A Phosphanyl‐Substituted Benzo‐1,3,2‐Dioxaborol as Ambiphilic Bifunctional Lewis Donor–Acceptor Unit
A Phosphanyl‐Substituted Benzo‐1,3,2‐Dioxaborol as Ambiphilic Bifunctional Lewis Donor–Acceptor Unit
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膦酰基取代的苯并-1,3,2-二氧杂硼醇作为两亲性双功能路易斯供体-受体单元
DOI：
10.1002/ejic.200800024
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发表时间：
2008
影响因子：
2.3
通讯作者：
T. Schleid
中科院分区：
文献类型：
--
作者：
Samir H. Chikkali;Silja Magens;D. Gudat;M. Nieger;I. Hartenbach;T. Schleid
3-[（二苯基膦基）甲基]苯-1，2-二醇（1）与苯基硼酸缩合得到膦官能化的苯并-1，3，2-二氧硼杂环戊烯3。通过与（cod）PdCl 2和一些氮供体（4-二甲氨基吡啶、二氮杂-[2.2.2]-双环辛烷、吡啶）的反应，证明了该物种通过P-中心供体作为刘易斯碱和通过B-中心受体位点作为刘易斯酸的能力。这些反应产生的钯膦配合物或胺硼烷加合物，其特征在于光谱数据，在某些情况下，通过单晶X-射线衍射研究。磷烷官能化的苯并-1，3，2-二氧硼杂环戊烯3与dabco的Pd络合物或3与（cod）PdCl 2的dmap加合物的反应得到的材料通过分析数据和固态NMR光谱数据表征为三重刘易斯酸/碱络合物，并且含有PPd和BN配价键。即使这些加合物在溶液中是不稳定的，这些实验的结果表明3作为双官能供体/受体配体，这是作为主链有机金属聚合物或多金属配合物的结构单元的潜在用途的能力。（© Wiley-VCH Verlag GmbH & Co. KGaA，69451魏因海姆，德国，2008）
Condensation of 3-[(diphenylphosphanyl)methyl]benzene-1,2-diol (1) with phenyl boronic acid gave a phosphane-functionalised benzo-1,3,2-dioxaborol 3. The ability of this species to act as a Lewis base through the P-centered donor and as a Lewis acid through the B-centered acceptor sites was demonstrated by the reactions with (cod)PdCl2 and some nitrogen donors (4-dimethylaminopyridine, diaza-[2.2.2]-bicyclooctane, pyridine). These reactions yielded either palladium–phosphane complexes or amine–borane adducts that were characterised by spectroscopic data and, in some cases, by single-crystal X-ray diffraction studies. Reactions of a Pd complex of the phosphane-functionalised benzo-1,3,2-dioxaborol 3 with dabco, or of the dmap adduct of 3 with (cod)PdCl2, gave materials that were characterised by analytical data and solid-state NMR spectroscopic data as triple Lewis acid/base complexes and that contain both PPd and BN dative bonds. Even though these adducts were unstable in solution, the results of these experiments demonstrate the ability of 3 to act as a bifunctional donor/acceptor ligand, which is of potential use as a building block for main chain organometallic polymers or multimetallic complexes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)