Rhodium(I) carbonyl complexes of quinoline carboxaldehyde ligands and their catalytic carbonylation reaction

Podma Pollov Sarmah, Biswajit Deb, Bibek Jyoti Borah, Amy L. Fuller, Alexandra M. Z. Slawin, J. Derek Woollins, Dipak Kumar Dutta

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16 Citations (Scopus)


The dimeric rhodium precursor [Rh(CO)(2)Cl](2) reacts with quinoline (a) and its three isomeric carboxaldehyde ligands [quinoline-2-carboxaldehyde (b), quinoline-3-carboxaldehyde (c), and quinoline-4-carboxaldehyde (d)] in 1: 2 mole ratio to afford complexes of the type cis-[Rh(CO)(2)Cl(L)] (1a-1d), where L = a-d. The complexes 1a-1d have been characterised by elemental analyses, mass spectrometry, IR and NMR (H-1, C-13) spectroscopy together with a single crystal X-ray structure determination of 1c. The X-ray crystal structure of 1c reveals square planar geometry with a weak intermolecular pseudo dimeric structure (Rh center dot center dot center dot Rh 3.573 angstrom). 1a-1d undergo oxidative addition (OA) with different electrophiles such as CH3I, C2H5I and I-2 to give Rh(III) complexes of the type [Rh(CO)(COR) Cl(L) I] {R = -CH3 (2a-2d), R = -C2H5 (3a-3d)} and [Rh(CO)Cl(L)I-2] (4a-4d) respectively. 1b exhibits facile reactivity with different electrophiles at room temperature (25 degrees C), while 1a, 1c and 1d show very slow reactivity under similar condition, however, significant reactivity was observed at a temperature similar to 40 degrees C. The complexes 1a-1d show higher catalytic activity for carbonylation of methanol to acetic acid and methyl acetate [Turn Over Frequency (TOF) 1551-1735 h(-1)] compared to that of the well known Monsanto's species [Rh(CO)(2)I-2](-) (TOF = 1000 h(-1)) under the reaction conditions: temperature 130 +/- 2 degrees C, pressure 33 +/- 2 bar, 450 rpm and time 1 h. The organometallic residue of 1a-1d was also isolated after the catalytic reaction and found to be active for further run without significant loss of activity. (C) 2010 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)2603-2608
Number of pages6
JournalJournal of Organometallic Chemistry
Issue number24
Publication statusPublished - 15 Nov 2010


  • Rhodium
  • Carbonyl ligand
  • Quinoline ligand
  • Carbonylation
  • Oxidative addition


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