Synthesis of the open-shell 3d-transition metal(II) bis(phosphinidenide) [Mn{P(sIDipp)}2].
Synthesis of the open-shell 3d-transition metal(II) bis(phosphinidenide) [Mn{P(sIDipp)}2].
复制标题
开壳层3d-过渡金属(II)双(膦酰亚胺)[Mn{P(sIDipp)}2]的合成
DOI：
10.1039/d1dt03805b
复制
发表时间：
2022
影响因子：
4
通讯作者：
C. G. Werncke
中科院分区：
文献类型：
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作者：
R. Weller;C. von Hänisch;C. G. Werncke
介绍了第一个均配开壳层过渡金属磷酰亚胺的合成和表征。通过 [MnL2] (L = -N(SiMe3)2) 与 [(sIDipp)PK] (sIDipp = 1,3-双(2,6-二异丙基苯基)-咪唑烷-2-亚基) 反应，观察到形成 [Mn{P(sIDipp)}2]，而不是最初预期的加合物 [KMn{P(sIDipp)}L2]。有趣的是，溶剂从甲苯变为正戊烷导致后处理后形成[(sIDipp)PK2(Et2O)4][MnL3]，其可以被视为[Mn{P(sIDipp)}2]形成过程中的中间体。与锰相反，高还原性磷酰亚胺 [(sIDipp)P]− 不能通过与低配位高自旋铁 (II) 中心配位以类似的方式稳定。
The synthesis and characterization of the first homoleptic open-shell transition metal phosphinidenide is presented. By reacting [MnL2] (L = −N(SiMe3)2) with [(sIDipp)PK] (sIDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolidine-2-ylidene), the formation of [Mn{P(sIDipp)}2] instead of the initially expected adduct [KMn{P(sIDipp)}L2] is observed. Interestingly, a solvent change from toluene to n-pentane leads to the formation of [(sIDipp)PK2(Et2O)4][MnL3] after work-up, which can be seen as intermediate in the formation process of [Mn{P(sIDipp)}2]. Contrary to manganese, the highly reducing phosphinidenide [(sIDipp)P]− cannot be stabilized in an analogous fashion by coordination to a low-coordinate high-spin iron(II) center.