1003195-75-2Relevant academic research and scientific papers
(Indenyl)ruthenium complexes containing 1,1′-bis(diphenylphosphanyl)- ferrocene (dppf) and thiolato ligands: Synthesis, X-ray structure analysis, electrochemistry and magnetic studies
Sin, Yee Ng,Weng, Kee Leong,Lai, Yoong Goh,Webster, Richard D.
, p. 463 - 471 (2007/10/03)
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.
