NHC‐Stabilized Parent Phosphinidene Adducts of Metal(II) Hexamethyldisilazanides of Manganese – Cobalt and Their Lability in Solution
NHC‐Stabilized Parent Phosphinidene Adducts of Metal(II) Hexamethyldisilazanides of Manganese – Cobalt and Their Lability in Solution
复制标题
NHCâ 锰钴金属 (II) 六甲基二硅氮烷化合物的稳定母膦加合物及其在溶液中的稳定性
DOI：
10.1002/zaac.202100338
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
C. G. Werncke
中科院分区：
文献类型：
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作者：
R. Weller;A. Gonzalez;H. Gottschling;C. von Hänisch;C. G. Werncke
描述了N-杂环卡宾（NHC）稳定的“母体”亚膦[（sIDipp）PH]（Dipp= 2，6-二异丙基苯基）对3d-金属（II）六甲基二硅氮烷的行为。这导致形成三配位的亚膦加合物[M{PH（sIDipp）}{N（SiMe 3）2}2]（M= Mn-Co），如通过X射线衍射分析所证明的。在溶液中，所有化合物都表现出强顺磁性，这限制了对钴的NMR光谱检查。在这里，它表明，该系统是协调的高度流动，这是减轻冷却。在低温下，少量的游离亚膦基通过31 P NMR光谱变得进一步明显，这暗示部分配体配位与[M{N（SiMe 3）2}2]二聚化竞争，并且亚膦基配体的整体结合较弱。在过量的亚膦或膦（PCy 3）的存在下证明了快速的化学交换，而乙醚被证明是更强的供体配体。
The behavior of theN‐heterocyclic carbene (NHC) stabilized ‘parent’ phosphinidene [(sIDipp)PH] (Dipp=2,6‐di‐isopropylphenyl) towards 3d‐metal(II) hexamethyldisilazanides is described. This leads to formation of the three‐coordinated phosphinidene adducts [M{PH(sIDipp)}{N(SiMe3)2}2] (M=Mn−Co), as evidenced by X‐Ray diffraction analysis. In solution, all compounds exhibit strong paramagnetism that limited NMR spectroscopic examinations to cobalt. Here it shows that the system is coordinatively highly fluxional, which is mitigtated upon cooling. At low temperatures, small amounts of free phosphinidene becomes further evident by31P NMR spectroscopy that implicates in part ligand coordination competes with [M{N(SiMe3)2}2] dimerisation and an overall weak binding of the phosphinidene ligand. The rapid chemical exchange is evidenced in the presence of an excess of phosphinidene or a phosphine (PCy3), whereas diethyl ether proved as a stronger donor ligand.