Photolysis of CH3Re(O2)2O induced by ligand-to-metal charge transfer and by peroxide intraligand excitation

被引：5

作者：

Kunkely, H ^{[1
]}

Vogler, A ^{[1
]}

机构：

[1] Univ Regensburg, Inst Anorgan Chem, D-93040 Regensburg, Germany

来源：

INORGANIC CHEMISTRY COMMUNICATIONS | 2005年 / 8卷 / 05期

关键词：

electronic spectra; photochemistry; rhenium; peroxo complexes; charge transfer;

D O I：

10.1016/j.inoche.2005.02.014

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The electronic spectrum of the diperoxo complex MeReVII(O-2)(2)O shows a peroxide IL (intraligand) absorption at lambda(max) similar to 260 nm in addition to the well-known peroxide to Re(VII) LMCT band at lambda(max) = 358 nm. Upon IL excitation, the diperoxo group undergoes a dismutation. Accordingly, MeRe(O-2)(2)O Photolyzes to (MeReO3)-O-VII and O-2. LMCT excitation at lambda(irr) = 405 nm is assumed to generate the radical pair MeReVII(O-2)O+/O-2(-) in the primary photochemical step. Back electron transfer and reaction with water leads finally to the monoperoxo complex MeReVII(O-2)O-2 and H2O2. (c) 2005 Elsevier B.V. All rights reserved.

引用

页码：467 / 470

页数：4

共 26 条

[1] Mechanism of the olefin epoxidation catalyzed by molybdenum diperoxo complexes: Quantum-chemical calculations give an answer to a long-standing question [J].

Deubel, DV ;

Sundermeyer, J ;

Frenking, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (41) :10101-10108

[2] Olefin epoxidation by peroxo complexes of Cr, Mo, and W.: A comparative density functional study [J].

Di Valentin, C ;

Gisdakis, P ;

Yudanov, IV ;

Rösch, N .

JOURNAL OF ORGANIC CHEMISTRY, 2000, 65 (10) :2996-3004

[3] Olefin epoxidation by molybdenum and rhenium peroxo and hydroperoxo compounds:: A density functional study of energetics and mechanisms [J].

Gisdakis, P ;

Yudanov, IV ;

Rösch, N .

INORGANIC CHEMISTRY, 2001, 40 (15) :3755-3765

[4]

GUBELMANN MH, 1983, STRUCT BOND, V55, P1

[5] Macrocyclic hydroperoxocobalt(III) complex: Photochemistry, spectroscopy, and crystal structure [J].

Guzei, IA ;

Bakac, A .

INORGANIC CHEMISTRY, 2001, 40 (10) :2390-2393

[6] Photochemical elimination of singlet oxygen from oxodiperoxo-molybdenum(VI) complexes with aromatic N,N'-chelate ligands [J].

Hatzopoulos, I ;

Thiel, WR ;

Brauer, HD .

JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 1997, 102 (2-3) :151-155

[7] Multiple bonds between main-group elements and transition metals .158. Photochemical and photophysical properties of the epoxidation catalyst CH3ReO(O-2)(2)center dot H2O [J].

Hatzopoulos, I ;

Brauer, HD ;

Geisberger, MR ;

Herrmann, WA .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1996, 520 (1-2) :201-209

[8] MULTIPLE BONDS BETWEEN MAIN-GROUP ELEMENTS AND TRANSITION-METALS .122. METHYLTRIOXORHENIUM(VII) AS CATALYST FOR EPOXIDATIONS - STRUCTURE OF THE ACTIVE SPECIES AND MECHANISM OF CATALYSIS [J].

HERRMANN, WA ;

FISCHER, RW ;

SCHERER, W ;

RAUCH, MU .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1993, 32 (08) :1157-1160

[9] MULTIPLE BONDS BETWEEN MAIN-GROUP ELEMENTS AND TRANSITION-METALS .144. PHOTOREACTIVITY OF ORGANORHENIUM(VII) OXIDES [J].

HERRMANN, WA ;

KUHN, FE ;

FIEDLER, DA ;

MATTNER, MR ;

GEISBERGER, MR ;

KUNKELY, H ;

VOGLER, A ;

STEENKEN, S .

ORGANOMETALLICS, 1995, 14 (11) :5377-5381

[10] The ''peroxo perrhenic acid'' H4Re2O13: An oxygen-rich metal peroxide and oxidation catalyst [J].

Herrmann, WA ;

Correia, JDG ;

Kuhn, FE ;

Artus, GRJ ;

Romao, CC .

CHEMISTRY-A EUROPEAN JOURNAL, 1996, 2 (02) :168-173

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