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Oxidative Addition Reactions of Organorhodium(I) Complexes Containing the Tridentate Ligand 2,6‐Bis(diphenylphosphanylmethyl)pyridine [Rh(PNP)R] (R = CH 3 , C 6 H 5 ) with Iodine and Methyl Iodide and Investigation of the Reductive Elimination
Author(s) -
Hahn Christine,
Spiegler Michael,
Herdtweck Eberhardt,
Taube Rudolf
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199903)1999:3<435::aid-ejic435>3.0.co;2-h
Subject(s) - chemistry , rhodium , oxidative addition , medicinal chemistry , reductive elimination , iodide , ligand (biochemistry) , hydroamination , methyl iodide , pyridine , iodine , stereochemistry , reaction mechanism , nuclear magnetic resonance spectroscopy , catalysis , organic chemistry , intramolecular force , biochemistry , receptor
As part of studies aimed at delineating the mechanism of the rhodium complex‐catalyzed hydroamination of olefins, the model complexes [Rh(PNP)R] (R = CH 3 1a , C 6 H 5 1b ) have been investigated with regard to oxidative addition reactions. The reaction of I 2 with 1a leads to both trans ‐ and cis ‐[Rh(PNP)(CH 3 )I 2 ] ( trans : 2a , cis : 2a′ ), whereas with 1b only trans ‐[Rh(PNP)(C 6 H 5 )I 2 ] ( 2b ) is obtained. The rhodium(III) complexes [Rh(PNP)(CH 3 )RI] ( 3a , b ) are formed by the reaction of 1a , b with CH 3 I. The new organorhodium(III) complexes 2a , b and 3a , b have been characterized by 31 P‐, 1 H‐, and 13 C‐NMR spectrometry, as well as by EI mass spectrometry. The hydrocarbons RCH 3 are reductively eliminated in the reaction of [Rh(PNP)(CH 3 )RI] ( 3a , b ) with TlBF 4 in acetone, while the reaction of 3b and TlBF 4 in THF/CH 3 CN leads to the stable rhodium(III) complex [Rh(PNP)(CH 3 )(C 6 H 5 )(CH 3 CN)]BF 4 ( 5 ). Complex 5 has been characterized by X‐ray crystallography.