Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 8, 2010
Previous Article Next Article

A theoretical study of X ligand effect on catalytic activity of complexes RuHX(diamine)(PPh3)2 (X = NCMe, CO, Cl, OMe, OPh, CCMe and H) in H2-hydrogenation of ketones

Author affiliations

Abstract

In this paper, the catalytic activities of RuHX(diamine)(PPh3)2 complexes with different X ligands (X = NCMe, CO, Cl, OMe, OPh, CCMe and H, corresponding catalytic processes are abbreviated in A, B, C, D, E, F and G systems, respectively) in the H2-hydrogenation of ketones were investigated using density functional theory (DFT) method. Calculated results indicate that the rate-determining step in the whole catalytic cycle is hydrogen transfer (HT) for A–E but dihydrogen activation (DA) for F and G. The free energy barriers of the HT step for A–G are 36.1, 32.3, 21.2, 14.9, 21.9, 9.4 and 6.9 kcal mol−1, respectively. The DA step consists of hydrogen coordination (HC) and hydrogen splitting (HS) steps if dihydrogen coordinates with the Ru center. The transition states (TSs) of H2 coordinating with the Ru atom for A–G except B are located. The free energy barriers of DA for A–G are 17.8 (17.8, 2.6), 21.5, 12.8 (12.8, 3.8), 12.2 (11.2, 6.2), 13.6 (13.6, 4.1), 17.1 (9.7, 7.5) and 22.0 (10.4, 11.0) kcal mol−1, respectively (the data in parentheses correspond to the barriers of HC and HS). HT barriers correlate well with the charges of hydride (H) in complex 1. HC barriers are closely related to the Ru[double bond, length as m-dash]N1 double bond in 4, and HS are in line with the proton-moved-distances (PMDs) from 5 to TS5-1. This study demonstrates that catalysts D, F and G show better catalytic activities than the others, which is in good agreement with experimental results.

Graphical abstract: A theoretical study of X ligand effect on catalytic activity of complexes RuHX(diamine)(PPh3)2 (X = NCMe, CO, Cl, OMe, OPh, CCMe and H) in H2-hydrogenation of ketones

Back to tab navigation

Supplementary files

Article information


Submitted
01 Sep 2009
Accepted
26 Nov 2009
First published
13 Jan 2010

Dalton Trans., 2010,39, 2036-2043
Article type
Paper

A theoretical study of X ligand effect on catalytic activity of complexes RuHX(diamine)(PPh3)2 (X = NCMe, CO, Cl, OMe, OPh, CCMe and H) in H2-hydrogenation of ketones

Z. Chen, Y. Chen, Y. Tang and M. Lei, Dalton Trans., 2010, 39, 2036
DOI: 10.1039/B917934H

Social activity

Search articles by author

Spotlight

Advertisements