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Title: A new structural form of tin in a double O-capped cluster
Authors: Chandrasekhar, V.
Baskar, V.
Vittal, J.J. 
Issue Date: 5-Mar-2003
Citation: Chandrasekhar, V., Baskar, V., Vittal, J.J. (2003-03-05). A new structural form of tin in a double O-capped cluster. Journal of the American Chemical Society 125 (9) : 2392-2393. ScholarBank@NUS Repository.
Abstract: Two new cyanorhenate complexes of potential utility in constructing magnetic and photomagnetic materials are reported. Reaction of (Bu4N)CN with [ReCl6]2- in acetonitrile affords yellow (Bu4N)3[Re(CN)7] (1), featuring the pentagonal bipyramidal complex [Re(CN)7]3-. The spectral and magnetic properties of 1 indicate that the complex has an S = 1/2 ground state with considerable anisotropy in the g tensor. In aqueous solution, 1 reacts with Mn2+ ions to generate the three-dimensional cyano-bridged solid [fac-Mn(H2O)3][cis-Mn(H2O)2][Re(CN)7]·3H2O (2) containing diamagnetic [Re(CN)7]4-. Addition of KIO4 to the reaction solution, originally intended to prevent reduction of the rhenium during solid formation, instead yields white (Bu4N)3[Re(CN)8] (3). As crystallized in K3[Re(CN)8]·2MeCN (4·2MeCN), the diamagnetic [Re(CN)8]3- complex adopts a nearly perfect square antiprismatic coordination geometry. In solution, this species behaves analogously to the isoelectronic [M(CN)8]4- (M = Mo, W) complexes, apparently converting to a dodecahedral geometry and photooxidizing under UV radiation to give paramagnetic [Re(CN)8]2-. Copyright © 2003 American Chemical Society.
Source Title: Journal of the American Chemical Society
ISSN: 00027863
DOI: 10.1021/ja0287478
Appears in Collections:Staff Publications

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