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Synthesis, characterisation and redox behaviour of isocyanide incorporated, chalcogen stabilised mixed-metal clusters

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Title Synthesis, characterisation and redox behaviour of isocyanide incorporated, chalcogen stabilised mixed-metal clusters
 
Creator MATHUR, PRADEEP
CHATTERJEE, SAURAV
LAHIRI, GOUTAM KUMAR
CHAKRABORTY, SOMA
KALDIS, JOHN H
MCGLINCHEY, MICHAEL J
 
Subject crystal structure
isomers
carbonylation
spectroscopy
x-ray diffraction
 
Description Room temperature reaction of a benzene solution of [Cp2Mo2Fe2(CO)7(μ3-E)(μ3-E′)] (EE′=Se2 (1), STe (2), SeTe (3)) with PriNC or ButNC resulted in the formation of iron bonded isocyanide clusters [Cp2Mo2Fe2(RNC)(CO)6 (μ3-E)(μ3-E′)], [E=E′=Se, R=Pri (5) or But (9); E=S, E′=Te, R=Pri (6a, 6b) or R=But (10a, 10b); E=Se, E′=Te, R=Pri (7a, 7b) or R=But (11a, 11b)] and molybdenum bonded isocyanide clusters [Cp2(RNC)Mo2Fe2(CO)6(μ3-E)(μ3-E′)], [E=E′=Se, R=Pri(13) or But (17); E=S, E′=Te, R=Pri (14) or R=But, (18); E=Se, E′=Te, R=Pri (15) or R=But (19)]. Two isomers (a and b) were detected by 1H NMR spectroscopy for the mixed-chalcogen clusters 6, 7, 10 and 11, where the isocyanide group is bonded to an iron atom. Thermolytic reaction conditions were necessary for the reaction of [(η5-C5H5)2Mo2Fe2(CO)7(μ3-Te)2] (4) with Pri NC or But NC to give [Cp2Mo2Fe2(RNC)(CO)6(μ3-Te)2] (R=Pri (8) or R=But, (12)) and [Cp2(RNC)Mo2Fe2(CO)6(μ3-Te)2] (R=Pri (8)). Compounds 5–19 have been characterised by IR and 1H and 13C NMR spectroscopy. The Se- and Te-bridged compounds have been further characterised by 77Se and 125Te NMR spectroscopy. The structures of compounds 12 and 14 were determined by single crystal X-ray diffraction methods. Redox properties of the mixed-metal clusters, 2, 6, 8, 12 and 14 have been studied by cyclic voltammetry in the potential range ±2.5 V at 298 K, using a platinum working electrode.
 
Publisher Elsevier
 
Date 2009-03-09T07:45:13Z
2011-11-25T18:54:12Z
2011-12-26T13:06:52Z
2011-12-27T05:54:51Z
2009-03-09T07:45:13Z
2011-11-25T18:54:12Z
2011-12-26T13:06:52Z
2011-12-27T05:54:51Z
2004
 
Type Article
 
Identifier Journal of Organometallic Chemistry 689(1), 122-133
0022-328X
http://dx.doi.org/10.1016/j.jorganchem.2003.09.039
http://hdl.handle.net/10054/911
http://dspace.library.iitb.ac.in/xmlui/handle/10054/911
 
Language en