{"title":"稀土和碱土元素配合物在催化多C-C键分子间加氢磷酸化中的作用","authors":"I. V. Lapshin, A. Kissel, A. Trifonov","doi":"10.22204/2410-4639-2019-102-02-58-73","DOIUrl":null,"url":null,"abstract":"In accordance with United Nations General Assembly resolution, the year 2019 was proclaimed the International Year of the Periodic Table of Chemical Elements. Rare-earth elements were discovered during the time of the Periodic System development. In the past few decades, their compounds have attracted great interest due to their unique reactivity. This review covers recent achievements in the field of intermolecular hydrophosphination of alkenes, dienes and alkynes, which is catalyzed by rare earth and alkaline-earth metal complexes. Catalytic hydrophosphination reaction is the addition of an P—H bond to С—С multiple bonds, and offers an efficient and elegant synthetic approach to production of the organophosphorus compounds widely used in industrial synthesis, pharmaceuticals, agrochemistry, and other areas. The high values of the ionic radii of rare earth and alkaline-earth metals in combination with the Lewis acidity provide their compounds with a pronounced tendency to complex formation and, accordingly, high coordination numbers. Due to high reactivity of M—E (E = C, H, N, P) bonds, ease of Ln—P ı-bond metathesis and multiple C—C bond insertions, these compounds offer new prospects for the catalysis of the alkenes and alkynes hydrophosphination. Therefore, complexes of non-toxic and relatively abundant in nature rare earth and alkaline earth metals can be a cheaper and more effective alternative to compounds of late transition metals in the catalysis of the C—P bond formation.","PeriodicalId":122949,"journal":{"name":"Vestnik RFFI","volume":"121 6 1","pages":"0"},"PeriodicalIF":0.0000,"publicationDate":"2019-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Complexes of Rare- and Alkaline-Earth Elements in Catalytic Intermolecular Hydrophosphination of Multiple C—C Bonds\",\"authors\":\"I. V. Lapshin, A. Kissel, A. Trifonov\",\"doi\":\"10.22204/2410-4639-2019-102-02-58-73\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"In accordance with United Nations General Assembly resolution, the year 2019 was proclaimed the International Year of the Periodic Table of Chemical Elements. Rare-earth elements were discovered during the time of the Periodic System development. In the past few decades, their compounds have attracted great interest due to their unique reactivity. This review covers recent achievements in the field of intermolecular hydrophosphination of alkenes, dienes and alkynes, which is catalyzed by rare earth and alkaline-earth metal complexes. Catalytic hydrophosphination reaction is the addition of an P—H bond to С—С multiple bonds, and offers an efficient and elegant synthetic approach to production of the organophosphorus compounds widely used in industrial synthesis, pharmaceuticals, agrochemistry, and other areas. The high values of the ionic radii of rare earth and alkaline-earth metals in combination with the Lewis acidity provide their compounds with a pronounced tendency to complex formation and, accordingly, high coordination numbers. Due to high reactivity of M—E (E = C, H, N, P) bonds, ease of Ln—P ı-bond metathesis and multiple C—C bond insertions, these compounds offer new prospects for the catalysis of the alkenes and alkynes hydrophosphination. Therefore, complexes of non-toxic and relatively abundant in nature rare earth and alkaline earth metals can be a cheaper and more effective alternative to compounds of late transition metals in the catalysis of the C—P bond formation.\",\"PeriodicalId\":122949,\"journal\":{\"name\":\"Vestnik RFFI\",\"volume\":\"121 6 1\",\"pages\":\"0\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2019-06-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Vestnik RFFI\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.22204/2410-4639-2019-102-02-58-73\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Vestnik RFFI","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.22204/2410-4639-2019-102-02-58-73","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
摘要
根据联合国大会决议,宣布2019年为化学元素周期表国际年。稀土元素是在周期系统发展时期发现的。在过去的几十年里,它们的化合物因其独特的反应性而引起了人们的极大兴趣。本文综述了稀土和碱土金属配合物催化烯烃、二烯烃和炔烃分子间加氢磷化反应的最新进展。催化氢化反应是将P-H键加到С -С多个键上,为生产有机磷化合物提供了一种高效、简便的合成方法,广泛应用于工业合成、制药、农业化学和其他领域。稀土和碱土金属的高离子半径值与刘易斯酸度相结合,使它们的化合物具有明显的络合物形成倾向,因此具有高配位数。由于M-E (E = C, H, N, P)键具有较高的反应活性,易于Ln-P ı-bond复分解和多个C - C键插入,这些化合物在催化烯烃和炔烃加氢磷酸化方面具有新的前景。因此,无毒且相对丰富的天然稀土和碱土金属配合物可以替代晚期过渡金属化合物更便宜、更有效地催化C-P键的形成。
Complexes of Rare- and Alkaline-Earth Elements in Catalytic Intermolecular Hydrophosphination of Multiple C—C Bonds
In accordance with United Nations General Assembly resolution, the year 2019 was proclaimed the International Year of the Periodic Table of Chemical Elements. Rare-earth elements were discovered during the time of the Periodic System development. In the past few decades, their compounds have attracted great interest due to their unique reactivity. This review covers recent achievements in the field of intermolecular hydrophosphination of alkenes, dienes and alkynes, which is catalyzed by rare earth and alkaline-earth metal complexes. Catalytic hydrophosphination reaction is the addition of an P—H bond to С—С multiple bonds, and offers an efficient and elegant synthetic approach to production of the organophosphorus compounds widely used in industrial synthesis, pharmaceuticals, agrochemistry, and other areas. The high values of the ionic radii of rare earth and alkaline-earth metals in combination with the Lewis acidity provide their compounds with a pronounced tendency to complex formation and, accordingly, high coordination numbers. Due to high reactivity of M—E (E = C, H, N, P) bonds, ease of Ln—P ı-bond metathesis and multiple C—C bond insertions, these compounds offer new prospects for the catalysis of the alkenes and alkynes hydrophosphination. Therefore, complexes of non-toxic and relatively abundant in nature rare earth and alkaline earth metals can be a cheaper and more effective alternative to compounds of late transition metals in the catalysis of the C—P bond formation.