Himo Fahmi, Demko Zachary P, Noodleman Louis, Sharpless K Barry
Department of Molecular Biology, TPC-15, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA.
J Am Chem Soc. 2003 Aug 20;125(33):9983-7. doi: 10.1021/ja030204q.
The mechanism by which zinc(II) catalyzes the union of an azide ion with organic nitriles to form tetrazoles is investigated by means of density functional theory using the hybrid functional B3LYP. The calculations indicate that coordination of the nitrile to the zinc ion is the dominant factor affecting the catalysis; this coordination substantially lowers the barrier for nucleophilic attack by azide. Relative reaction rates of catalyzed and uncatalyzed tetrazole formation also provide experimental support for this conclusion.
采用密度泛函理论中的杂化泛函B3LYP，研究了锌（II）催化叠氮离子与有机腈结合形成四唑的反应机理。计算结果表明，腈与锌离子的配位是影响催化作用的主要因素；这种配位作用显著降低了叠氮亲核进攻的势垒。催化和未催化形成四唑的相对反应速率也为这一结论提供了实验支持。
