

引用

页码：5829 / 5847

页数：19

共 79 条

[1] [Anonymous], SHELXTL 6 14
[2] [Anonymous], 2000, EXAFSPAK EDG_FIT
[3] [Anonymous], 2006, SADABS, Bruker-Siemens Area Detector Absorption and Other Correction
[4] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE
BECKE, AD
[J]. JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) : 5648 - 5652
[5] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR
BECKE, AD
[J]. PHYSICAL REVIEW A, 1988, 38 (06): : 3098 - 3100
[6] LARGE INTENSITY ENHANCEMENT OF THE SPIN-FORBIDDEN 4A2G-]2EG TRANSITION IN CHROMIUM(III) SEMIQUINONE COMPLEXES
BENELLI, C
DEI, A
GATTESCHI, D
GUDEL, HU
PARDI, L
[J]. INORGANIC CHEMISTRY, 1989, 28 (16) : 3089 - 3091
[7] Electronic structure and spectroscopy of "superoxidized" iron centers in model systems: theoretical and experimental trends
Berry, John F.
George, Serena DeBeer
Neese, Frank
[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2008, 10 (30) : 4361 - 4374
[8] STRUCTURE AND PROPERTIES OF TRIS(QUINOXALINE-2,3-DITHIOLATO)MOLYBDATE(IV)
BOYDE, S
GARNER, CD
ENEMARK, JH
ORTEGA, RB
[J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1987, (02): : 297 - 302
[9] CRYSTAL-STRUCTURE OF TRIS(QUINOXALINE-2,3-DITHIOLATO)MOLYBDATE(V) - A DISTORTED TRIGONAL PRISMATIC COMPLEX
BOYDE, S
GARNER, CD
ENEMARK, JH
BRUCK, MA
KRISTOFZSKI, JG
[J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1987, (09): : 2267 - 2271
[10] 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]
BROWN, GF
STIEFEL, EI
[J]. INORGANIC CHEMISTRY, 1973, 12 (09) : 2140 - 2147

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