Basma al Janabi, Francisco Reigosa, Juan M. Ortigueira, José M. Vila
{"title":"双齿[C,N]和三齿[C,N,S]环金属钯配合物作为交叉偶联反应的预催化剂。","authors":"Basma al Janabi, Francisco Reigosa, Juan M. Ortigueira, José M. Vila","doi":"10.1002/open.202400253","DOIUrl":null,"url":null,"abstract":"<p>Treatment of halide substituted bidentate [C,N] and tridentate [C,N,S] Schiff base ligands with palladium(II) acetate or with lithium tetrachloropalladate, as appropriate, afforded through C−H activation of the organic ligand, the dinuclear (<b>1 a</b>, <b>1 b</b>) and mononuclear (<b>1 c</b>, <b>1 d</b>, <b>1 e</b>) palladacycles, respectively. Reaction of the μ-acetate dinuclear complexes with aqueous sodium chloride in a metathesis process, gave the μ-chloride dinuclear complexes (<b>2 a</b>, <b>2 b</b>). Treatment of the latter with triphenylphosphine or with bis(diphenylphosphino)methane (dppm)/ammonium hexafluorophosphate in complex/ phosphine 1 : 2 ratio, gave the phosphine derivatives (<b>3 a</b>, <b>3 b</b>, <b>4 a</b>, <b>4 b</b>). Reaction of <b>1 c</b> and of <b>1 e</b> with triphenylphosphine/silver perchlorate and dppm/silver perchlorate, respectively, gave compounds <b>2 c</b> and <b>2 e</b> with removal of the chloride ligand by precipitation of the silver halide. The compounds were characterized by microanalysis (CHN), IR and <sup>1</sup>H and <sup>31</sup>P{<sup>1</sup>H} NMR spectroscopy. The crystal structures of three complexes, <b>4 a</b>, <b>1 c</b> and <b>1 e</b> were studied by single-crystal X-ray diffraction. Furthermore, the performance of the palladacycles were tested as pre-catalysts, namely Suzuki-Miyaura cross-coupling reaction and those furnishing the better results are also reported.</p>","PeriodicalId":9831,"journal":{"name":"ChemistryOpen","volume":"14 4","pages":""},"PeriodicalIF":2.5000,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/open.202400253","citationCount":"0","resultStr":"{\"title\":\"Bidentate [C,N] and Tridentate [C,N,S] Palladium Cyclometallated Complexes as Pre-Catalysts in Cross-Coupling Reactions\",\"authors\":\"Basma al Janabi, Francisco Reigosa, Juan M. Ortigueira, José M. Vila\",\"doi\":\"10.1002/open.202400253\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Treatment of halide substituted bidentate [C,N] and tridentate [C,N,S] Schiff base ligands with palladium(II) acetate or with lithium tetrachloropalladate, as appropriate, afforded through C−H activation of the organic ligand, the dinuclear (<b>1 a</b>, <b>1 b</b>) and mononuclear (<b>1 c</b>, <b>1 d</b>, <b>1 e</b>) palladacycles, respectively. Reaction of the μ-acetate dinuclear complexes with aqueous sodium chloride in a metathesis process, gave the μ-chloride dinuclear complexes (<b>2 a</b>, <b>2 b</b>). Treatment of the latter with triphenylphosphine or with bis(diphenylphosphino)methane (dppm)/ammonium hexafluorophosphate in complex/ phosphine 1 : 2 ratio, gave the phosphine derivatives (<b>3 a</b>, <b>3 b</b>, <b>4 a</b>, <b>4 b</b>). Reaction of <b>1 c</b> and of <b>1 e</b> with triphenylphosphine/silver perchlorate and dppm/silver perchlorate, respectively, gave compounds <b>2 c</b> and <b>2 e</b> with removal of the chloride ligand by precipitation of the silver halide. The compounds were characterized by microanalysis (CHN), IR and <sup>1</sup>H and <sup>31</sup>P{<sup>1</sup>H} NMR spectroscopy. The crystal structures of three complexes, <b>4 a</b>, <b>1 c</b> and <b>1 e</b> were studied by single-crystal X-ray diffraction. Furthermore, the performance of the palladacycles were tested as pre-catalysts, namely Suzuki-Miyaura cross-coupling reaction and those furnishing the better results are also reported.</p>\",\"PeriodicalId\":9831,\"journal\":{\"name\":\"ChemistryOpen\",\"volume\":\"14 4\",\"pages\":\"\"},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-11-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/open.202400253\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ChemistryOpen\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/open.202400253\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemistryOpen","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/open.202400253","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Bidentate [C,N] and Tridentate [C,N,S] Palladium Cyclometallated Complexes as Pre-Catalysts in Cross-Coupling Reactions
Treatment of halide substituted bidentate [C,N] and tridentate [C,N,S] Schiff base ligands with palladium(II) acetate or with lithium tetrachloropalladate, as appropriate, afforded through C−H activation of the organic ligand, the dinuclear (1 a, 1 b) and mononuclear (1 c, 1 d, 1 e) palladacycles, respectively. Reaction of the μ-acetate dinuclear complexes with aqueous sodium chloride in a metathesis process, gave the μ-chloride dinuclear complexes (2 a, 2 b). Treatment of the latter with triphenylphosphine or with bis(diphenylphosphino)methane (dppm)/ammonium hexafluorophosphate in complex/ phosphine 1 : 2 ratio, gave the phosphine derivatives (3 a, 3 b, 4 a, 4 b). Reaction of 1 c and of 1 e with triphenylphosphine/silver perchlorate and dppm/silver perchlorate, respectively, gave compounds 2 c and 2 e with removal of the chloride ligand by precipitation of the silver halide. The compounds were characterized by microanalysis (CHN), IR and 1H and 31P{1H} NMR spectroscopy. The crystal structures of three complexes, 4 a, 1 c and 1 e were studied by single-crystal X-ray diffraction. Furthermore, the performance of the palladacycles were tested as pre-catalysts, namely Suzuki-Miyaura cross-coupling reaction and those furnishing the better results are also reported.
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