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Reactivity of 1,3-bis(2-pyridyl)benzene, N^CH^N, with gold(III) chlorides: salts, adducts and cyclometalated pincer derivatives: crystal and molecular structures of [HN^CH^N][AuCl4], [Au(N^C^N)Cl][PF6] and [Au(N^C^N)Cl(PPh3)2][PF6]

Stoccoro, Sergio and Alesso, Giuseppe Andrea and Cinellu, Maria Agostina and Minghetti, Giovanni and Zucca, Antonio and Manassero, Mario and Manassero, Carlo (2009) Reactivity of 1,3-bis(2-pyridyl)benzene, N^CH^N, with gold(III) chlorides: salts, adducts and cyclometalated pincer derivatives: crystal and molecular structures of [HN^CH^N][AuCl4], [Au(N^C^N)Cl][PF6] and [Au(N^C^N)Cl(PPh3)2][PF6]. Dalton Transactions, Vol. 2009 (18), p. 3467-3477. eISSN 1477-9234. Article.

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DOI: 10.1039/b822842f

Abstract

The reaction of 1,3-bis(2-pyridyl)benzene, N^CH^N, with H[AuCl4] has been studied under different conditions. Mono- ([N^CH^NH][AuCl4]) and di-protonated salts ([HN^CH^NH][AuCl4]2), as well as an adduct, [(N^CH^N)(AuCl3)2], have been isolated. Very rare cyclometalated pincer derivatives, [Au(N^C^N)Cl]+ have been obtained as different salts, either by transmetallation from the corresponding mercury(II) derivative, [Hg(N^C^N)Cl], or by direct C–H activation. The structures in the solid state of [N^CH^NH][AuCl4] and [Au(N^C^N)Cl][PF6] have been solved by X-ray diffraction. Reaction of the pincer derivatives with PPh3, dppm (bis(diphenylphosphino)methane) and dppe (1,2-bis(diphenylphosphino)ethane) occurs with displacement of the coordinated nitrogen atoms to afford [Au(N^C^N)(Cl)(PPh3)2]+, [Au(N^C^N)(Cl)(dppm)2]+ and [Au(N^C^N)(Cl)(dppe)]+, respectively. The X-ray structure of [Au(N^C^N)(Cl)(PPh3)2][PF6] confirms that the ligand N^C^N is only δ-carbon bonded and the PPh3 molecules are in a trans-arrangement. The pattern of the 31P{1H}NMR spectrum of [Au(N^C^N)(Cl)(dppm)2]+, a pair of “triplets”, deserves comments: the spectrum is not of the A2X2 type but a case of a deceptively simple AA’XX’ spin system.

Item Type:Article
ID Code:4264
Status:Published
Refereed:Yes
Uncontrolled Keywords:Organometallic complexes, pincer ligands, reactivity
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 01 Dipartimenti > Chimica
Publisher:Royal Society of Chemistry
eISSN:1477-9234
Deposited On:23 Jul 2010 18:21

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