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二叔丁基二磷酸四面体烷的活化:通过P-C键裂解获得(tBuCP)(n = 2, 4)配体框架。

Activation of Di-tert-butyldiphosphatetrahedrane: Access to (tBuCP) (n=2, 4) Ligand Frameworks by P-C Bond Cleavage.

作者信息

Hierlmeier Gabriele, Wolf Robert

机构信息

Universität Regensburg, Institut für Anorganische Chemie, 93040, Regensburg, Germany.

出版信息

Angew Chem Int Ed Engl. 2021 Mar 15;60(12):6435-6440. doi: 10.1002/anie.202015680. Epub 2021 Feb 9.

Abstract

The first mixed phosphatetrahedranes were reported only recently and their reactivity is virtually unexplored. Herein, we present a reactivity study on di-tert-butyldiphosphatetrahedrane (1), which is the dimer of tert-butylphosphaalkyne. The (tBuCP) tetrahedron is activated selectively by N-heterocyclic carbene (NHC) nickel(I) and nickel(0) complexes, resulting in novel complexes featuring diverse (tBuCP) -frameworks (n=2, 4). Release of the (tBuCP) framework from one of the complexes was achieved by addition of CO gas. Furthermore, 1 can be used as a source for P  units by elimination of di-tert-butylacetylene in the coordination sphere of nickel.

摘要

首例混合磷四面体烷直到最近才被报道,其反应活性几乎尚未被探索。在此,我们展示了对二叔丁基二磷四面体烷(1)的反应活性研究,它是叔丁基磷炔的二聚体。(tBuCP)四面体通过氮杂环卡宾(NHC)镍(I)和镍(0)配合物被选择性活化,生成具有不同(tBuCP)骨架(n = 2, 4)的新型配合物。通过添加CO气体实现了从其中一种配合物中释放(tBuCP)骨架。此外,在镍的配位球中通过消除二叔丁基乙炔,1可以用作P单元的来源。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/72d4/7986217/5e573d2bf4ca/ANIE-60-6435-g002.jpg

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