σ or π? Bonding interactions in a series of rhenium metallotetrylenes
σ or π? Bonding interactions in a series of rhenium metallotetrylenes
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Ï 还是 Ï？
DOI：
10.1039/d1dt00129a
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发表时间：
2021
影响因子：
4
通讯作者：
Arnold, John
中科院分区：
文献类型：
--
作者：
Ouellette, Erik T.;Carpentier, Ambre;Joseph Brackbill, I.;Lohrey, Trevor D.;Douair, Iskander;Maron, Laurent;Bergman, Robert G.;Arnold, John
低价铼(I)配合物Na[Re(η5-Cp)(BDI)]（BDI = N,N′-双(2,6-二异丙基苯基)-3,5-二甲基-β-二酮亚胺盐）和一系列脒基负载的ECl[PhC(NtBu)2]（E = Si, Ge, Sn）形式的三萘嵌苯之间的盐复分解反应生成铼金属四萘嵌苯Re(E[PhC(NtBu)2])(η5-Cp)(BDI) (E = Si (1a), Ge (2), Sn (4)) 具有不同程度的 Re-E 多重键合。铼-亚锡基 4 采用具有 Re-E 单键的 σ-金属四亚萘基排列，而铼-亚甲硅基 (1a) 和-亚甲锗烷基 (2) 均通过 π 相互作用形成短 Re-E 多重键。研究发现温度在 Na[Re(η5-Cp)(BDI)] 和 SiCl[PhC(NtBu)2] 之间的反应中起着至关重要的作用，因为控制反应条件可以分离出不寻常的铼-硅烷 (BDI)Re(μ-η5:η1-C5H4)(SiH[PhC(NtBu)2]) (1b) 和二氮桥接的铼-硅烯， (η5-Cp)(BDI)Re(μ-N2)Si[PhC(NtBu)2] (1c)，以及 1a。最后，Na[Re(η5-Cp)(BDI)] 与 GeCl2·二恶烷反应生成了一种罕见的 μ2-tetrelido 配合物，μ2-Ge[Re(η5-Cp)(BDI)]2 (3)。通过各种光谱、结构和计算研究的视角讨论了这些复合物内的键合相互作用。
Salt metathesis reactions between a low-valent rhenium(I) complex, Na[Re(η5-Cp)(BDI)] (BDI = N,N′-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate), and a series of amidinate-supported tetrylenes of the form ECl[PhC(NtBu)2] (E = Si, Ge, Sn) led to rhenium metallotetrylenes Re(E[PhC(NtBu)2])(η5-Cp)(BDI) (E = Si (1a), Ge (2), Sn (4)) with varying extents of Re–E multiple bonding. Whereas the rhenium–stannylene 4 adopts a σ-metallotetrylene arrangement featuring a Re–E single bond, the rhenium–silylene (1a) and –germylene (2) both engage in π-interactions to form short Re–E multiple bonds. Temperature was found to play a crucial role in reactions between Na[Re(η5-Cp)(BDI)] and SiCl[PhC(NtBu)2], as manipulation of reaction conditions led to isolation of an unusual rhenium–silane, (BDI)Re(μ-η5:η1-C5H4)(SiH[PhC(NtBu)2]) (1b) and a dinitrogen bridged rhenium–silylene, (η5-Cp)(BDI)Re(μ-N2)Si[PhC(NtBu)2] (1c), in addition to 1a. Finally, the reaction of Na[Re(η5-Cp)(BDI)] with GeCl2·dioxane led to a rare μ2-tetrelido complex, μ2-Ge[Re(η5-Cp)(BDI)]2 (3). Bonding interactions within these complexes are discussed through the lens of various spectroscopic, structural, and computational investigations.