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Oxidative addition of different electrophiles with rhodium(I) carbonyl complexes of unsymmetrical phosphine–phosphine monoselenide ligands
Author(s) -
Chutia Pratap,
Sarmah Bhaskar Jyoti,
Dutta Dipak Kumar
Publication year - 2006
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.1098
Subject(s) - chemistry , phosphine , rhodium , electrophile , oxidative addition , carbonylation , medicinal chemistry , ligand (biochemistry) , chelation , stereochemistry , reactivity (psychology) , methanol , kinetics , phosphine oxide , catalysis , inorganic chemistry , organic chemistry , carbon monoxide , medicine , biochemistry , physics , receptor , alternative medicine , pathology , quantum mechanics
Dimeric chlorobridge complex [Rh(CO) 2 Cl] 2 reacts with two equivalents of a series of unsymmetrical phosphine–phosphine monoselenide ligands, Ph 2 P(CH 2 ) n P(Se)Ph 2 { n = 1( a ), 2( b ), 3( c ), 4( d )}to form chelate complex [Rh(CO)Cl(P∩Se)] ( 1a ) {P∩Se = η 2 ‐(P,Se) coordinated} and non‐chelate complexes [Rh(CO) 2 Cl(P∼Se)] ( 1b–d ) {P∼Se = η 1 ‐(P) coordinated}. The complexes 1 undergo oxidative addition reactions with different electrophiles such as CH 3 I, C 2 H 5 I, C 6 H 5 CH 2 Cl and I 2 to produce Rh(III) complexes of the type [Rh(COR)ClX(P∩Se)] {where R = C 2 H 5 ( 2a ), X = I; R = CH 2 C 6 H 5 ( 3a ), X = Cl}, [Rh(CO)ClI 2 (P∩Se)] ( 4a ), [Rh(CO)(COCH 3 )ClI(P∼Se)] ( 5b–d ), [Rh(CO)(COH 5 )ClI‐(P∼Se)] ( 6b–d ), [Rh(CO)(COCH 2 C 6 H 5 )Cl 2 (P∼Se)] ( 7b–d ) and [Rh(CO)ClI 2 (P∼Se)] ( 8b–d ). The kinetic study of the oxidative addition (OA) reactions of the complexes 1 with CH 3 I and C 2 H 5 I reveals a single stage kinetics. The rate of OA of the complexes varies with the length of the ligand backbone and follows the order 1a > 1b > 1c > 1d . The CH 3 I reacts with the different complexes at a rate 10–100 times faster than the C 2 H 5 I. The catalytic activity of complexes 1b–d for carbonylation of methanol is evaluated and a higher turnover number (TON) is obtained compared with that of the well‐known commercial species [Rh(CO) 2 I 2 ] − . Copyright © 2006 John Wiley & Sons, Ltd.