{"title":"s-和d-金属双锥体和夹层配合物的诱导芳构性和电子计数规则","authors":"T. Gribanova, R. M. Minyaev, V. Minkin","doi":"10.2174/1874364101105010062","DOIUrl":null,"url":null,"abstract":"Structures and stability of an extended series of bipyramidal, sandwich and sandwich-bipyramidal mixed complexes formed by conjugated cyclic hydrocarbons (CH)n with s(Li, Na, K, Be, Mg, Ca) and d(Cr, Mn, Fe) metals have been studied using DFT B3LYP/6-311+G(df,p) calculations. Stable structures of the compounds satisfy a general (6n + 6d + 12c) electron-count rule, where n stands for total number of the basal hydrocarbon rings, d is total number of d-metal centers (or separate sandwich moieties) and is total number of apical metal-carbonyl groups. It is shown that stabilization of the studied polyhedral organometallic structures (induced aromaticity) is caused by filling 6 -electronic shells of basal (4-6)-membered cycles provided by donation of additional electrons from metal centers thereby acquiring closed 18-","PeriodicalId":23020,"journal":{"name":"The Open Organic Chemistry Journal","volume":"24 1","pages":"62-78"},"PeriodicalIF":0.0000,"publicationDate":"2011-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"7","resultStr":"{\"title\":\"Induced Aromaticity and Electron-Count Rules for Bipyramidal and Sandwich Complexes of s- and d-Metals\",\"authors\":\"T. Gribanova, R. M. Minyaev, V. Minkin\",\"doi\":\"10.2174/1874364101105010062\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Structures and stability of an extended series of bipyramidal, sandwich and sandwich-bipyramidal mixed complexes formed by conjugated cyclic hydrocarbons (CH)n with s(Li, Na, K, Be, Mg, Ca) and d(Cr, Mn, Fe) metals have been studied using DFT B3LYP/6-311+G(df,p) calculations. Stable structures of the compounds satisfy a general (6n + 6d + 12c) electron-count rule, where n stands for total number of the basal hydrocarbon rings, d is total number of d-metal centers (or separate sandwich moieties) and is total number of apical metal-carbonyl groups. It is shown that stabilization of the studied polyhedral organometallic structures (induced aromaticity) is caused by filling 6 -electronic shells of basal (4-6)-membered cycles provided by donation of additional electrons from metal centers thereby acquiring closed 18-\",\"PeriodicalId\":23020,\"journal\":{\"name\":\"The Open Organic Chemistry Journal\",\"volume\":\"24 1\",\"pages\":\"62-78\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2011-09-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"7\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Open Organic Chemistry Journal\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.2174/1874364101105010062\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Open Organic Chemistry Journal","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.2174/1874364101105010062","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Induced Aromaticity and Electron-Count Rules for Bipyramidal and Sandwich Complexes of s- and d-Metals
Structures and stability of an extended series of bipyramidal, sandwich and sandwich-bipyramidal mixed complexes formed by conjugated cyclic hydrocarbons (CH)n with s(Li, Na, K, Be, Mg, Ca) and d(Cr, Mn, Fe) metals have been studied using DFT B3LYP/6-311+G(df,p) calculations. Stable structures of the compounds satisfy a general (6n + 6d + 12c) electron-count rule, where n stands for total number of the basal hydrocarbon rings, d is total number of d-metal centers (or separate sandwich moieties) and is total number of apical metal-carbonyl groups. It is shown that stabilization of the studied polyhedral organometallic structures (induced aromaticity) is caused by filling 6 -electronic shells of basal (4-6)-membered cycles provided by donation of additional electrons from metal centers thereby acquiring closed 18-