{"title":"Supramolecular chemistry of organoplatinum(IV) complexes: A syndiotactic polymer with uracil substituents","authors":"Michael J Nieradko, R. Puddephatt","doi":"10.1177/17475198221114610","DOIUrl":null,"url":null,"abstract":"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.","PeriodicalId":15318,"journal":{"name":"Journal of Chemical Research-s","volume":"126 1","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2022-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Research-s","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1177/17475198221114610","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
Abstract
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.
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.
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