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首页> 外文期刊>Organometallics >Reversible Borylene Formation from Ring Opening of Pinacolborane and Other Intermediates Generated from Five-Coordinate Tris-Boryl Complexes: Implications for Catalytic C-H Borylation
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Reversible Borylene Formation from Ring Opening of Pinacolborane and Other Intermediates Generated from Five-Coordinate Tris-Boryl Complexes: Implications for Catalytic C-H Borylation

机译：五碳三配位三芳基配合物生成的频哪醇硼烷和其他中间体的开环形成可逆的亚芳基：催化C-H硼化反应的意义

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摘要

Catalytic C-H borylation using the five-coordinate tris-boryl complex (dippe)Ir(Bpin)(3) (5a, dippe = 1,2-bis(diisopropylphosphino) ethane) has been examined using P-31 {H-1} and NMR spectroscopy. Compound 5a was shown to react rapidly and reversibly with HBpin to generate a six-coordinate borylene complex, (dippe)Ir(H)-(Bpin)(2)(BOCMe(2)CMe(2)OBpin) (6), whose structure was confirmed by X-ray crystallography. Under catalytic conditions, the H-2 generated from C-H borylation converted compound 6 to a series of intermediates. The first is tentatively assigned from P-31{H-1} and H-1 NMR spectra as (dippe)Ir(H(2)B(3)pin(3)) (7), which is the product of formal H-2 addition to compound 5a. As catalysis progressed, compound 7 was converted to a new species with the formula (dippe)Ir(H(3)B(2)pin(2)) (8), which arose from H-2 addition to compound 7 with loss of HBpin. Compound 8 was characterized by P-31{H-1} and H-1 NMR spectroscopy, and its structure was confirmed by X-ray crystallography, where two molecules with different ligand orientations were found in the unit cell. DFT calculations support the formulation of compound 8 as an Ir-III agostic borane complex, (dippe)IrH2(Bpin)(eta(2)-HBpin). Compound 8 was gradually converted to (dippe)Ir(H(4)Bpin) (9), which was characterized by P-31{H-1} and H-1 NMR spectroscopy and X-ray crystallography. DFT calculations favor its formulation as an agostic borane complex of Ir-III with the formula (dippe)IrH3(eta(2)-HBpin). Compound 9 reacted further with H-2 to afford the dimeric structure [(dippe)IrH2(mu(2)-H)](2) (10), which was characterized by H-1 NMR and X-ray crystallography. Compounds 7-10 are in equilibrium when H2 and HBpin are present.
机译：使用P-31 {H-1}和P-31（H-1）考察了使用五配位三硼烷基配合物（dippe）Ir（Bpin）（3）（5a，dippe = 1,2-bis（diisopropylphosphino）乙烷）催化的CH硼化反应。 NMR光谱。已显示化合物5a与HBpin快速可逆地反应，生成六配位的硼烯络合物（dippe）Ir（H）-（Bpin）（2）（BOCMe（2）CMe（2）OBpin）（6），其X射线晶体学证实了其结构。在催化条件下，由C-H硼化反应生成的H-2将化合物6转化为一系列中间体。暂时从P-31 {H-1}和H-1 NMR光谱中暂定为（dippe）Ir（H（2）B（3）pin（3））（7），这是形式H的产物-2加至化合物5a。随着催化的进行，化合物7转化为具有式（dippe）Ir（H（3）B（2）pin（2））（8）的新物种，该化合物是由H-2加成化合物7而损失的。 HBpin。化合物8通过P-31 {H-1}和H-1 NMR谱表征，并通过X射线晶体学确认其结构，其中在单位细胞中发现两个具有不同配体取向的分子。 DFT计算支持将化合物8制成Ir-III异硼烷络合物（dippe）IrH2（Bpin）（eta（2）-HBpin）。化合物8逐渐转化为（dippe）Ir（H（4）Bpin）（9），其特征在于通过P-31 {H-1}和H-1 NMR光谱学和X射线晶体学表征。 DFT计算有利于将其配方为Ir-III的硼烷络合物，分子式为（dippe）IrH3（eta（2）-HBpin）。化合物9进一步与H-2反应，得到二聚结构[（dippe）IrH2（mu（2）-H）]（2）（10），其通过H-1 NMR和X射线晶体学表征。当存在H2和HBpin时，化合物7-10处于平衡状态。

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