Dimetalloylene (M‐E‐M) Complexes of Heavier Main Group Elements Ge, Sn, Pb, Bi via Cleavage of E‐X Bonds (X=N(SiMe 3 ) 2 , O t Bu) with an Iridium Hydride
Dimetalloylene (M‐E‐M) Complexes of Heavier Main Group Elements Ge, Sn, Pb, Bi via Cleavage of E‐X Bonds (X=N(SiMe 3 ) 2 , O t Bu) with an Iridium Hydride
复制标题
通过 E-X 键 (X=N(SiMe 3 ) 2 , O t Bu) 与氢化铱断裂，形成较重主族元素 Ge、Sn、Pb、Bi 的二亚金属烯 (M-E-M) 配合物
DOI：
10.1002/chem.202301863
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Tilley, T. Don
中科院分区：
文献类型：
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作者：
Saint‐Denis, Tyler G.;Zhang, Bowen;Settineri, Nicholas S.;Handford, Rex C.;Hall, Michael B.;Tilley, T. Don
二氢化物[MeBDIDipp]IrH4{BDI=(Dipp)NC(Me)CH(Me)CN（Dipp）的反应Dipp=2,6‐iPr2C6H3}与E[N(SiMe3)2]2（E=Sn, Pb）结合可得到不同寻常的二聚二金属四乙烯（[MeBDIDipp]IrH）2(μ2‐E)2)，收率高。此外，由[MeBDIDipp]Ir(H)2Ge[N(SiMe3)2]2热分解原位生成（[MeBDIDipp]IrH）2(μ2‐Ge)2。这些反应伴随着Ir - H对E - N(SiMe3)2键的明显裂解，从而使HN(SiMe3)2和h2分离。与此相反，（[MeBDIDipp]IrH）2(μ2‐E)2与过量的h2o2反应生成[MeBDIDipp]IrH4。改变反应物的浓度导致三聚体（[MeBDIDipp]IrH2）3(μ2‐E)3的形成。用15族酰胺进一步研究了这一合成路线的范围，并通过[MeBDIDipp] irh4与Bi(NMe2)3或Bi(OtBu)3反应制备了（[MeBDIDipp] irh4）2(μ2‐Bi)2，提供了第一个完全与过渡金属结合的“裸”双配位Bi原子。提出了一种可行的机理来解释这些产物的形成。对Ir2E2（E=Sn, Pb）化合物的计算研究表明，它们是在E中心具有受限非键孤对的开壳单线态化合物。相反，ir2bi2具有闭合壳层单重态基态。
Reactions of the IrVhydride [MeBDIDipp]IrH4{BDI=(Dipp)NC(Me)CH(Me)CN(Dipp); Dipp=2,6‐iPr2C6H3} with E[N(SiMe3)2]2(E=Sn, Pb) afforded the unusual dimeric dimetallotetrylenes ([MeBDIDipp]IrH)2(μ2‐E)2in good yields. Moreover, ([MeBDIDipp]IrH)2(μ2‐Ge)2was formed in situ from thermal decomposition of [MeBDIDipp]Ir(H)2Ge[N(SiMe3)2]2. These reactions are accompanied by liberation of HN(SiMe3)2and H2through the apparent cleavage of an E−N(SiMe3)2bond by Ir−H. In a reversal of this process, ([MeBDIDipp]IrH)2(μ2‐E)2reacted with excess H2to regenerate [MeBDIDipp]IrH4. Varying the concentrations of reactants led to formation of the trimeric ([MeBDIDipp]IrH2)3(μ2‐E)3. The further scope of this synthetic route was investigated with group 15 amides, and ([MeBDIDipp]IrH)2(μ2‐Bi)2was prepared by the reaction of [MeBDIDipp]IrH4with Bi(NMe2)3or Bi(OtBu)3to afford the first example of a “naked” two‐coordinate Bi atom bound exclusively to transition metals. A viable mechanism that accounts for the formation of these products is proposed. Computational investigations of the Ir2E2(E=Sn, Pb) compounds characterized them as open‐shell singlets with confined nonbonding lone pairs at the E centers. In contrast, Ir2Bi2is characterized as having a closed‐shell singlet ground state.