将磷鎓离子插入双环[1.1.0]四磷杂丁烷铁配合物中。
Insertion of Phosphenium Ions into a Bicyclo[1.1.0]Tetraphosphabutane Iron Complex.
作者信息
Weber Martin, Balázs Gábor, Virovets Alexander V, Peresypkina Eugenia, Scheer Manfred
机构信息
Institute of Inorganic Chemistry, University of Regensburg, Universitätsstrasse 31, 93040 Regensburg, Germany.
出版信息
Molecules. 2021 Jun 26;26(13):3920. doi: 10.3390/molecules26133920.
By reacting [{Cp‴Fe(CO)}(µ,η-P)] () with in situ generated phosphenium ions [PhP][A] ([A] = [OTf] = [OSCF], [PF]), a mixture of two main products of the composition [{Cp‴Fe(CO)}(µ,η-P(CH))][PF] ( and ) could be identified by extensive P NMR spectroscopic studies at 193 K. Compound was also characterized by X-ray diffraction analysis, showing the rarely observed bicyclo[2.1.0]pentaphosphapentane unit. At room temperature, the novel compound [{Cp‴Fe}(µ,η-PPh){Cp‴(CO)Fe}][PF] () is formed by decarbonylation. Reacting with in situ generated diphenyl arsenium ions gives short-lived intermediates at 193 K which disproportionate at room temperature into tetraphenyldiarsine and [{Cp‴Fe(CO)}(µ,η-P)][OTf] () containing a tetracyclo[3.3.0.0.0]octaphosphaoctane ligand.
通过使[{Cp‴Fe(CO)}(µ,η-P)]（）与原位生成的鏻离子[PhP][A]（[A] = [OTf] = [OSCF]，[PF]）反应，在193 K下通过广泛的磷核磁共振光谱研究可以鉴定出两种主要产物[{Cp‴Fe(CO)}(µ,η-P(CH))][PF]（和）的混合物。化合物也通过X射线衍射分析进行了表征，显示出罕见的双环[2.1.0]戊磷戊烷单元。在室温下，新型化合物[{Cp‴Fe}(µ,η-PPh){Cp‴(CO)Fe}][PF]（）通过脱羰基反应形成。使与原位生成的二苯基砷离子反应，在193 K下产生寿命短暂的中间体，该中间体在室温下歧化为四苯基二砷和含有四环[3.3.0.0.0]八磷辛烷配体的[{Cp‴Fe(CO)}(µ,η-P)][OTf]（）。
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