Hierlmeier Gabriele, Coburger Peter, Bodensteiner Michael, Wolf Robert
University of Regensburg, Institute of Inorganic Chemistry, 93040, Regensburg, Germany.
Angew Chem Int Ed Engl. 2019 Nov 18;58(47):16918-16922. doi: 10.1002/anie.201910505. Epub 2019 Oct 24.
While tetrahedranes as a family are scarce, neutral heteroatomic species are all but unknown, with the only reported example being AsP . Herein, we describe the isolation of a neutral heteroatomic X Y molecular tetrahedron (X, Y=p-block elements), which also is the long-sought-after free phosphaalkyne dimer. Di-tert-butyldiphosphatetrahedrane, (tBuCP) , is formed from the monomer tBuCP in a nickel-catalyzed dimerization reaction using [(NHC)Ni(CO) ] (NHC=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (IMes) and 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene (IPr)). Single-crystal X-ray structure determination of a silver(I) complex confirms the structure of (tBuCP) . The influence of the N-heterocyclic carbene ligand on the catalytic reaction was investigated, and a mechanism was elucidated using a combination of synthetic and kinetic studies and quantum chemical calculations.
虽然四面体烷作为一类化合物较为稀少，但中性杂原子物种几乎不为人知，唯一报道的例子是砷化磷。在此，我们描述了一种中性杂原子X Y分子四面体（X、Y为p区元素）的分离，它也是长期以来备受追寻的游离磷炔二聚体。二叔丁基二磷四面体烷（(tBuCP) ）由单体tBuCP在镍催化的二聚反应中形成，该反应使用[(NHC)Ni(CO) ]（NHC = 1,3 - 双（2,4,6 - 三甲基苯基）咪唑啉 - 2 - 亚基（IMes）和1,3 - 双（2,6 - 二异丙基苯基）咪唑啉 - 2 - 亚基（IPr））。对一种银（I）配合物的单晶X射线结构测定证实了(tBuCP) 的结构。研究了氮杂环卡宾配体对催化反应的影响，并通过综合合成研究、动力学研究和量子化学计算阐明了反应机理。
