P Csp3 P and P Csp2 P Palladium(II) Hydride Pincer Complexes: Small Structural Difference—Large Effect on Reactivity

Roman Gerber Thomas Fox Dr. Christian M. Frech Dr.

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P Csp3 P and P Csp2 P Palladium(II) Hydride Pincer Complexes: Small Structural Difference—Large Effect on Reactivity

机译：P Csp 3 P和P Csp 2 P氢化钯钳夹配合物：结构差异小-对反应活性的较大影响

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Little and large! The aliphatic palladium(II) pincer hydride complex undergoes smooth dihydrogen evolution and formation of the stable palladium(II) hydroxide complex when an excess of water is added to a solution of the complex in THF. This reactivity is strikingly different when compared to its aromatic analogue and can be attributed to the stronger trans influence of the aliphatic pincer unit. The reaction is reversible and fast hydrogenolysis is observed (see scheme).

机译：小和大！当将过量的水加入到该络合物的THF溶液中时，该脂肪族钯（II）氢化夹钳的氢化物会顺利发生二氢释放并形成稳定的氢氧化钯（II）络合物。与芳香族类似物相比，该反应性显着不同，并且可以归因于脂肪族钳子单元更强的反式影响。该反应是可逆的，并且观察到快速氢解（参见方案）。

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《Chemistry - A European Journal》 |2010年第23期|p.6771-6775|共5页
作者
Roman Gerber Thomas Fox Dr. Christian M. Frech Dr.;
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正文语种 eng
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coordination modes; hydride ligands; hydrogenolysis; NMR spectroscopy; palladium; pincer ligands;

机译：配位模式;氢化物配体;氢解;NMR光谱;钯;钳夹配体;

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1. PCsp~3P and PCsp~2P palladium(II) hydride pincer complexes: Small structural difference-large effect on reactivity [J] . Gerber R., Fox T., Frech C.M. Chemistry: A European journal . 2010,第23期

机译：PCsp〜3P和PCsp〜2P氢化钯（II）配合物：结构差异小-对反应性的影响大
2. Carbon-oxygen bond formation at metal(IV) centers: Reactivity of palladium(II) and platinum(II) complexes of the [2,6-(dimethylaminomethyl)phenyl-N,C,N](-)(pincer) ligand toward iodomethane and dibenzoyl peroxide; Structural studies of M(II) and M(IV [J] . Canty AJ, Denney MC, van Koten G, Organometallics . 2004,第23期

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4. Reductive Allylation of Carbon Dioxide Catalyzed by Newly Designed PSiP-Pincer Type Palladium Hydride Complex [C] . Jun Takaya, Nobuharu lvvasavva Symposium on Organometallic Chemistry . 2008

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5. I. Synthesis, reactivity, and structural studies of rhodium(III) and rhodium(II) complexes of novel bis(oxazoline) pincer ligands. II. Synthesis and reactivity of novel rhenium methylidene complexes. [D] . Krumper, Jennifer. 2003

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6. Reactivity studies of pincer bis-protic N-heterocyclic carbene complexes of platinum and palladium under basic conditions [O] . David C Marelius, Curtis E Moore, Arnold L Rheingold, 2016

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机译：金属（IV）中心的碳 - 氧键形成：2,6-（二甲基氨基氨基甲基）苯基-N，C，N-（钳子）配体的钯（II）和铂（II）络合物的反应性朝向碘甲烷和二苯甲酰基的过氧化氢; M（II）和M（IV）复合物的结构研究

P Csp3 P and P Csp2 P Palladium(II) Hydride Pincer Complexes: Small Structural Difference—Large Effect on Reactivity

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