有机铂(IV)配合物的超分子化学:具有尿嘧啶取代基的同规聚合物

Journal of Chemical Research-s Pub Date : 2022-07-01 DOI:10.1177/17475198221114610

Michael J Nieradko, R. Puddephatt

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引用次数: 0

摘要

RCH2X与[PtMe2(DPA)]， 1， (DPA =二-2-吡啶胺)反应得到[PtXMe2(CH2R)(DPA)]，当R = 6-尿嘧啶，X = Cl时，通过顺式氧化加成得到2a;当R = CO2H, X = Br时，通过顺式和反式混合氧化加成，R = 4-C6H4CO2H, X = Br时，得到4a/4b。氧化加成的不寻常的顺式立体化学在热力学上是合理的，在2a和3a中形成了分子内氢键，而在4a中没有，在动力学上是由配体DPA NH基团在与卤化物的氢键中所起的作用。在固体状态下，配合物2a通过形成两种不同的分子间nh2形成一种不寻常的超分子共规聚合物。O=C的氢键与邻近分子成键。

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Supramolecular chemistry of organoplatinum(IV) complexes: A syndiotactic polymer with uracil substituents

The reaction of RCH2X with [PtMe2(DPA)], 1, (DPA = di-2-pyridylamine) has given [PtXMe2(CH2R)(DPA)] by cis oxidative addition to give 2a, when R = 6-uracil, X = Cl, or 3a, when R = CO2H, X = Br, but by a mixture of cis and trans oxidative addition to give 4a/4b when R = 4-C6H4CO2H, X = Br. The unusual cis stereochemistry of oxidative addition is rationalized thermodynamically by the formation of an intramolecular hydrogen bond in 2a and 3a but not 4a, and kinetically by the role of the ligand DPA NH group in hydrogen bonding to halide. Complex 2a in the solid state forms an unusual supramolecular syndiotactic polymer by forming two different intermolecular NH..O=C hydrogen bonds to neighbouring molecules.

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来源期刊

Journal of Chemical Research-s 化学科学, 有机化学, 有机合成

自引率

0.00%

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审稿时长

1 months

期刊介绍： The Journal of Chemical Research is a peer reviewed journal that publishes full-length review and research papers in all branches of experimental chemistry. The journal fills a niche by also publishing short papers, a format which favours particular types of work, e.g. the scope of new reagents or methodology, and the elucidation of the structure of novel compounds. Though welcome, short papers should not result in fragmentation of publication, they should describe a completed piece of work. The Journal is not intended as a vehicle for preliminary publications. The work must meet all the normal criteria for acceptance as regards scientific standards. Papers that contain extensive biological results or material relating to other areas of science may be diverted to more appropriate specialist journals. Areas of coverage include: Organic Chemistry; Inorganic Chemistry; Materials Chemistry; Crystallography; Computational Chemistry.