FigsharePub Date : 2016-06-03DOI: 10.1021/ja7107454.s005
Liam P. Spencer (1993702), Ping Yang (56755), Brian L. Scott (1455997), Enrique R. Batista (1342752), James M. Boncella (1750702)
{"title":"Imido Exchange in Bis(imido) Uranium(VI) Complexes with Aryl Isocyanates","authors":"Liam P. Spencer (1993702), Ping Yang (56755), Brian L. Scott (1455997), Enrique R. Batista (1342752), James M. Boncella (1750702)","doi":"10.1021/ja7107454.s005","DOIUrl":"https://doi.org/10.1021/ja7107454.s005","url":null,"abstract":"Addition of 1 and 2 equiv of ArNCO (ArPh, 2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>) to U(N<i><sup>t</sup></i><sup></sup>Bu)<sub>2</sub>(I)<sub>2</sub>(OPPh<sub>3</sub>)<sub>2</sub> yields the aryl−imido complexes U(NAr)(N<i><sup>t</sup></i><sup></sup>Bu)(I)<sub>2</sub>(OPPh<sub>3</sub>)<sub>2</sub> and U(NAr)<sub>2</sub>(I)<sub>2</sub>(OPPh<sub>3</sub>)<sub>2</sub>, respectively. Unlike analogous transition metal reactions this imido exchange reaction does not proceed through a metal oxo intermediate. Density functional theory calculations and <sup>15</sup>N-labeling studies suggest this transformation involves the [2 + 2] cycloaddition of the aryl isocyanate CN bond across the UN imido ligand to form an <i>N</i>,<i>N</i>-bound ureato intermediate.","PeriodicalId":522850,"journal":{"name":"Figshare","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2016-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147904627","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}