Homogeneous catalytic hydroformylation of vinylarenes: a selective rhodium diphosphine catalyst system for higher branched/linear product ratios

Abstract

A rhodium diphosphine catalyst containing electron-withdrawing substituents on the ligand is highly regioselective in the hydroformylation of vinylarenes giving high branched/linear product ratios.

A New, Efficient, and in Some Cases Highly Regioselective Water-Soluble Polymer Rhodium Catalyst for Olefin Hydroformylation

“…This interesting result proves that the water-soluble catalyst Rh/PPA(Na + )/DPPEA is more active and much more regioselective than the water-soluble system Rh−PEVV which gave very low conversion of styrene 10d and Rh(acac)(CO) 2 /TPPTS or Rh(acac)(CO) 2 /PR[(CH 2 ) 8 C 6 H 4 - p -SO 3 Na] 2 , which afforded the products in B/L ratios ranging from 66/34 to 73/27 10b. This system is also more active and appreciably more regiselective than the supported aqueous phase catalyst 8e and shows comparable regioselectivity with some homogeneous systems such as Rh(cod)(η 6 -PhBPh 3 ) and [Rh(NBD)(L−L)]BF 4 where L−L is 1,2-bis[bis(pentafluorophenyl)phosphino]ethane , entries 3−7).…”

Synthesis and Molecular Structure of Pd2(C6F5)2[μ-P(C6F5)CH2CH2P(C6F5)2]2. A Rare Example of P−C Bond Cleavage in a Fluoroaryl Phosphine

“…Fluorinated phosphines are of interest as sterically tunable, π -acceptor ligands capable of supporting electron-poor metal centers . One commercially available member of this class of ligands is the chelating fluoroaryl phosphine (C 6 F 5 ) 2 PCH 2 CH 2 P(C 6 F 5 ) 2 , dfppe, which is reported to give enhanced hydroformylation and olefin polymerization catalytic activities compared to its more common, perprotio analogue, (C 6 H 5 ) 2 PCH 2 CH 2 P(C 6 H 5 ) 2 . While dfppe was first synthesized some 20 years ago, only a handful of coordination complexes containing it have been isolated …”

A Novel Water-Soluble Rhodium−Poly(enolate-co-vinyl alcohol-co-vinyl acetate) Catalyst for the Hydroformylation of Olefins

“…Although the hydroformylation of styrene gave poor selectivity at 90 °C using Rh−PEVV as the catalyst precursor, excellent selectivity (up to a 36.7 ratio of B/L) for the catalytic hydroformylation of styrene and its derivatives was achieved at 40 °C (Table ). These results can be compared with the homogeneous system using a zwitterionic rhodium complex and the rhodium complex of electron deficient phosphine ligands as catalyst precursors . Change of the H 2 /CO ratio or addition of PPh 3 , did not improve the B/L selectivity and reactivity (entries 2−5, Table ) as was found in the hydroformylation of aliphatic olefins.…”