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Electrochemical behaviour of cyclometallated gold(III) complexes: evidence of transcyclometallation in the fate of electroreduced species

Sanna, Gavino and Pilo, Maria Itria and Spano, Nadia and Minghetti, Giovanni and Cinellu, Maria Agostina and Zucca, Antonio and Seeber, Renato (2001) Electrochemical behaviour of cyclometallated gold(III) complexes: evidence of transcyclometallation in the fate of electroreduced species. Journal of Organometallic Chemistry, Vol. 622 (1-2), p. 47-53. ISSN 0022-328X. Article.

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DOI: 10.1016/S0022-328X(00)00822-6

Abstract

The electrochemical behaviour of a series of neutral and cationic N-C and N-N-C cyclometallated gold(III) species: ([Au(py1)(Cl)2], Hpy1=2-benzylpyridine; [Au(bipyn)(Cl)][PF6], Hbipy1=6-benzyl-2,2′-bipyridine, Hbipy2=6-(1-methylbenzyl)-2,2′-bipyridine, Hbipy3=6-(1,1-dimethylbenzyl)-2,2′-bipyridine, Hbipy4=6-phenyl-2,2′-bipyridine) has been investigated in different solvent systems using cyclic voltammetry and controlled-potential coulometry. All the species considered show, in cyclic voltammetry, an irreversible one-electron reduction in the potential range -0.9/-1.2 V versus Fc+/0, using a Pt electrode. On the other hand, exhaustive coulometries have shown the consumption of a number of Faraday per mole within the range 1-2. The very complex decomposition of the electrogenerated species affords elemental gold and significant amounts of different gold by-products. In some situations (e.g. reduction of [Au(bipy4)(Cl)][PF6]), working with 0.1 mol dm-3 Na[PF6], CH3CN solvent system, it has been possible to characterise the most abundant gold(III) compound, by NMR, FAB-MS, and elemental analysis. The analytical and spectroscopic data provide evidence for the N-C bis-cyclometallated gold(III) derivative (e.g. [Au(bipy4)2][PF6]); the result entails quite an unusual transcyclometallation process. The same compound can also be obtained, albeit in very minor yield, by chemical reduction of [Au(bipy4)(Cl)][PF6].

Item Type:Article
ID Code:3686
Status:Published
Refereed:Yes
Uncontrolled Keywords:Gold compounds, cyclometallated species, electrochemistry
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Area 03 - Scienze chimiche > CHIM/01 Chimica analitica
Divisions:001 Università di Sassari > 01 Dipartimenti > Chimica
Publisher:Elsevier
ISSN:0022-328X
Copyright Holders:© 2001 Elsevier Science
Deposited On:06 Apr 2010 12:51

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