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Nickel/zinc-catalyzed decarbonylative addition of anhydrides to alkynes: A DFT study

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Abstract

Density functional theory (DFT) was used to investigate the nickel- or nickel(0)/zinc- catalyzed decarbonylative addition of phthalic anhydrides to alkynes. All intermediates and transition states were optimized completely at the B3LYP/6-31+G(d,p) level. Calculated results indicated that the decarbonylative addition of phthalic anhydrides to alkynes was exergonic, and the total free energy released was −87.6 kJ mol−1. In the five-coordinated complexes M4a and M4b, the insertion reaction of alkynes into the Ni-C bond occurred prior to that into the Ni-O bond. The nickel(0)/zinc-catalyzed decarbonylative addition was much more dominant than the nickel-catalyzed one in whole catalytic decarbonylative addition. The reaction channel CA→M1'→T1'→M2'→T2'→M3a'→M4a'→T3a1'→M5a1' →T4a1'→M6a'→P was the most favorable among all reaction pathways of the nickel- or nickel(0)/zinc- catalyzed decarbonylative addition of phthalic anhydrides to alkynes. And the alkyne insertion reaction was the rate-determining step for this channel. The additive ZnCl2 had a significant effect, and it might change greatly the electron and geometry structures of those intermediates and transition states. On the whole, the solvent effect decreased the free energy barriers.

DFT study suggests that NiL4/ZnCl2 (L=PMe3) has higher catalysis than NiL4 in the synthesis of isocoumarin from phthalic anhydrides and alkynes.

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Acknowledgments

This work was supported by the Key Project of Science and Technology of the Ministry of Education, P. R. (grant No. 104263), Natural Science Foundation of Chongqing City, P. R. (grant No. CSTC-2004BA4024). Contract grant sponsor: Science and Technology of the Ministry of Education, People’s Republic of China (NO: 104263); Natural Science Foundation of Chongqing City, P. R. (No: CSTC-2004BA4024).

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, People’s Republic of China

    Qingxi Meng & Ming Li

  2. College of Chemistry and Material Science, Shandong Agricultural University, Taian, Shandong, 271018, People’s Republic of China

    Qingxi Meng

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  1. Qingxi Meng
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Correspondence to Qingxi Meng or Ming Li.

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Meng, Q., Li, M. Nickel/zinc-catalyzed decarbonylative addition of anhydrides to alkynes: A DFT study. J Mol Model 19, 4545–4554 (2013). https://doi.org/10.1007/s00894-013-1968-8

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  • DOI: https://doi.org/10.1007/s00894-013-1968-8

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