Theoretical study on the C-H activation in decarbonylation of acetaldehyde by NiL₂ (L=SO₃CH₃) using density functional theory

Abstract

Density functional theory calculations were carried out to explore the potential energy surface (PES) associated with the gas-phase reaction of NiL₂(L=SO₃CH₃) with acetone. The geometries and energies of the reactants, intermediates, products and transition states of the triplet ground potential energy surfaces of [Ni, O, C₂, H₄] were obtained at the B3LYP/6-311++G(d,p) levels in C,H,O atoms and B3LYP/Lanl2dz in Ni atom. It was found through our calculations that the decabonylation of acetaldehyde contains four steps including encounter complexation, C-C activation, aldehyde H-shift and nonreactive dissociation. The results revealed that C-C activation induced by NiL₂(L=SO₃CH₃) led to the decarbonylation of acetaldehyde.

Keywords

density functional theory / decarbonylation / transition state / energy / C-C activation

References

[1] Corderman RR, Beauchamp J Ion Cyclotron Reaonance Investigation of the Decarbonylation of Aldehydes by (.eta.5-cyclopentadienyl) Nickel(1+)[J]. J.Am.Chem.Soc., 1976, 98: 5 700-5 702.

[2] Halle LF, Crowe WE, Armentrout PB, . Reactions of Atomic Cobalt Ions with Aldehydes and Ketones: Observation of Decarbonylation Processes Leading to Formation of Metal Alkyls and Metallacycles in the Gas Phase[J]. Organometallics, 1984, 3: 1 694-1 706.

[3] Tolbert MA, Beauchamp JL Homolytic and Heterolytic Bond Dissociation Energies of the Second Row Group 8,9,and 10 Diatomic Transition-metal Hydrides: Correlation with Electronic Structure[J]. J.Phys.Chem., 1986, 90: 5 015-5 022.

[4] Allison J, Ridge DP The Gas-phase Chemistry of Chlorotitanium Ions with Oxygen-containing Organic Compounds[J]. J.Am.Chem.Soc., 1978, 100: 163-169.

[5] Cassady CJ, Freiser BS Gas-phase Reactions of Transition-Metal Ions with Methyl Nitrite and Nitromethane[J]. J.Am.Chem.Soc., 1985, 107: 1 566-1 573.

[6] Burnier RC, Byrd GD, Freiser BS Gas-phase Reactions of Fe with Ketones and Ethers[J]. J.Am.Chem.Soc., 1981, 103: 4 360-4 367.

[7] Carpenter CJ, van M PA, Koppen M T Bowers. Details of Potential Energy Surfaces Involving C-C Bond Activation: Reactions of Fe,Co, and Ni with Acetone[J]. J.Am.Chem.Soc., 1995, 117: 10 976-10 985.

[8] Sonnenfroh DM, Farrar JM Crossed-beam Studies of Energy and Angular Distributions of Organometallic Reactions: Decarbonylation of Acetaldehyde by Fe+ and Cr+[J]. J.Am.Chem.Soc., 1986, 108: 3 521-3 522.

[9] Frisch MJ, Trucks GW, Schlegel HB, . Gaussian 03 (revision B.05), 2003 Pittsburgh, PA Gaussian, Inc.

[10] Gonzalez C, Schlegel HB Reaction Path Following in Mass-weighted Internal Coordinates[J]. J.Phys.Chem., 1990, 94: 5 523-5 527.