Oxidative addition of methyl iodide to [Rh(CO)2I]2: synthesis, structure and reactivity of neutral rhodium acetyl complexes, [Rh(CO)(NCR)(COMe)I2]2

Oxidative addition of different electrophiles with rhodium(I) carbonyl complexes of unsymmetrical phosphine–phosphine monoselenide ligands

“…The Rh-CO bonds become destabilized as a result of decrease in π -back bonding due to insufficient electron on the metal center 43 and, consequently, one of the CO groups is eliminated to form a stable monocarbonyl Rh(III) acyl compound. The decrease in π -back bonding is evidenced from the higher shifting (6-14 cm −1 ) of the terminal ν(CO) band in the oxidized complexes 8b-d compared with the parent complexes 1b-d. 44 The ν(PSe) values are consistent with the non-chelating behavior of the ligands.…”

Dicarbonylrhodium(I) Complexes of Bipyridine Ligands with Proximate H‐Bonding Substituents and Their Application in Methyl Acetate Carbonylation

“…During the course of the reaction, the ν(CO) bands of [Rh (1) [38] The IR spectra in Figure 7, which were determined in acetonitrile because of the poor solubility of the ionic 3 ], before CO migratory insertion can take place. [7,63] The absence of iodide with its weak trans effect and a decrease of the negative charge at the metal centre facilitate the migratory insertion process.…”

“…In an attempt to prepare the final complex [RhI-(COMe)(1)(NCMe) 2 ]SbF 6 by an independent route, the dimeric complex [RhI(μ-I)(COMe)(CO)(NCMe)] 2 , previously prepared by Haynes and co-workers, [63] was treated with 2,2Ј-bipyridine. This resulted in the formation of a new complex [RhI 2 (COMe)(1)(CO)], which was fully characterised and shows ν(CO) and ν(COMe) IR bands (in Nujol) at 2058 and 1694 cm -1 , respectively.…”

“…Acetone was dried with B 2 O 3 and distilled under nitrogen. The starting materials [RhCl(CO) 2 ] 2 , [66] [RhCl(cod)] 2 , [67] [RhI 2 (COMe)-(CO)(MeCN)] 2 , [63] 2,2Ј-dipyridone, [68] and the ligands 6,6Ј-diamino-2,2Ј-bipyridine (2) [42] and diethyl 2,2Ј-bipyridine-6,6Ј-bis-(phosphonate) (5) [69] were prepared according to published procedures. The preparation of diethyl 2,2Ј-bipyridine-6,6Ј-bis(carboxylate) (4) was adapted from a previously published procedure.…”

Carbon Monoxide as a Chemical Feedstock: Carbonylation Catalysis

“…The corresponding dinuclear species [Rh 2 I 6 (CO) 2 (COMe) 2 ] 2-was isolated in the form of its trimethylphenylammonium salt and characterized by XRD. The possibility that neutral dinuclear methyl and acetyl Rh(III) species play an important role in the Monsanto process has very recently been reconsidered [121]. These neutral species should lead to faster CO migratory insertions and reductive eliminations than their anionic analogs, and surely in the future new ligands able to generate more active dinuclear systems for methanol carbonylation will be developed.…”