ISSN:
1434-1948
Keywords:
Rhodium(III) complexes
;
Tridentate ligand
;
Oxidative addition
;
Reductive elimination
;
C-C coupling
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
As part of studies aimed at delineating the mechanism of the rhodium complex-catalyzed hydroamination of olefins, the model complexes [Rh(PNP)R] (R = CH31a, C6H51b) have been investigated with regard to oxidative addition reactions. The reaction of I2 with 1a leads to both trans- and cis-[Rh(PNP)(CH3)I2] (trans: 2a, cis: 2a′), whereas with 1b only trans-[Rh(PNP)(C6H5)I2] (2b) is obtained. The rhodium(III) complexes [Rh(PNP)(CH3)RI] (3a,b) are formed by the reaction of 1a,b with CH3I. The new organorhodium(III) complexes 2a,b and 3a,b have been characterized by 31P-, 1H-, and 13C-NMR spectrometry, as well as by EI mass spectrometry. The hydrocarbons RCH3 are reductively eliminated in the reaction of [Rh(PNP)(CH3)RI] (3a,b) with TlBF4 in acetone, while the reaction of 3b and TlBF4 in THF/CH3CN leads to the stable rhodium(III) complex [Rh(PNP)(CH3)(C6H5)(CH3CN)]BF4 (5). Complex 5 has been characterized by X-ray crystallography.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
