Synthesis and theoretical analysis of palladium complexes of polydimethylsiloxane functionalised pyridine and their catalytic activity in alcohol oxidations under low polar conditions

Herbert M.; Montilla F.; Galindo A.

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Synthesis and theoretical analysis of palladium complexes of polydimethylsiloxane functionalised pyridine and their catalytic activity in alcohol oxidations under low polar conditions

机译：低极性条件下聚二甲基硅氧烷官能化吡啶钯配合物的合成及理论分析及其在醇氧化中的催化活性

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Palladium(II) complexes of polydimethylsiloxane (PDMS)-functionalised pyridine (1), [Pd(OAc)_2(1)_2] (2) and [PdCl _2(1)_2] (3), were synthesised and characterised. The cis/trans isomerism of models of complex 3 was investigated using DFT calculations. Models of complex 2 were also theoretically analysed, to identify any possible C-H?O interactions. Complex 2 was investigated as a catalyst for selective alcohol oxidations both under solventless conditions and in supercritical carbon dioxide (scCO_2). In scCO_2 the presence of 1 was found to stabilise the palladium complex, inhibiting its decomposition to Pd(0), a stabilisation not witnessed with non-PDMS functionalised pyridine analogues.

机译：合成并表征了聚二甲基硅氧烷（PDMS）官能化吡啶（1），[Pd（OAc）_2（1）_2]（2）和[PdCl _2（1）_2]（3）的钯（II）配合物。使用DFT计算研究了配合物3模型的顺/反异构现象。理论上还对复合物2的模型进行了分析，以识别任何可能的C-H2O相互作用。研究了络合物2作为无溶剂条件和超临界二氧化碳（scCO_2）中选择性醇氧化的催化剂。在scCO_2中，发现1的存在可以稳定钯配合物，抑制其分解为Pd（0），这是非PDMS官能化吡啶类似物所没有的稳定作用。

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《Polyhedron: The International Journal for Inorganic and Organometallic Chemistry》 |2010年第18期|共7页
作者
Herbert M.; Montilla F.; Galindo A.;
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正文语种 eng
中图分类无机化学;
关键词
Alcohol; Homogeneous catalysis; Oxidation; Palladium; Supercritical carbon dioxide;

机译：酒精;均相催化;氧化;钯;超临界二氧化碳;

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1. Synthesis and theoretical analysis of palladium complexes of polydimethylsiloxane functionalised pyridine and their catalytic activity in alcohol oxidations under low polar conditions [J] . Herbert M., Montilla F., Galindo A. Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 2010,第18期

机译：低极性条件下聚二甲基硅氧烷官能化吡啶钯配合物的合成及理论分析及其在醇氧化中的催化活性
2. Methyltrioxorhenium Complexes of Polydimethylsiloxane-Functionalized Pyridine as Efficient Olefin Epoxidation Catalysts in Solventless and Low-Polar Solvent Conditions [J] . Herbert Matthew, Galindo Agustin, Montilla Francisco Organometallics . 2009,第9期

机译：聚二甲基硅氧烷官能化吡啶的甲基三氧or络合物在无溶剂和低极性溶剂条件下作为高效烯烃环氧化催化剂
3. Synthesis and Structures of Ruthenium Carbonyl Complexes Bearing Pyridine-Alkoxide Ligands and Their Catalytic Activity in Alcohol Oxidation [J] . Xinlong Yan, Xiaohui Yue, Kang Liu, Frontiers in Chemistry . 2019,第2期

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4. Ru complexes containing pyridine dicarboxylate ligands: electronic effects on their catalytic activity toward water oxidation [C] . Junxue An, Lele Duan, Licheng Sun General Discussion on Artificial Photosynthesis . 2012

机译：Ru含有吡啶二羧酸酯配体的复合物：电子效应对水氧化的催化活性
5. New palladium and platinum complexes based on ligands bearing nitronylnitroxide radicals. Magnetic properties and catalytic activity in oxidation of alcohols [D] . Shemsi, Ahsan Mushir 2008

机译：基于带有硝酰基硝基氧自由基的配体的新型钯和铂配合物。醇氧化的磁性和催化活性
6. Synthesis and Structures of Ruthenium Carbonyl Complexes Bearing Pyridine-Alkoxide Ligands and Their Catalytic Activity in Alcohol Oxidation [O] . Xinlong Yan, Xiaohui Yue, Kang Liu, 1970

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Synthesis and theoretical analysis of palladium complexes of polydimethylsiloxane functionalised pyridine and their catalytic activity in alcohol oxidations under low polar conditions

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