Please use this identifier to cite or link to this item: https://doi.org/10.1002/ejic.200600879
Title: (Indenyl)ruthenium complexes containing 1,1′-bis(diphenylphosphanyl)- ferrocene (dppf) and thiolato ligands: Synthesis, X-ray structure analysis, electrochemistry and magnetic studies
Authors: Sin, Y.N.
Weng, K.L. 
Lai, Y.G. 
Webster, R.D.
Keywords: (Indenyl)ruthenium
Cyclic voltammetry
dppf
ESR
Ruthenium
Thiolates
Issue Date: 2007
Source: Sin, Y.N., Weng, K.L., Lai, Y.G., Webster, R.D. (2007). (Indenyl)ruthenium complexes containing 1,1′-bis(diphenylphosphanyl)- ferrocene (dppf) and thiolato ligands: Synthesis, X-ray structure analysis, electrochemistry and magnetic studies. European Journal of Inorganic Chemistry (3) : 463-471. ScholarBank@NUS Repository. https://doi.org/10.1002/ejic.200600879
Abstract: The reaction of [(Ind)Ru(dppf)Cl] (Ind = η5-C 9H7) (2) with RSNa {R = Me, Et, Ph, Ph 2P(CH2)2) proceeds in MeOH to give [(Ind)Ru(dppf)(SR)] {R = Me (3), Et (4), Ph (5), Ph2P(CH 2)2 (7)}, as well as [(Ind)Ru(dppf)H] (6), in all cases except for R = Ph. This R-dependence of the product mixture was rationalised on a RS-/MeOH ↔ MeO-/RSH equilibrium involving the interaction of thiolate (RS-) with MeOH, and the relative nucleophilicities of RS- versus MeO-; 6 arose from β-H elimination from an OMe derivative. Cyclic voltammetric measurements on 2, 3, 4 and 5, as well as the Cp (η5-C5H5) and Cp* (η5-C5Me5) analogues of 2, indicated that the formal oxidation potentials for [LRu(dppf)Cl] complexes {L = Ind (2), Cp (2A) and Cp* (2B)} occurred in the order Cp* < Ind < Cp, correlating with the more electron-donating groups lowering the oxidation potentials. EPR experiments performed on the one-electron oxidised forms of 3 and 5 indicated paramagnetic compounds with g values close to 2, while the two-electron oxidised forms of 3 and 5 were diamagnetic. All the complexes were characterised spectroscopically, and 5 and 6 also crystallographically. © Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Source Title: European Journal of Inorganic Chemistry
URI: http://scholarbank.nus.edu.sg/handle/10635/92877
ISSN: 14341948
DOI: 10.1002/ejic.200600879
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