期刊
JOURNAL OF COORDINATION CHEMISTRY
卷 76, 期 3-4, 页码 449-455出版社
TAYLOR & FRANCIS LTD
DOI: 10.1080/00958972.2023.2190854
关键词
Ruthenium diphosphine; NN donors; transfer-hydrogenation; ketones
The complexes trans/cis-[RuCl2(DPEphos)(ampy)] (1a, 1b) and trans/cis-[RuCl2(DPEphos)(en)] (2a, 2b) were synthesized from the reactions of mer-[RuCl2(DPEphos)(PPh3)] with the corresponding amine. Isomer 1a was observed in situ at room temperature, while 1b was obtained when the reaction was performed under reflux. Isomer 2a was obtained at room temperature, and 2b was observed under reflux or when a CH2Cl2 solution of 2a was exposed to light. Cyclic voltammetry studies showed reversible processes for 1b and 2a. Both 1b and 2a exhibited high conversions and TOF values as pre-catalysts for the reduction of acetophenone and p-substituted acetophenones.
The complexes trans/cis-[RuCl2(DPEphos)(ampy)] (trans - 1a; cis - 1b) and trans/cis-[RuCl2(DPEphos)(en)] (trans - 2a; cis - 2b) were obtained from the reactions of mer-[RuCl2(DPEphos)(PPh3)] (PPh3 = triphenylphosphine) with the corresponding amine in CH2Cl2. The isomer 1a was observed in situ when the reaction was carried out at r.t.; isolation leads to mixtures with 1b, while the latter was isolated when the reaction was performed under reflux. On the other hand, trans-[RuCl2(DPEphos)(en)] (2a) was obtained at r.t., in good yield and the cis-isomer 2b was observed when the reaction was carried out under reflux or when a CH2Cl2 solution of 2a is exposed to ambient light, but 2b was not isolated in pure form even under reflux for one week. Cyclic voltammetry studies revealed the presence of one reversible process with E-1/2 0.57 and 0.40V for 1b and 2a, respectively. Both 1b and 2a were used as pre-catalysts for reduction of acetophenone and p-substituted acetophenones (F-, Me- and MeO-) in transfer-hydrogenation conditions (isopropanol, 82 degrees C, and pre-catalyst:KOH:acetophenones in molar ratio 1:20:500 and/or 1:20:1000) showing conversions of 93-99% and TOF values up to 4.2 10(4) h(-1).
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