Oxidative Addition Reactions of Organorhodium(I) Complexes Containing the Tridentate Ligand 2,6-Bis(diphenylphosphanylmethyl)pyridine [Rh(PNP)R] (R = CH3, C6H5) with Iodine and Methyl Iodide and Investigation of the Reductive Elimination

✍ Scribed by Christine Hahn; Michael Spiegler; Eberhardt Herdtweck; Rudolf Taube

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 261 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/(sici)1099-0682(199903)1999:3<435::aid-ejic435>3.0.co;2-h

✦ Synopsis

As part of studies aimed at delineating the mechanism of the rhodium(III) complexes 2a,b and 3a,b have been characterized by 31 P-, 1 H-, and 13 C-NMR spectrometry, as rhodium complex-catalyzed hydroamination of olefins, the model complexes [Rh(PNP)R] (R = CH 3 1a, C 6 H 5 1b) have well as by EI mass spectrometry. The hydrocarbons RCH 3 are reductively eliminated in the reaction of [Rh(PNP)(CH 3 )RI] been investigated with regard to oxidative addition reactions. The reaction of I 2 with 1a leads to both trans-and (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) cis-[Rh(PNP)(CH 3 )I 2 ] (trans: 2a, cis: 2aЈ), whereas with 1b only trans-[Rh(PNP)(C 6 H 5 )I 2 ] (2b) is obtained. The complex [Rh(PNP)(CH 3 )(C 6 H 5 )(CH 3 CN)]BF 4 (5). Complex 5 has been characterized by X-ray crystallography. rhodium(III) complexes [Rh(PNP)(CH 3 )RI] (3a,b) are formed by the reaction of 1a,b with CH 3 I. The new organodition of the protic acid, could not be isolated or detected