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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Hemilabile bonding of 1-oxa-4,7-dithiacyclononane in cyclometallated palladium(ii) complexes
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Hemilabile bonding of 1-oxa-4,7-dithiacyclononane in cyclometallated palladium(ii) complexes

机译：血管基钯（II）复合物中1-OXA-4,7-二乙酰丙烷的血管键合

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摘要

The synthesis and characterization of a series of cyclometallated complexes of Pd(ii) incorporating the mixed donor ligand 1-oxa-4,7-dithiacyclononane ([9]aneS(2)O) are presented in this study. Complexes of the form [Pd((CN)-N-boolean AND)([9]aneS(2)O)](PF6) ((CN)-N-boolean AND = 2-phenylpyridine (ppy) 1b, 4-(2-pyridyl)benzaldehyde (ppyCHO) 2b, 7,8-benzoquinoline (bzq) 3b, 2-benzothienylpyridine (btp) 4b, 2-phenylbenzothiazole (pbt) 5b), were obtained in high-yield from a simple two-step synthetic scheme. All of these complexes were fully characterized by NMR, ESI-MS, IR, combustion analyses, and most (1b, 2b, 4b, 5b) by X-ray crystallography. Solution H-1 and C-13 NMR studies of [Pd((CN)-N-boolean AND)([9]aneS(2)O)](PF6) complexes demonstrate complicated [9]aneS(2)O behavior at room temperature. Variable temperature NMR reveals dynamic bonding of the [9]aneS(2)O ligand consistent with the presence of both endodentate and exodentate bonding modes. This is in stark contrast to the related [9]aneS(3) (1,4,7-trithiacyclononane) cogeners that demonstrate fluxional endodentate bonding only in solution. X-ray structures reveal only exodenate [9]aneS(2)O bonding in this series, unlike the related [9]aneS(3) complexes that show endodenate bonding with an axial PdMIDLINE HORIZONTAL ELLIPSISS interaction. DFT calculations performed on endo and exo [9]aneS(2)O bonding forms of 4b, as well as a transition state calculation for interconversion, suggest reasonable access to both bonding forms based on the energy barrier. Natural bond order calculations provide further evidence for a weak axial PdMIDLINE HORIZONTAL ELLIPSISO interaction in the endo form of 4b.
机译：一系列（ⅱ）将所述混合供体的Pd环金属化配合物的合成和表征配体1-氧杂-4,7- dithiacyclononane（[9] ANES（2）O）在本研究中提出。形式的配合物[钯（（CN）-N-布尔AND）（[9] ANES（2）O）]（PF 6）（（CN）-N-布尔AND = 2-苯基吡啶（PPY）1b中，4- （2-吡啶基）苯甲醛（ppyCHO）2b中，7,8-苯并喹啉（BZQ）3B，2-苯并噻（BTP）4B，2-苯基苯并噻唑（PBT）5b）中，分别在高产量从一个简单的两步骤中获得合成路线。所有这些络合物的通过X射线晶体学进行了完全表征通过NMR，ESI-MS，IR，燃烧分析，最（1B，2B，4B，5B）。溶液H-1和[（（CN）-N-布尔AND）的Pd（[9] ANES（2）O）]的C-13核磁共振研究（PF6）络合物演示了复杂[9] ANES（2）O行为在室内温度。可变温度NMR揭示[9] ANES的动态接合（2）O配体与两个endodentate和exodentate接合模式的存在一致。与此形成鲜明对比的是仅在溶液中表现出fluxional endodentate接合相关的[9] ANES（3）（1,4,7- trithiacyclononane）cogeners。 X射线结构仅露出exodenate [9] ANES（2）O键在这一系列中，不同于现有[9] ANES，显示具有轴向PdMIDLINE HORIZONTAL ELLIPSISS相互作用endodenate接合（3）的复合物。 DFT计算上内型和外型进行[9] ANES（2）O键合形式4b的，以及用于相互转换的过渡状态计算，建议基于该能量势垒二者结合的形式合理的访问。自然键顺序计算提供一种弱轴向在4b的内切形式PdMIDLINE HORIZONTAL ELLIPSISO相互作用的进一步证据。

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