Quick Search:

uzh logo
Browse by:

Zurich Open Repository and Archive

Maintenance: Tuesday, 5.7.2016, 07:00-08:00

Maintenance work on ZORA and JDB on Tuesday, 5th July, 07h00-08h00. During this time there will be a brief unavailability for about 1 hour. Please be patient.

Permanent URL to this publication: http://dx.doi.org/10.5167/uzh-3184

Gleich, D; Hutter, J (2004). Computational approaches to activity in rhodium-catalysed hydroformylation. Chemistry - A European Journal, 10(10):2435-2444.

[img] PDF - Registered users only
View at publisher


In this theoretical study on rhodium-catalysed hydroformylation we examine an unmodified hydrido-rhodium(I) carbonyl system a together with three variants modified by the model phosphane ligands PF3 (System b) PH3 (system c) and PMe3 (system d), which show increasing basicity on the Tolman parameter scale. The olefinic substrate for all systems is ethene. Based on the dissociative hydroformylation mechanism, static and dynamic quantum-mechanical approaches are made for preequilibria and the whole catalytic cycle. Agreement with experimental results was achieved with regard to the predominance of phosphane monocoordination in systems b-d, different sensitivity of unmodified and modified systems towards hydrogen pressure and the early location of the rate-determining step. Neither the catalytic cycle as a whole nor olefin insertion as an important selectivity-determining step gives a clear picture of activity differences among a-d. However, the crucial first catalytic step, association of ethene to the active species [HRhL3] (L=CO, PR3), may play the key role in the experimentally observed higher activity of a and systems with less basic phosphane ligands modelled by b.


33 citations in Web of Science®
37 citations in Scopus®
Google Scholar™



1 download since deposited on 26 Mar 2009
0 downloads since 12 months

Detailed statistics

Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Date:May 2004
Deposited On:26 Mar 2009 21:09
Last Modified:05 Apr 2016 12:26
Publisher DOI:10.1002/chem.200305179
PubMed ID:15146517

Users (please log in): suggest update or correction for this item

Repository Staff Only: item control page