1562340-35-5Relevant academic research and scientific papers
(η5-Cp)Rh(III)/Ir(III) complexes with bis(chalcogenoethers) (E, E′ Ligands: E = S/Se; E′ = S/Se): Synthesis, structure, and applications in catalytic oppenauer-type oxidation and transfer hydrogenation
Prakash, Om,Sharma, Kamal Nayan,Joshi, Hemant,Gupta, Pancham L.,Singh, Ajai K.
, p. 983 - 993 (2014)
The air- and moisture-insensitive half-sandwich complexes [(η5-Cp)Rh(L)Cl][PF6] (1-3) and [(η5- Cp)Ir(L)Cl][PF6] (4-6) have been prepared by reacting L = L1-L3 (1,2-bis(phenylthio)ethane (L1), 1-(phenylseleno)-2-(phenylthio)ethane (L2) and 1,2-bis(phenylseleno)ethane (L3)) with [(η5-Cp)RhCl(μ-Cl)] 2 and [(η5-Cp)IrCl(μ-Cl)]2, respectively, at room temperature followed by treatment with NH 4PF6. Their HR-MS and 1H, 13C{ 1H}, and 77Se{1H} NMR spectra have authenticated them. The single-crystal structures of 1-6 have been established by X-ray crystallography. Complexes 1-6 have been explored for catalytic Oppenauer-type oxidation of alcohols and transfer hydrogenation of ketones with 2-propanol. 3 and 6 were the most efficient in the two catalytic reactions (TON values up to 9.9 × 102 and 9.8 × 103, respectively) and were therefore investigated in detail. 3 is the first example of a Rh(III) species explored for Oppenauer-type oxidation. The catalysis appears to be homogeneous. In transfer hydrogenation it appears that one of the catalytic species is without a Cp* ring. DFT calculations indicate higher reactivity for Rh complexes in comparison to Ir complexes. This order has also been found for the two catalytic reactions experimentally. The calculated bond lengths/angles by DFT are generally consistent with the experimental values.
