{"title":"六氰丁酸盐(I)阴离子还原丁酸-1,3-二烯","authors":"D. Bingham, M. G. Burnett","doi":"10.1039/J19710001782","DOIUrl":null,"url":null,"abstract":"The kinetics of the reaction of buta-1,3-diene with an aqueous solution of sodium hexacyanodinickelate(I) and the subsequent formation of butenes have been studied at 25° and at an ionic strength of 1·1. The kinetics of the removal of butadiene show that the slow step in complex formation is reaction (i), in which ki= 1·4 ± 0·1 l mol–1 s–1. The kinetics of the formation of the butenes are interpreted in terms of the rate-controlling reduction of two Ni2(CN)64–+ C4H6→(π-C4H6)Ni2(CN)64–(i), cyano-nickel intermediates, π1 and π2, containing a π-1-methylallyl ligand and a π-buta-1,3-diene ligand respectively. The two intermediates react by kinetically distinct paths yielding predominantly trans-but-2-ene, (π1), and cis-but-2-ene, (π2). The presence of a π-1-methylallylnickel complex in the reaction mixture has been confirmed by n.m.r. spectroscopy.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"6","resultStr":"{\"title\":\"Reduction of buta-1,3-diene by the hexacyanodinickelate(I) anion\",\"authors\":\"D. Bingham, M. G. Burnett\",\"doi\":\"10.1039/J19710001782\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The kinetics of the reaction of buta-1,3-diene with an aqueous solution of sodium hexacyanodinickelate(I) and the subsequent formation of butenes have been studied at 25° and at an ionic strength of 1·1. The kinetics of the removal of butadiene show that the slow step in complex formation is reaction (i), in which ki= 1·4 ± 0·1 l mol–1 s–1. The kinetics of the formation of the butenes are interpreted in terms of the rate-controlling reduction of two Ni2(CN)64–+ C4H6→(π-C4H6)Ni2(CN)64–(i), cyano-nickel intermediates, π1 and π2, containing a π-1-methylallyl ligand and a π-buta-1,3-diene ligand respectively. The two intermediates react by kinetically distinct paths yielding predominantly trans-but-2-ene, (π1), and cis-but-2-ene, (π2). The presence of a π-1-methylallylnickel complex in the reaction mixture has been confirmed by n.m.r. spectroscopy.\",\"PeriodicalId\":17321,\"journal\":{\"name\":\"Journal of The Chemical Society A: Inorganic, Physical, Theoretical\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1971-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"6\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of The Chemical Society A: Inorganic, Physical, Theoretical\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1039/J19710001782\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1039/J19710001782","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Reduction of buta-1,3-diene by the hexacyanodinickelate(I) anion
The kinetics of the reaction of buta-1,3-diene with an aqueous solution of sodium hexacyanodinickelate(I) and the subsequent formation of butenes have been studied at 25° and at an ionic strength of 1·1. The kinetics of the removal of butadiene show that the slow step in complex formation is reaction (i), in which ki= 1·4 ± 0·1 l mol–1 s–1. The kinetics of the formation of the butenes are interpreted in terms of the rate-controlling reduction of two Ni2(CN)64–+ C4H6→(π-C4H6)Ni2(CN)64–(i), cyano-nickel intermediates, π1 and π2, containing a π-1-methylallyl ligand and a π-buta-1,3-diene ligand respectively. The two intermediates react by kinetically distinct paths yielding predominantly trans-but-2-ene, (π1), and cis-but-2-ene, (π2). The presence of a π-1-methylallylnickel complex in the reaction mixture has been confirmed by n.m.r. spectroscopy.