{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T15:26:27Z","timestamp":1760369187953,"version":"build-2065373602"},"reference-count":76,"publisher":"Wiley","issue":"19","license":[{"start":{"date-parts":[[2014,3,27]],"date-time":"2014-03-27T00:00:00Z","timestamp":1395878400000},"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":[[2014,5,5]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>On the basis of isolated diastereomeric triorganylstannyl\u2010P<jats:sub>5<\/jats:sub>\u2010deltacyclenes <jats:bold>7\u2032<\/jats:bold> and <jats:bold>7\u2032\u2032<\/jats:bold>, almost pure enantiomers of their destannylation products <jats:bold>8\u2032<\/jats:bold> and <jats:bold>8\u2032\u2032<\/jats:bold> are now available. These stereochemically inert cage chiral species contain a configurationally labile P1\uf8ffH1 group that defines two epimers <jats:bold>8\u2009a<\/jats:bold> and <jats:bold>8\u2009b<\/jats:bold> of each of the enantiomers, which are connected by a rapid equilibrium. Mirror\u2010symmetric circular dichroism (CD) spectra of the enantiomeric cages are compatible with the identification of epimers. A simulation of the CD spectrum of the major epimer <jats:bold>8\u2032a<\/jats:bold> relates the cage chirality of the system to the observed chiroptical effects. Both cage epimers and two of the phosphorus cage atoms are active as ligands with respect to [M(CO)<jats:sub>5<\/jats:sub>] fragments of Cr, Mo, and W. Four almost isoenergetic regio\u2010 and stereoisomers of the resulting mononuclear complexes are formed for these metals, but only one of the isomers per metal crystallized in the case of the racemic series of the complexes. The enantiopure versions of cages and cage complexes, however, did not crystallize at all, a well\u2010known phenomenon for chiral compounds. CD spectra of the optically active complex isomer mixtures are close to identical with the CD spectra of the related free cages and point again to the chiral cages as the dominant source of the CD effects of the complexes. [(Benzene)RuCl<jats:sub>2<\/jats:sub>] complexes of the cage ligand <jats:bold>8<\/jats:bold> behave totally differently. Only a single species <jats:bold>12<\/jats:bold>=[(benzene)RuCl<jats:sub>2<\/jats:sub><jats:bold>\u22c58\u2009b<\/jats:bold>] is formed in almost quantitative yield and the minor epimer <jats:bold>8\u2009b<\/jats:bold> plays the role of the ligand exclusively. The reaction works as well for the separated enantiomeric cage versions to yield the highly enriched enantiomers <jats:bold>12\u2032<\/jats:bold> and <jats:bold>12\u2032\u2032<\/jats:bold> separately. An efficient kinetic resolution process was identified as the main reason for this finding. It is based on a high stereo\u2010 and regiochemical flexibility of the P\uf8ffC cage ligand that is capable of adjusting to the specific requirements of a suitable transition\u2010metal complex fragment. Such ligand flexibility is regularly observed in metalloenzymes, but is a very rare case in classical and organometallic complex chemistry.<\/jats:p>","DOI":"10.1002\/chem.201303821","type":"journal-article","created":{"date-parts":[[2014,3,27]],"date-time":"2014-03-27T13:47:57Z","timestamp":1395928077000},"page":"5708-5720","source":"Crossref","is-referenced-by-count":6,"title":["Optically Active Tetra\u2010<i>tert<\/i>\u2010butyl\u2010P<sub>5<\/sub>\u2010deltacyclene Epimers: Preparation, Spectroscopy, Dynamic Equilibriums, H\/D Exchange, and Transition\u2010Metal Complex Chemistry"],"prefix":"10.1002","volume":"20","author":[{"given":"Lars","family":"Rohwer","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Christine","family":"H\u00f6hn","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jochen","family":"Autschbach","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Walter","family":"Bauer","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Frank W.","family":"Heinemann","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sergi","family":"Huguet\u2005Torrell","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Irene","family":"Keller","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Tatyana E.","family":"Shubina","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jacob","family":"Steffen","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ulrich","family":"Zenneck","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2014,3,27]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1515\/znb-1981-0105"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19891010715"},{"key":"e_1_2_6_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198909001"},{"key":"e_1_2_6_2_4","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19891010808"},{"key":"e_1_2_6_2_5","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198910131"},{"key":"e_1_2_6_2_6","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(89)85103-4"},{"volume-title":"Phosphorus: The Carbon Copy","year":"1998","author":"Dillon K. 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Peralta F. Ogliaro M. Bearpark J.\u2005J. Heyd E. Brothers K.\u2005N. Kudin V.\u2005N. Staroverov R. Kobayashi J. Normand K. Raghavachari A. Rendell J.\u2005C. Burant S.\u2005S. Iyengar J. Tomasi M. Cossi N. Rega J.\u2005M. Millam M. Klene J.\u2005E. Knox J.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski R.\u2005L. Martin K. Morokuma V.\u2005G. Zakrzewski G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg S. Dapprich A.\u2005D. Daniels \u00d6. Farkas J.\u2005B. Foresman J.\u2005V. Ortiz J. Cioslowski and D.\u2005J. Fox Gaussian Inc. 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