Mono- and Dicoordinate Germanium(0) as a Four-Electron Donor.
Mono- and Dicoordinate Germanium(0) as a Four-Electron Donor.
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DOI：
10.1002/chem.201800071
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发表时间：
2018-02
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通讯作者：
Debdeep Mandal;Debabrata Dhara;Avijit Maiti;Lukas Klemmer;V. Huch;Michael Zimmer;H. Rzepa;D. Scheschkewitz;Anukul Jana
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作者：
Debdeep Mandal;Debabrata Dhara;Avijit Maiti;Lukas Klemmer;V. Huch;Michael Zimmer;H. Rzepa;D. Scheschkewitz;Anukul Jana
我们报道了 Fe3 Ge 和 Fe2 Ge 化学计量中的分子铁锗化物基序的合成和分离，这些基序通过 N-杂环卡宾 (NHC) 和一氧化碳 (CO) 配体的配位来稳定。 NHCiPr2Me2 ⋅Ge[Fe(CO)4 ][Fe2 (CO)8 ] (NHCiPr2Me2 =1,3-二异丙基-4,5-二甲基咪唑-2-亚基)，一种只有一个 NHC 作为辅助配体的锗(0)配体，在单核 [Fe(CO)4 ] 和双核 [(CO)4 之间呈现桥接配位模式FeFe(CO)4]单元在溶液中两种结合模式之间快速交换。通过 NBO 和 ELF 计算以及 DFT 方法分析了该物质的电子结构，以及其流变配位行为的机制细节。用空间要求较低的 NHCMe4 (NHCMe4 =1,3,4,5-四甲基咪唑-2-亚基)处理 NHCiPr2Me2 ⋅Ge[Fe(CO)4 ] [Fe2 (CO)8 ] 会产生双核铁络合物 (NHCMe4 )2 Ge[Fe(CO)4 ]2，其中包含具有两个稳定 NHC 当量的桥联甲芽酮配体。
We report the synthesis and isolation of molecular iron germanide motifs in the stoichiometry of Fe3 Ge and Fe2 Ge, which are stabilized by the coordination of N-heterocyclic carbene (NHC) and carbon monoxide (CO) ligands. NHCiPr2Me2 ⋅Ge[Fe(CO)4 ][Fe2 (CO)8 ] (NHCiPr2Me2 =1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene), a germanium(0) ligand with just one NHC as an auxiliary ligand, assumes a bridging coordination mode between a mononuclear [Fe(CO)4 ] and a dinuclear [(CO)4 FeFe(CO)4 ] unit with rapid exchange between the two binding modes in solution. The electronic structure of this species is analysed by NBO and ELF calculations with DFT methods, as well as the mechanistic details of its fluxional coordination behaviour. Treatment of NHCiPr2Me2 ⋅Ge[Fe(CO)4 ] [Fe2 (CO)8 ] with the sterically less demanding NHCMe4 (NHCMe4 =1,3,4,5-tetramethylimidazol-2-ylidene) leads to a dinuclear iron complex (NHCMe4 )2 Ge[Fe(CO)4 ]2 that contains a bridging germylone ligand with two stabilizing NHC equivalents.