ELECTROCHEMICAL GENERATION OF 19-ELECTRON AND 20-ELECTRON RHODOCENIUM COMPLEXES AND THEIR PROPERTIES

被引：51

作者：

GUSEV, OV ^{[1
]}

DENISOVICH, LI ^{[1
]}

PETERLEITNER, MG ^{[1
]}

RUBEZHOV, AZ ^{[1
]}

USTYNYUK, NA ^{[1
]}

MAITLIS, PM ^{[1
]}

机构：

[1] UNIV SHEFFIELD,DEPT CHEM,SHEFFIELD S3 7HF,S YORKSHIRE,ENGLAND

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1993年 / 452卷 / 1-2期

关键词：

D O I：

10.1016/0022-328X(93)83193-Y

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The electrochemical reduction of the rhodocenium salts [Rh(eta5-C5Me5)(eta5-L)]+PF6- (2+, L=C5H5; 3+ L=C5Me5; 4+ L=C9H7) has been studied by cyclic voltammetry. All three complexes (2+-4+) are reduced in two one-electron processes, first to the 19-electron radicals (2-4) and then to the 20-electron anions (2--4-). When complex 2+ was reduced in bulk (Na-Hg in THF) the dinuclear complex, [(eta5-C5H5)Rh(mu-eta4:eta4-C5Me5-C5H5)Rh(eta5-C5Me5)] (6a), obtained by dimerization of 2, was isolated as sole product. Analogous reduction of 3+ gave the eta4-pentamethylcyclopentadiene complex, [Rh(eta5-C5Me5)(eta4-C5Me5H)] (7). Reduction of 4+ leads to formation of a stable radical 4.

引用

页码：219 / 222

页数：4

共 12 条

[1] 19-ELECTRON COMPLEXES AND THEIR ROLE IN ORGANOMETALLIC MECHANISMS [J].

ASTRUC, D .

CHEMICAL REVIEWS, 1988, 88 (07) :1189-1216

[2]

ASTRUC D, 1991, COMMUNICATION

[3] ELECTROCHEMICAL REDUCTION PATHWAYS OF THE RHODOCENIUM ION - DIMERIZATION AND REDUCTION OF RHODOCENE [J].

ELMURR, N ;

SHEATS, JE ;

GEIGER, WE ;

HOLLOWAY, JDL .

INORGANIC CHEMISTRY, 1979, 18 (06) :1443-1446

[4] UBER AROMATENKOMPLEXE VON METALLEN .88. UBER MONOMERES UND DIMERES DICYCLOPENTADIENYLRHODIUM UND DICYCLOPENTADIENYLIRIDIUM UND UBER EIN NEUES VERFAHREN ZUR DARSTELLUNG UNGELADENER METALL-AROMATEN-KOMPLEXE [J].

FISCHER, EO ;

WAWERSIK, H .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1966, 5 (06) :559-&

[5]

GUSEV OV, UNPUB

[6] ORGANOMETALLIC ELECTRON RESERVOIRS .3. SYNTHESES, CHARACTERIZATIONS, AND STEREOELECTRONIC STABILIZATION OF ORGANOMETALLIC ELECTRON RESERVOIRS - THE 19-ELECTRON-D-7 REDOX CATALYSTS ETA-5-C5R5FEI-ETA-6-C6R'6 [J].

HAMON, JR ;

ASTRUC, D ;

MICHAUD, P .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (04) :758-766

[7] SPECTROSCOPIC INVESTIGATIONS ON COMPLEX COMPOUNDS .6. EPR SPECTRA OF (C5H5)2RH AND (C5H5)2IR [J].

KELLER, HJ ;

WAWERSIK, H .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1967, 8 (01) :185-&

[8] PENTAMETHYLCYCLOPENTADIENYL-RHODIUM AND PENTAMETHYLCYCLOPENTADIENYL-IRIDIUM HALIDES .2. REACTIONS WITH MONO-OLEFINS, DI-OLEFINS, AND TRI-OLEFINS [J].

MOSELEY, K ;

KANG, JW ;

MAITLIS, PM .

JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1970, (17) :2875-&

[9] RING-SLIPPAGE CHEMISTRY OF TRANSITION-METAL CYCLOPENTADIENYL AND INDENYL COMPLEXES [J].

OCONNOR, JM ;

CASEY, CP .

CHEMICAL REVIEWS, 1987, 87 (02) :307-318

[10] BIS-INDENYL DERIVATIVES OF IRON AND COBALT [J].

PAUSON, PL ;

WILKINSON, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1954, 76 (07) :2024-2026

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