Cucullu, Michèle E. and Li, Chunbang and Nolan, Steven P. and Nguyen, SonBinh T. and Grubbs, Robert H. (1998) Thermochemical Investigation of Phosphine Ligand Substitution Reactions Involving trans-(PR_3)_2Cl_2RuCH−CHCPh_2 Complexes. Organometallics, 17 (25). pp. 5565-5568. ISSN 0276-7333. doi:10.1021/om9806343. https://resolver.caltech.edu/CaltechAUTHORS:20180518-140610266
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Abstract
The enthalpies of reaction of (PPh_3)_2Cl_2RuCH−CHCPh_2 (1) with a series of tertiary phosphine ligands, leading to the formation of (PR_3)_2Cl_2RuCH−CHCPh_2 complexes (PR_3 = P^iPr_3, PBz_3, PPh_2Cy, PPhCy_2, PCy_3, and PiBu_3) have been measured by solution calorimetry in CH_2Cl_2 at 30 °C. The range of reaction enthalpies spans some 6.5 kcal/mol and helps to establish a relative order of complex stability for these six ruthenium carbene complexes. The enthalpies of reaction for tertiary phosphine complexes, trans-(PR_3)_2Cl2RuCH−CHCPh_2, are as follows (PR_3, kcal/mol): PPh_3, 0; PBz_3, −1.3 (0.2); PCyPh_2, −1.8 (0.2); PCy_2Ph, −3.8 (0.2); PiBu_3, −3.8 (0.2); P^iPr_3, −5.2 (0.1); PCy_3, −6.5 (0.3). The thermodynamics of the exchange of these sterically demanding tertiary phosphine ligands for PPh_3 in 1 provides a measurement of the relative importance of phosphine steric and electronic properties/character to the enthalpy of reaction in this system. Correlations of various factors gauging the electron-donating properties of the phosphine ligands clearly show the electronic factor to be the overwhelming contributor to the enthalpy of reaction in this system.
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Alternate Title: | Thermochemical Investigation of Phosphine Ligand Substitution Reactions Involving trans-(PR3)2Cl2RuCH−CHCPh2 Complexes | ||||||
Additional Information: | © 1998 American Chemical Society. Received July 27, 1998. The National Science Foundation is gratefully acknowledged for support of this research. | ||||||
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Issue or Number: | 25 | ||||||
DOI: | 10.1021/om9806343 | ||||||
Record Number: | CaltechAUTHORS:20180518-140610266 | ||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180518-140610266 | ||||||
Official Citation: | Thermochemical Investigation of Phosphine Ligand Substitution Reactions Involving trans-(PR3)2Cl2RuCH−CHCPh2 Complexes Michèle E. Cucullu,Chunbang Li, and, Steven P. Nolan*, SonBinh T. Nguyen and, and Robert H. Grubbs Organometallics 1998 17 (25), 5565-5568 DOI: 10.1021/om9806343 | ||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||
ID Code: | 86460 | ||||||
Collection: | CaltechAUTHORS | ||||||
Deposited By: | George Porter | ||||||
Deposited On: | 21 May 2018 15:55 | ||||||
Last Modified: | 15 Nov 2021 20:38 |
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