Weller Ruth, Balmer Markus, Hänisch Carsten von, Gunnar Werncke C
Department of Chemistry, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, D-35032 Marburg, Germany.
Dockweiler Chemicals GmbH, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, D-35032 Marburg, Germany.
Dalton Trans. 2022 Feb 1;51(5):1765-1768. doi: 10.1039/d1dt03805b.
The synthesis and characterization of the first homoleptic open-shell transition metal phosphinidenide is presented. By reacting [MnL] (L = -N(SiMe)) with [(sIDipp)PK] (sIDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolidine-2-ylidene), the formation of [Mn{P(sIDipp)}] instead of the initially expected adduct [KMn{P(sIDipp)}L] is observed. Interestingly, a solvent change from toluene to -pentane leads to the formation of [(sIDipp)PK(EtO)][MnL] after work-up, which can be seen as intermediate in the formation process of [Mn{P(sIDipp)}]. 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.
首次报道了首例同配开壳层过渡金属次膦化物的合成与表征。通过使[MnL]（L = -N(SiMe)）与[(sIDipp)PK]（sIDipp = 1,3 - 双(2,6 - 二异丙基苯基) - 咪唑啉 - 2 - 亚基）反应，观察到形成的是[Mn{P(sIDipp)}]而非最初预期的加合物[KMn{P(sIDipp)}L]。有趣的是，将溶剂从甲苯换为正戊烷后，后处理得到[(sIDipp)PK(EtO)][MnL]，它可视为[Mn{P(sIDipp)}]形成过程中的中间体。与锰不同，高还原性的次膦化物[(sIDipp)P]不能通过与低配位高自旋铁(II)中心配位以类似方式得到稳定。
