title: Nickel/zinc-catalyzed decarbonylative addition of anhydrides to alkynes: a DFT study.
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.
authors: College of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, People's Republic of China, qingxim@sdau.edu.cn.
authors: Qingxi
authors: Q
authors: Meng
authors: Ming
authors: M
authors: Li
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D002712:Chlorides / Q000737:chemistry*; D003198:Computer Simulation; D005740:Gases / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*; D010796:Phthalic Anhydrides / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics; D017967:Zinc Compounds / Q000737:chemistry*
chemical_list: D000480:Alkynes; D002712:Chlorides; D005740:Gases; D010796:Phthalic Anhydrides; D017967:Zinc Compounds; D009532:Nickel; C016837:zinc chloride
references: Phys Rev B Condens Matter. 1988 Jan 15;37(2):785-789
references: 9944570
references: Cancer Res. 2004 Dec 1;64(23):8512-6
references: 15574755
references: J Am Chem Soc. 2008 Dec 24;130(51):17226-7
references: 19049285
references: Org Lett. 2007 Feb 15;9(4):587-9
references: 17243709
references: J Am Chem Soc. 2007 Mar 7;129(9):2718-25
references: 17295486
references: Angew Chem Int Ed Engl. 2007;46(43):8250-3
references: 17893896
references: Curr Pharm Des. 2004;10(30):3781-96
references: 15579071
references: J Am Chem Soc. 2003 Sep 3;125(35):10498-9
references: 12940714