TY - JOUR

T1 - Comparison of Zinc and Magnesium Clusters in Their Reaction with Organochlorides: Toward a Molecular Picture of Grignard Reagent Formation

AU - Barsukov, Yu. V.

AU - Porsev, V. V.

AU - Tulub, A. V.

PY - 2012

Y1 - 2012

N2 - The reaction channels of Znn and Mgn clusters (n ¼ 4, 10) with RCl organochlorides are compared to the investigation of relative activity of metals in the reaction of Grignard reagent formation within a framework of quantum chemical modeling of a reaction path. R radicals are chosen from a list of alkyl (CH3, C2H5, i-C3H7, and t-C4H9) and residues with p-bond (C2H3 and C6H5). Quantum chemistry calculations are made using the density function theory DFT) approach at the B3PW91/6-311þG(d) level. The reaction channels for both zinc and magnesium can be classified as radical and nonradical according to the nature of reaction products. The calculation of activation energies shows much similarity in their dependence on the nature of R radical but in the case of zinc, barriers are significantly higher. Both for zinc and magnesium clusters, the radical channels are more preferable in the case of alkyl residues, for vinyl and phenyl residues barriers of radical and nonradical channels are comparable

AB - The reaction channels of Znn and Mgn clusters (n ¼ 4, 10) with RCl organochlorides are compared to the investigation of relative activity of metals in the reaction of Grignard reagent formation within a framework of quantum chemical modeling of a reaction path. R radicals are chosen from a list of alkyl (CH3, C2H5, i-C3H7, and t-C4H9) and residues with p-bond (C2H3 and C6H5). Quantum chemistry calculations are made using the density function theory DFT) approach at the B3PW91/6-311þG(d) level. The reaction channels for both zinc and magnesium can be classified as radical and nonradical according to the nature of reaction products. The calculation of activation energies shows much similarity in their dependence on the nature of R radical but in the case of zinc, barriers are significantly higher. Both for zinc and magnesium clusters, the radical channels are more preferable in the case of alkyl residues, for vinyl and phenyl residues barriers of radical and nonradical channels are comparable

KW - B3PW91 magnesium cluster zinc cluster Grignard reagent formation radicals

U2 - 10.1002/qua.24187

DO - 10.1002/qua.24187

M3 - Article

VL - 112

SP - 3002

EP - 3007

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

ER -