Journal
APPLIED ORGANOMETALLIC CHEMISTRY
Volume 16, Issue 5, Pages 258-264Publisher
JOHN WILEY & SONS LTD
DOI: 10.1002/aoc.293
Keywords
carbonylrhodium(I); pyridine ligands; reactivity; kinetics; catalytic activity; carbonylation of methanol
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The cis-[Rh(CO)(2)CIL] (1) complexes, where L = 2-methylpyridine (a), 3-methylpyridine (b), 4-methylpyridine (c), 2-phenylpyridine (d), 3-phenylpyridine (e), 4-phenylpyridine (f), undergo oxidative addition reactions with various electrophiles, like CH3I C2H5I, C6H5CH2Cl or I-2, to yield complexes of the types [Rh(CO)(COR)ClXL] (2) (where R = CH3 (i), C2H5 (ii), X = I; R = C6H5CH2 (iii), X = Cl) or [Rh(CO)C1I2L] (3) and [Rh(CO)(2)ClI2L] (4). The pseudo-first-order rate constants of CH3I addition with complexes 1 containing pyridine (g) and 2-substituted pyridine (a and d) ligands were found to follow the order pyridine >2-methylpyri dine >2-phenylpyridine. The catalytic activity of complexes I containing different pyridine ligands (a-g) on carbonylation of methanol was studied and, in general, a higher turnover number was obtained compared with that of the well-known species [Rh(CO)(2)I-2](-) Copyright (C) 2002 John Wiley Sons, Ltd.
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