Rhodium(I) carbonyl complexes of quinoline carboxylic acid: Synthesis, reactivity and catalytic carbonylation reaction

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Title:	Rhodium(I) carbonyl complexes of quinoline carboxylic acid: Synthesis, reactivity and catalytic carbonylation reaction
Authors:	戴帕克;Sarmah, Podma Pollov;Dutta, Dipak Kumar
Contributors:	資訊電機學院電機工程學系
Keywords:	acetates;acetic acid;Carbonyl ligand;Carbonylation;Catalysis;catalytic activity;Chemistry;Exact sciences and technology;Fourier transform infrared spectroscopy;General and physical chemistry;iodine;mass spectrometry;methanol;methyl iodide;N-donor ligand;nuclear magnetic resonance spectroscopy;Oxidative addition;quinoline;Rhodium;temperature;Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
Date:	2013-06-01
Issue Date:	2026-04-23 14:37:20 (UTC+8)
Publisher:	Elsevier BV;Amsterdam: Elsevier B.V
Abstract:	摘要： [Display omitted] ► Two new rhodium dicarbonyl complexes of quinoline carboxylic acid were synthesized. ► Activation of small molecules like CH3I, C2H5I etc. was studied with the complexes. ► Kinetics of oxidative addition of CH3I with synthesized complexes has been studied. ► Catalytic efficiency of the complexes in carbonylation reaction was evaluated. The dimeric rhodium precursor [Rh(CO)2Cl]2 reacts with the ligands (L) quinoline-2-carboxylic acid (a) or quinoline-8-carboxylic acid (b) in 1:2 mole ratio to afford complexes of the type cis-[Rh(CO)2ClL] (1a and 1b). The complexes have been characterized by elemental analysis, Mass spectrometry, FT-IR and NMR (1H, 13C) spectroscopy. 1a and 1b undergo oxidative addition (OA) with different electrophiles such as CH3I, C2H5I and I2 to give Rh(III) complexes of the type [Rh(CO)(COR)ClIL] {R=CH3 (2a and 2b), R=C2H5 (3a and 3b)} and [Rh(CO)ClI2L] (4a and 4b) respectively. OA of the CH3I with 1a forms relatively stable acyl intermediate which is evident from IR spectroscopy. The complexes 1a and 1b show higher catalytic activity for carbonylation of methanol to acetic acid and methyl acetate [Turn over number (TON) upto 1775 in 1h] compared to that of the well known Monsanto's species [Rh(CO)2I2]− (TON=1000 in 1h) under the reaction conditions: temperature 130±2°C, pressure 30±2bar, 450rpm and 1h reaction time. 出版者： Amsterdam: Elsevier B.V 出版日期： 2013-06-01 出處： Journal of molecular catalysis. A, Chemical, 2013-06, Vol.372, p.1-5 版權： 2013 Elsevier B.V. 版權： 2014 INIST-CNRS 識別號： ISSN: 1381-1169 識別號： EISSN: 1873-314X 識別號： DOI: 10.1016/j.molcata.2013.02.005
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