Synthesis, characterization and hydroformylation activity of 7-azaindolate-bridged dinuclear rhodium(I)phosphines with pendant polar-groups

✍ Scribed by Chandra Sekhar Vasam; Sarangapani Modem; Shravankumar Kankala; Geeta Budige; Ravinder Vadde

• Publisher: John Wiley and Sons
• Year: 2009
• Tongue: English
• Weight: 199 KB
• Volume: 23
• Category: Article
• ISSN: 0268-2605
• DOI: 10.1002/aoc.1546

✦ Synopsis

Abstract

New dinuclear Rh(I)–Phosphines of the types [Rh(µ‐azi)(CO)(L)]~2~ (1,3–7) and [Rh(µ‐azi)(L)]~2~ (8) with pendant polar groups, and a chealated mononuclear compound [Rh(azi‐H)(CO)(L)] (2) (where azi = 7‐azaindolate, L = polar phosphine) were isolated from the reaction of [Rh(µ‐Cl)(CO)~2~]~2~ with 7‐azaindolate followed by some polar mono‐ and bis‐phosphines (L~1~–L~8~). A relationship between Δδ^31^P‐NMR and ν(CO) values was considered to define the impact of polar‐groups on σ‐donor properties of the phosphines. These compounds were evaluated as catalyst precursors in the hydroformylation of 1‐hexene and 1‐dodecene both in mono‐ and biphasic aqueous organic systems. While the biphasic hydroformylations (water + toluene) gave exclusively the aldehydes, the monophasic one (aqueous ethanol) showed propensity to form both aldehydes and alcohols. The influence of bimetallic cooperative effects, and σ‐donor and hydrophilic properties of the phosphines with pendant polar‐groups in enhancing the yields and selectivity of hydroformylation products was emphasized. In addition, when strong σ‐donor phosphine was used, the π‐acceptor nature of pyridine ring of 7‐azaindolate spacer was found to be a considerable factor in facilitating the facile cleavage of CO group during hydroformylation and in supplementing the cooperative effects. Copyright © 2009 John Wiley & Sons, Ltd.