Hydrodeoxygenative Cyclotetramerization of Carbon Monoxide by a Trinuclear Titanium Polyhydride Complex,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.)

Hydrodeoxygenative Cyclotetramerization of Carbon Monoxide by a Trinuclear Titanium Polyhydride Complex
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-11-10 , DOI: 10.1021/jacs.0c10403
Shaowei Hu ₁ , Takanori Shima _{1,

2} , Zhaomin Hou _{1,

2}

Affiliation

The reductive coupling of carbon monoxide (CO) by metal hydrides is of fundamental interest and practical importance. Herein we report an unprecedented hydrodeoxygenative cyclotetramerization of CO by a trinuclear titanium polyhydride complex [(C5Me4SiMe3)Ti]3(μ3-H)(μ2-H)6 (1). The reaction of CO with 1 at -78 °C gave an ethen-1,2-diyl species [CH═CH]2- through the hydrodeoxygenative dimerization of two molecules of CO, which upon cycloaddition to another two molecules of CO afforded a cyclobuten-3,4-diyl-1,2-diolate unit [C4H2O2]4-. The hydrogenolysis of the [C4H2O2]4- species with H2 yielded a tetrahydrocyclobuten-1,2-diolate species [C4H4O2]2-, which on heating at 100 °C gave a cyclobuten-2-yl-1-olate product [C4H4O]2-. The acidolysis of the [C4H2O2]4- and [C4H4O]2- species with HCl afforded γ-butyrolactone and cyclobutanone, respectively.

中文翻译：

三核钛多氢化物配合物对一氧化碳的加氢脱氧环四聚反应

金属氢化物对一氧化碳 (CO) 的还原偶联具有重要意义和实际意义。在此，我们报告了一种前所未有的 CO 加氢脱氧环四聚反应，由三核多氢化钛络合物 [(C5Me4SiMe3)Ti]3(μ3-H)(μ2-H)6 (1) 进行。CO 与 1 在 -78 °C 下的反应通过两分子 CO 的加氢脱氧二聚反应得到了一种 ethen-1,2-diyl 物质 [CH=CH]2-，在与另外两分子 CO 环加成后得到环丁烯-3,4-二基-1,2-二醇单元[C4H2O2]4-。[C4H2O2]4- 物质与 H2 的氢解产生四氢环丁烯-1,2-二醇物质 [C4H4O2]2-，在 100°C 加热时得到环丁烯-2-基-1-醇酸酯产物 [C4H4O] 2-。[C4H2O2]4- 和 [C4H4O]2- 物质与 HCl 的酸解分别得到 γ-丁内酯和环丁酮。

更新日期：2020-11-10

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11