Assessment of Stereoelectronic Effects in Grubbs First-Generation Olefin Metathesis Catalysis Using Molecular Electrostatic Potential

Abstract

Quantum mechanically derived molecular electrostatic potential (MESP) based descriptors have been proposed for the assessment of both the steric and electronic effects of phosphines in several first-generation Grubbs olefin metathesis catalysts. The MESP at the P nucleus of the active form of the catalyst Cl2(PR3)Ru═CH2 (1) and its ethylene-coordinated complex (2) are determined. Further, frozen structures corresponding to 1 and 2 are located by replacing the P−R bonds with P−H bonds. The MESP at the P of a frozen geometry is free from the electronic effect of R but is influenced by steric effects due to the structural restrictions imposed in the geometry. The difference between the MESP values at the P nucleus of Cl2(PH3)Ru═CH2 and Cl2(PR3)Ru═CH2 is taken as a measure of the combined steric and electronic effects of PR3 (VSE1) in 1. Similarly, the combined steric and electronic effect of PR3 in 2 (VSE2) is also calculated. The frozen structures allowed calculation of the steric-only effects for 1 (VS1) as well as 2 (VS2). Thus, the electronic effect of PR3, VE1, in 1 is VSE1 − VS1 and that of PR3, VE2 ,in 2 is VSE2 − VS2. Both VS1 and VS2 showed impressive linear correlations with popular geometric steric parameters: viz. the Tolman cone angle (θ) and the symmetric deformation coordinate (S4′). Moreover, VE1 and VS1 showed linear relationships to the binding energy of ethylene (E1), suggesting that the steric effect is 1.88 times more dominant than the electronic effect in the olefin binding process. Similarly, both VE2 and VS2 showed linear correlation with the activation energy (E2) for the formation of metallacyclobutane. In both the olefin binding process and the transition state formation leading to C−C bond coupling, a drastic reduction in E1 as well as in E2 is observed with an increase in the steric bulkiness of PR3, while only a moderate decrease in energy parameters is observed with an increase in the electron-rich character of PR3. The stereoelectronic correlation studies presented herein demonstrate that the success of the first-generation Grubbs catalysts is primarily due to the choice of the right mix of steric (bulky R substituents on P) and electronic (electron-donating R substituents on P) effects of the PR3 ligand.