DEB , BISWAJIT and SARMAH , PODMA POLLOV and SAIKIA , KOKIL and FULLER , A L and RANDALL , R A M and SLAWIN , A M Z and WOOLLINS , J D and DUTTA , D K
(2011)
Rhodium(I) carbonyl complexes of tetradentate chalcogen functionalized phosphines, [P/(X)(CH2CH2P(X)Ph2)3] {X = O, S, Se}: Synthesis, reactivity and catalytic carbonylation reaction.
J Organometallic Chemistry, 696.
pp. 3279-3283.
Abstract
The reaction of [Rh(CO)2Cl] 2 with 0.5 mol equivalent of the ligands [P0(X)(CH 2eCH 2P(X)Ph 2) 3](P0P 3X 4)
{where X
� O(a), S(b) and Se(c)} affords tetranuclear complexes of the type [Rh 4(CO) 8Cl 4(P0P 3X 4)]
(1ae1c). The complexes 1ae1c have been characterized by elemental analyses, mass spectrometry, IR
and multinuclear NMR spectroscopy, and the ligandsb andc are structurally determined bysingle crystal
X-ray diffraction.1ae1c undergo oxidative addition (OA) reactions with CH3I to generate Rh(III) oxidised
products. Kinetic data for the reaction of 1a and 1b with excess CH 3I indicate a pseudo�01rst order
reaction. The catalytic activity of 1ae1c for the carbonylation of methanol to acetic acid and its ester
show a higher Turn Over Frequency (TOF
� 1349e1748 h �021) compared to the well-known species
[Rh(CO)2I2] �02 (TOF
� 1000 h�021) under the similar experimental conditions. However, 1b and 1c exhibit
lower TOF than 1a, which may be due to the desulfurization and deselinization of the ligands in the
respective complexes under the reaction conditions.
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