{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,24]],"date-time":"2025-10-24T12:52:59Z","timestamp":1761310379790,"version":"build-2065373602"},"reference-count":66,"publisher":"Wiley","issue":"7","license":[{"start":{"date-parts":[[2006,11,29]],"date-time":"2006-11-29T00:00:00Z","timestamp":1164758400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2007,2,23]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The compound <jats:italic>syn\u2010<\/jats:italic>[{Rh(\u03bc\u2010NH{<jats:italic>p<\/jats:italic>\u2010tolyl})(CN<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>}<jats:sub>2<\/jats:sub>] (<jats:bold>1<\/jats:bold>) oxidatively adds C\uf8ffCl bonds of alkyl chlorides (RCl) and dichloromethane to each metal centre to give the cationic complexes <jats:italic>syn<\/jats:italic>\u2010[{Rh(\u03bc\u2010NH{<jats:italic>p<\/jats:italic>\u2010tolyl})(\u03b7<jats:sup>1<\/jats:sup>\u2010R)(CN<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>}<jats:sub>2<\/jats:sub>(\u03bc\u2010Cl)]Cl and <jats:italic>anti<\/jats:italic>\u2010[{Rh(\u03bc\u2010NH{<jats:italic>p<\/jats:italic>\u2010tolyl})Cl(CN<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>}<jats:sub>2<\/jats:sub>(\u03bc\u2010CH<jats:sub>2<\/jats:sub>)]. Reaction of <jats:bold>1<\/jats:bold> with the chiral alkyl chloride (\u2212)\u2010(<jats:italic>S<\/jats:italic>)\u2010ClCH(Me)CO<jats:sub>2<\/jats:sub>Me (R*Cl) gave [{Rh(\u03bc\u2010NH{<jats:italic>p<\/jats:italic>\u2010tolyl})(\u03b7<jats:sup>1<\/jats:sup>\u2010R*)(CN<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>}<jats:sub>2<\/jats:sub>(\u03bc\u2010Cl)]Cl ([<jats:bold>3<\/jats:bold>]Cl) as an equimolecular mixture of the <jats:italic>meso<\/jats:italic> form (<jats:italic>R<\/jats:italic>,<jats:italic>S<\/jats:italic>)\u2010[<jats:bold>3<\/jats:bold>]Cl\u2010<jats:italic>C<jats:sub>s<\/jats:sub><\/jats:italic> and one enantiomer of the chiral form [<jats:bold>3<\/jats:bold>]Cl\u2010<jats:italic>C<\/jats:italic><jats:sub>2<\/jats:sub>. This reaction, which takes place in two steps, was modeled step\u2010by\u2010step by reacting the mixed\u2010ligand complex <jats:italic>syn\u2010<\/jats:italic>[(cod)Rh(\u03bc\u2010NH{<jats:italic>p\u2010<\/jats:italic>tolyl})<jats:sub>2<\/jats:sub>Rh(CN<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>] (<jats:bold>4<\/jats:bold>) with R*Cl, as a replica of the first step, to give [(cod)Rh(\u03bc\u2010NH{<jats:italic>p\u2010<\/jats:italic>tolyl})<jats:sub>2<\/jats:sub>RhCl(\u03b7<jats:sup>1<\/jats:sup>\u2010R*)(CN<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>] (<jats:bold>5<\/jats:bold>) with racemization of the chiral carbon. Further treatment of <jats:bold>5<\/jats:bold> with CN<jats:italic>t<\/jats:italic>Bu to give the intermediate [(CN<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>Rh(\u03bc\u2010NH{<jats:italic>p\u2010<\/jats:italic>tolyl})<jats:sub>2<\/jats:sub>RhCl(\u03b7<jats:sup>1<\/jats:sup>\u2010R*)(CN<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>], followed by reaction with R*Cl reproduced the regioselectivity of the second step to give (<jats:italic>R<\/jats:italic>,<jats:italic>S<\/jats:italic>)\u2010[<jats:bold>3<\/jats:bold>]Cl\u2010<jats:italic>C<jats:sub>s<\/jats:sub><\/jats:italic> and [<jats:bold>3<\/jats:bold>]Cl\u2010<jats:italic>C<\/jats:italic><jats:sub>2<\/jats:sub> in a 1:1 molar ratio. Support for an S<jats:sub>N<\/jats:sub>2 type of reaction with inversion of the configuration in the second step was obtained from a similar sequence of reactions of <jats:bold>4<\/jats:bold> with ClCH<jats:sub>2<\/jats:sub>CO<jats:sub>2<\/jats:sub>Me first, then with CN<jats:italic>t<\/jats:italic>Bu, and finally with R*Cl to give [(CN<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>(\u03b7<jats:sup>1<\/jats:sup>\u2010CH<jats:sub>2<\/jats:sub>R)Rh(\u03bc\u2010NH{<jats:italic>p\u2010<\/jats:italic>tolyl})<jats:sub>2<\/jats:sub>(\u03bc\u2010Cl)Rh(\u03b7<jats:sup>1<\/jats:sup>\u2010R*)(CN<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>]Cl (R = CO<jats:sub>2<\/jats:sub>Me, [<jats:bold>7<\/jats:bold>]Cl) as a single enantiomer with the <jats:italic>R<\/jats:italic> configuration at the chiral carbon. The reactions of <jats:bold>1<\/jats:bold> with (+)\u2010(<jats:italic>S<\/jats:italic>)\u2010XCH<jats:sub>2<\/jats:sub>CH(CH<jats:sub>3<\/jats:sub>)CH<jats:sub>2<\/jats:sub>CH<jats:sub>3<\/jats:sub> (X = Br, I) gave the related complexes [{Rh(\u03bc\u2010NH{<jats:italic>p\u2010<\/jats:italic>tolyl})(\u03b7<jats:sup>1<\/jats:sup>\u2010CH<jats:sub>2<\/jats:sub>CH(CH<jats:sub>3<\/jats:sub>)CH<jats:sub>2<\/jats:sub>CH<jats:sub>3<\/jats:sub>)(CN<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>}<jats:sub>2<\/jats:sub>(\u03bc\u2010X)]X, probably by following an S<jats:sub>N<\/jats:sub>2 profile in both steps.<\/jats:p>","DOI":"10.1002\/chem.200600971","type":"journal-article","created":{"date-parts":[[2006,11,29]],"date-time":"2006-11-29T13:51:02Z","timestamp":1164808262000},"page":"2044-2053","source":"Crossref","is-referenced-by-count":25,"title":["One\u2010Electron versus Two\u2010Electron Mechanisms in the Oxidative Addition Reactions of Chloroalkanes to Amido\u2010Bridged Rhodium Complexes"],"prefix":"10.1002","volume":"13","author":[{"given":"Cristina","family":"Tejel","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Miguel\u2005A.","family":"Ciriano","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jos\u00e9\u2005A.","family":"L\u00f3pez","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sonia","family":"Jim\u00e9nez","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Marta","family":"Bordonaba","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Luis\u2005A.","family":"Oro","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2007,2,8]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19891011035"},{"key":"e_1_2_6_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198913861"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(94)85014-3"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00028a008"},{"key":"e_1_2_6_5_2","unstructured":"\u00a0"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar00155a007"},{"volume-title":"Principles and Applications of Organotransition Metal Chemistry","year":"1987","author":"Collman J. 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