期刊
ACS CATALYSIS
卷 7, 期 7, 页码 4796-4804出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.7b00978
关键词
dinuclear; catalysis; density functional theory; nickel; alkyne cyclotrimerization
资金
- BYU College of Physical and Mathematical Sciences
- BYU Department of Chemistry and Biochemistry
Homodinuclear transition-metal catalysts with a direct metal metal bond have the potential to induce novel reaction mechanisms and selectivity compared with mononuclear catalysts. The dinuclear (i-PrNDI)Ni-2(C6H6) (NDI = naphthyridine-diimine) complex catalyzes selective cyclotrimerization of monosubstituted alkynes, whereas mononuclear Ni catalysts generally give cyclotetramerization of alkynes. Density functional theory calculations reveal that the homodinuclear Ni-Ni catalyst induces a spin crossover mechanism that involves metallacyclopentadiene and nonclassical bridging metallacycloheptatriene intermediates. The cis configuration of the nonclassical bridging metallacycloheptatriene Ni-vinyl bonds results in alkyne cyclotrimerization by fast reductive elimination. This dinuclear mechanism differs from previously reported mononuclear Ni mechanisms and provides an explanation for cyclotrimerization versus cyclotetramerization selectivity and arene regioselectivity.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据