A Highly-Reduced Cobalt Terminal Carbyne: Divergent Metal- and α-Carbon-Centered Reactivity,Journal of the American Chemical Society

当前位置： X-MOL 学术 › J. Am. Chem. Soc. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

A Highly-Reduced Cobalt Terminal Carbyne: Divergent Metal- and α-Carbon-Centered Reactivity
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-06-15 , DOI: 10.1021/jacs.8b05019
Charles C. Mokhtarzadeh ₁ , Curtis E. Moore ₁ , Arnold L. Rheingold ₁ , Joshua S. Figueroa ₁

Affiliation

Reported here is the isolation of a dianionic cobalt terminal carbyne derived from chemical reduction of an encumbering isocyanide ligand. Crystallographic, spectroscopic and computational data reveal that this carbyne possesses a low-valent cobalt center with an extensively filled d-orbital manifold. This electronic character renders the cobalt center the primary site of nucleophilicity upon reaction with protic substrates and silyl electrophiles. However, reactions with internal alkynes result in [2+2] cycloaddition with the carbyne carbon to form a new C-C bond.

中文翻译：

高度还原的钴末端卡宾：不同的金属和 α-碳中心反应性

这里报道的是从阻碍异氰化物配体的化学还原衍生的双阴离子钴末端碳炔的分离。晶体学、光谱学和计算数据表明，这种碳炔拥有一个低价钴中心和一个广泛填充的 d 轨道流形。这种电子特性使钴中心成为与质子底物和甲硅烷基亲电试剂反应时亲核性的主要位点。然而，与内部炔烃的反应会导致 [2+2] 环加成与碳炔碳形成新的 CC 键。

更新日期：2018-06-15

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南