Yi Ding, Yinghua Ma, Yongheng Tang, Yang Fu, Jiayi Wan, Zhiyuan Xu, Yifei He, Zhenhai Shi, Mohd Nazish, Peng Wu and Herbert W. Roesky
{"title":"β-二氯胺酮氢化铝与有机磷基化合物的发散反应性","authors":"Yi Ding, Yinghua Ma, Yongheng Tang, Yang Fu, Jiayi Wan, Zhiyuan Xu, Yifei He, Zhenhai Shi, Mohd Nazish, Peng Wu and Herbert W. Roesky","doi":"10.1039/D4DT03397C","DOIUrl":null,"url":null,"abstract":"<p >The reactions of LAlH<small><sub>2</sub></small> (L = HC(CMeNAr)<small><sub>2</sub></small>, Ar = 2,6-<small><sup><em>i</em></sup></small>Pr<small><sub>2</sub></small>C<small><sub>6</sub></small>H<small><sub>3</sub></small>) (<strong>1</strong>) with diphenylphosphane oxide [Ph<small><sub>2</sub></small>P(O)H], diphenylphosphinamide [Ph<small><sub>2</sub></small>P(O)NH<small><sub>2</sub></small>], and diaryl/alkyl phosphane [(RO)<small><sub>2</sub></small>P(O)H (R = Ph, or <small><sup><em>i</em></sup></small>Pr)] afford their corresponding compounds with compositions LAl(H)OP(Ph)<small><sub>2</sub></small> (<strong>2</strong>), LAl[OP(Ph)<small><sub>2</sub></small>]<small><sub>2</sub></small> (<strong>3</strong>), LAl{[N(H)P(O)(Ph)<small><sub>2</sub></small>][OP(Ph)<small><sub>2</sub></small>]} (<strong>4</strong>), LAl(O<small><sup><em>i</em></sup></small>Pr)<small><sub>2</sub></small> (<strong>5</strong>), and LAl(OPh)<small><sub>2</sub></small> (<strong>6</strong>), respectively. These reactions probably undergo a process of dehydrogenation coupling, deaminating dehydrogenation coupling, or chain-breaking coupling. It is noteworthy to mention that the reaction of compound <strong>1</strong> with 2 equiv. of Ph<small><sub>2</sub></small>P(O)NH<small><sub>2</sub></small> results in <strong>4</strong> and its isomer <strong>4a</strong>, where both the complexes exhibit different coordination towards the aluminium centre. The structure of <strong>4a</strong> is very rare, where the aluminium centre connects with a nacnac ligand as well as with N and O to form a six-membered and a four-membered ring, respectively. All the compounds were well characterized by multinuclear NMR spectroscopy, elementary analysis, and single-crystal X-ray diffraction.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 9","pages":" 3827-3832"},"PeriodicalIF":3.3000,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"The divergent reactivity of β-diketiminato aluminium hydrides with organophosphoryl compounds†\",\"authors\":\"Yi Ding, Yinghua Ma, Yongheng Tang, Yang Fu, Jiayi Wan, Zhiyuan Xu, Yifei He, Zhenhai Shi, Mohd Nazish, Peng Wu and Herbert W. Roesky\",\"doi\":\"10.1039/D4DT03397C\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The reactions of LAlH<small><sub>2</sub></small> (L = HC(CMeNAr)<small><sub>2</sub></small>, Ar = 2,6-<small><sup><em>i</em></sup></small>Pr<small><sub>2</sub></small>C<small><sub>6</sub></small>H<small><sub>3</sub></small>) (<strong>1</strong>) with diphenylphosphane oxide [Ph<small><sub>2</sub></small>P(O)H], diphenylphosphinamide [Ph<small><sub>2</sub></small>P(O)NH<small><sub>2</sub></small>], and diaryl/alkyl phosphane [(RO)<small><sub>2</sub></small>P(O)H (R = Ph, or <small><sup><em>i</em></sup></small>Pr)] afford their corresponding compounds with compositions LAl(H)OP(Ph)<small><sub>2</sub></small> (<strong>2</strong>), LAl[OP(Ph)<small><sub>2</sub></small>]<small><sub>2</sub></small> (<strong>3</strong>), LAl{[N(H)P(O)(Ph)<small><sub>2</sub></small>][OP(Ph)<small><sub>2</sub></small>]} (<strong>4</strong>), LAl(O<small><sup><em>i</em></sup></small>Pr)<small><sub>2</sub></small> (<strong>5</strong>), and LAl(OPh)<small><sub>2</sub></small> (<strong>6</strong>), respectively. These reactions probably undergo a process of dehydrogenation coupling, deaminating dehydrogenation coupling, or chain-breaking coupling. It is noteworthy to mention that the reaction of compound <strong>1</strong> with 2 equiv. of Ph<small><sub>2</sub></small>P(O)NH<small><sub>2</sub></small> results in <strong>4</strong> and its isomer <strong>4a</strong>, where both the complexes exhibit different coordination towards the aluminium centre. The structure of <strong>4a</strong> is very rare, where the aluminium centre connects with a nacnac ligand as well as with N and O to form a six-membered and a four-membered ring, respectively. All the compounds were well characterized by multinuclear NMR spectroscopy, elementary analysis, and single-crystal X-ray diffraction.</p>\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":\" 9\",\"pages\":\" 3827-3832\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2025-01-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d4dt03397c\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d4dt03397c","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
The divergent reactivity of β-diketiminato aluminium hydrides with organophosphoryl compounds†
The reactions of LAlH2 (L = HC(CMeNAr)2, Ar = 2,6-iPr2C6H3) (1) with diphenylphosphane oxide [Ph2P(O)H], diphenylphosphinamide [Ph2P(O)NH2], and diaryl/alkyl phosphane [(RO)2P(O)H (R = Ph, or iPr)] afford their corresponding compounds with compositions LAl(H)OP(Ph)2 (2), LAl[OP(Ph)2]2 (3), LAl{[N(H)P(O)(Ph)2][OP(Ph)2]} (4), LAl(OiPr)2 (5), and LAl(OPh)2 (6), respectively. These reactions probably undergo a process of dehydrogenation coupling, deaminating dehydrogenation coupling, or chain-breaking coupling. It is noteworthy to mention that the reaction of compound 1 with 2 equiv. of Ph2P(O)NH2 results in 4 and its isomer 4a, where both the complexes exhibit different coordination towards the aluminium centre. The structure of 4a is very rare, where the aluminium centre connects with a nacnac ligand as well as with N and O to form a six-membered and a four-membered ring, respectively. All the compounds were well characterized by multinuclear NMR spectroscopy, elementary analysis, and single-crystal X-ray diffraction.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.