Syntheses and reactivity studies of solvated dirhenium acetonitrile complexes

Bera, Jitendra K. ; Schelter, Eric J. ; Patra, Sanjib K. ; Bacsa, John ; Dunbar, Kim R. (2006) Syntheses and reactivity studies of solvated dirhenium acetonitrile complexes Dalton Transactions, 2006 (33). pp. 4011-4019. ISSN 0300-9246

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Official URL: http://pubs.rsc.org/en/content/articlelanding/2006...

Related URL: http://dx.doi.org/10.1039/B601463A

Abstract

Fully and partially solvated triply-bonded [Re2]4+ complexes have been synthesized and their X-ray structures are described. A fully solvated dirhenium salt with BArf [tetrakis(3,5-bis(trifluoromethyl)phenyl)borate] as the counter anion [Re2(CH3CN)10][BArf]4 (1) has been characterized. The solubility of the complex in CH2Cl2 and THF in addition to CH3CN offers the possibility of improved reactivity. The structure of [Re2(µ-O)(CH3CN)10][BF4]4 (2) that possesses a linear [ReIII–O–ReIII]4+ unit is reported. Protonation reactions of cis-Re2Cl2(dppm)2(O2CCH3)2 and trans-Re2Cl4(dppm)2 with HBF4·Et2O in acetonitrile afforded cis and trans [Re2(dppm)2(CH3CN)6][BF4]4 (3 and 4), respectively. Prolonging the reaction time, however, does not lead to fully solvated complex [Re2(CH3CN)10][BF4]4. The neutral nitrogen donor ligands pynp (2-(2-pyridyl)-1,8-naphthyridine) and tznp (2-(2-thiazolyl)-1,8-naphthyridine) react readily with [Re2(CH3CN)10][BF4]4 to provide trans-[Re2(pynp)2(CH3CN)4][BF4]4 and trans-[Re2(tznp)2(CH3CN)4][BF4]4. The X-ray structures trans-[Re2(pynp)2(CH3CN)4][BF4]4 (5) and trans-[Re2(tznp)2(CH3CN)4][BF4]3[PF6] (6) have been determined.

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