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Cyclometallated derivatives of rhodium(III): activation of C(sp3)–H vs. C(sp2)–H bonds

Zucca, Antonio and Stoccoro, Sergio and Cinellu, Maria Agostina and Minghetti, Giovanni and Manassero, Mario (1999) Cyclometallated derivatives of rhodium(III): activation of C(sp3)–H vs. C(sp2)–H bonds. Journal of the Chemical Society. Dalton Transactions, Vol. 1999 (19), p. 3431-3437. ISSN 0300-9246. Article.

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DOI: 10.1039/A903614h

Abstract

The reaction of RhCl3·3H2O with a series of 6-substituted-2,2′-bipyridines HL (N2C10H7R, R = CH2Ph, HLb; C(CH3)2Ph, HLdm; CH(CH3)2, HLip; C(CH3)3, HLtb; or CH2C(CH3)3, HLnp) in refluxing water–acetonitrile gave cyclometallated species, either neutral, [Rh(L)(CH3CN)Cl2], or cationic, [Rh(L)(CH3CN)2Cl]+, resulting from direct activation of C(sp2)–H or C(sp3)–H bonds. Surprisingly, in the case of R = C(CH3)2Ph metallation involved one of the methyls rather than the phenyl group. The crystal structure of [Rh(Lb)(CH3CN)Cl2] has been determined by X-ray diffraction. Adducts [Rh(HL)(CH3CN)Cl3], likely to be intermediates in the synthesis of the metallated species, have been isolated and characterized. Some aspects of the reactivity of the adducts and of the cyclometallated species are also reported.

Item Type:Article
ID Code:5354
Status:Published
Refereed:Yes
Uncontrolled Keywords:RhCl3·3H2O, cyclometallated species, rhodium(III)
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 01 Dipartimenti > Chimica
Publisher:Royal Society of Chemistry
ISSN:0300-9246
Deposited On:27 Jan 2011 11:25

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