{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,13]],"date-time":"2026-01-13T04:55:44Z","timestamp":1768280144830,"version":"3.49.0"},"reference-count":87,"publisher":"Wiley","issue":"35","license":[{"start":{"date-parts":[[2008,10,31]],"date-time":"2008-10-31T00:00:00Z","timestamp":1225411200000},"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":[[2008,12,8]]},"abstract":"Abstract<\/jats:title>Reactions of the methoxo complexes [{M(\u03bc\u2010OMe)(cod)}2<\/jats:sub>] (cod=1,5\u2010cyclooctadiene, M=Rh, Ir) with 2,2\u2010dimethylaziridine (Haz) give the mixed\u2010bridged complexes [{M2<\/jats:sub>(\u03bc\u2010az)(\u03bc\u2010OMe)(cod)2<\/jats:sub>}] [(M=Rh, 1<\/jats:bold>; M=Ir, 2<\/jats:bold>). These compounds are isolated intermediates in the stereospecific synthesis of the amido\u2010bridged complexes [{M(\u03bc\u2010az)(cod)}2<\/jats:sub>] (M=Rh, 3<\/jats:bold>; M=Ir, 4<\/jats:bold>). The electrochemical behavior of 3<\/jats:bold> and 4<\/jats:bold> in CH2<\/jats:sub>Cl2<\/jats:sub> and CH3<\/jats:sub>CN is greatly influenced by the solvent. On a preparative scale, the chemical oxidation of 3<\/jats:bold> and 4<\/jats:bold> with [FeCp2<\/jats:sub>]+<\/jats:sup> gives the paramagnetic cationic species [{M(\u03bc\u2010az)(cod)}2<\/jats:sub>]+<\/jats:sup> (M=Rh, [3<\/jats:bold>]+<\/jats:bold><\/jats:sup>; M=Ir, [4<\/jats:bold>]+<\/jats:bold><\/jats:sup>). The Rh complex [3<\/jats:bold>]+<\/jats:bold><\/jats:sup> is stable in dichloromethane, whereas the Ir complex [4<\/jats:bold>]+<\/jats:bold><\/jats:sup> transforms slowly, but quantitatively, into a 1:1 mixture of the allyl compound [(\u03b73<\/jats:sup>,\u03b72<\/jats:sup>\u2010C8<\/jats:sub>H11<\/jats:sub>)Ir(\u03bc\u2010az)2<\/jats:sub>Ir(cod)] ([5<\/jats:bold>]+<\/jats:bold><\/jats:sup>) and the hydride compound [(cod)(H)Ir(\u03bc\u2010az)2<\/jats:sub>Ir(cod)] ([6<\/jats:bold>]+<\/jats:bold><\/jats:sup>). Addition of small amounts of acetonitrile to dichloromethane solutions of [3<\/jats:bold>]+<\/jats:bold><\/jats:sup> and [4<\/jats:bold>]+<\/jats:bold><\/jats:sup> triggers a fast disproportionation reaction in both cases to produce equimolecular amounts of the starting materials 3<\/jats:bold> and 4<\/jats:bold> and metal\uf8ffmetal bonded MII<\/jats:sup>\uf8ffMII<\/jats:sup> species. These new compounds are isolated by oxidation of 3<\/jats:bold> and 4<\/jats:bold> with [FeCp2<\/jats:sub>]+<\/jats:sup> in acetonitrile as the mixed\u2010ligand complexes [(MeCN)3<\/jats:sub>M(\u03bc\u2010az)2<\/jats:sub>M(NCMe)(cod)](PF6<\/jats:sub>)2<\/jats:sub> (M=Rh, [8<\/jats:bold>]2+<\/jats:bold><\/jats:sup>; M=Ir, [9<\/jats:bold>]2+<\/jats:bold><\/jats:sup>). The electronic structures of [3<\/jats:bold>]+<\/jats:bold><\/jats:sup> and [4<\/jats:bold>]+<\/jats:bold><\/jats:sup> have been elucidated through EPR measurements and DFT calculations showing that their unpaired electron is primarily delocalized over the two metal centers, with minor spin densities at the two bridging amido nitrogen groups. The HOMO of 3<\/jats:bold> and 4<\/jats:bold> and the SOMO of [3<\/jats:bold>]+<\/jats:bold><\/jats:sup> and [4<\/jats:bold>]+<\/jats:bold><\/jats:sup> are essentially M\uf8ffM d\u2013d \u03c3*\u2010antibonding orbitals, explaining the formation of a net bonding interaction between the metals upon oxidation of 3<\/jats:bold> and 4<\/jats:bold>. Mechanisms for the observed allylic H\u2010atom abstraction reactions from the paramagnetic (radical) complexes are proposed.<\/jats:p>","DOI":"10.1002\/chem.200801615","type":"journal-article","created":{"date-parts":[[2008,10,31]],"date-time":"2008-10-31T05:10:34Z","timestamp":1225429834000},"page":"10985-10998","source":"Crossref","is-referenced-by-count":11,"title":["Intervalent Bis(\u03bc\u2010aziridinato)MII<\/sup>\uf8ffMI<\/sup> Complexes (M=Rh, Ir): Delocalized Metallo\u2010Radicals or Delocalized Aminyl Radicals?"],"prefix":"10.1002","volume":"14","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":"Vincenzo","family":"Passarelli","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jos\u00e9\u2005A.","family":"L\u00f3pez","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Bas","family":"de\u2005Bruin","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2008,12]]},"reference":[{"key":"e_1_2_6_1_2","volume-title":"Electron Transfer and Radical Processes in Transition\u2010Metal Chemistry","author":"Astruc D.","year":"1995"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470144428.ch5"},{"key":"e_1_2_6_3_2","unstructured":"\u00a0"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0612798"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1106070"},{"key":"e_1_2_6_6_2","unstructured":"\u00a0"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200605170"},{"key":"e_1_2_6_7_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200605170"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.crci.2007.03.017"},{"key":"e_1_2_6_9_2","unstructured":"\u00a0"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/om7009705"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/om060777m"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/om050594k"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20020715)8:14<3128::AID-CHEM3128>3.0.CO;2-F"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0109952"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/om990844v"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1522-2675(20000119)83:1<119::AID-HLCA119>3.0.CO;2-Q"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(96)06907-0"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00045a004"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00254a001"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200305378"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja052473h"},{"key":"e_1_2_6_22_2","unstructured":"\u00a0"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja016213l"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/om050044m"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00033a014"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200600971"},{"key":"e_1_2_6_27_2","volume-title":"Aziridines and Epoxides in Organic Synthesis","year":"2006"},{"key":"e_1_2_6_28_2","unstructured":"\u00a0"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0708666"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1039\/b711638a"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar050038m"},{"key":"e_1_2_6_32_2","unstructured":"\u00a0"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0660756"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja017652n"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.poly.2007.11.023"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/om960005y"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp021799z"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0439470"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200600711"},{"key":"e_1_2_6_40_2","unstructured":"Considering the large amount of parameters contributing to the shape and HFI multiplets in the spectrum of [4]+ it is not clear how unique the obtained fit is to the particular set of parameters in Table\u20054."},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0277-5387(00)81730-1"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20010216)113:4<737::AID-ANGE7370>3.0.CO;2-0"},{"key":"e_1_2_6_42_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010216)40:4<715::AID-ANIE7150>3.0.CO;2-4"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19991018)111:20<3228::AID-ANGE3228>3.0.CO;2-Q"},{"key":"e_1_2_6_43_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19991018)38:20<3043::AID-ANIE3043>3.0.CO;2-2"},{"key":"e_1_2_6_44_2","unstructured":"\u00a0"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1021\/om034218g"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/om980801z"},{"key":"e_1_2_6_47_2","doi-asserted-by":"publisher","DOI":"10.1021\/om030192h"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)89448-6"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39830000580"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01848a504"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470132548.ch25"},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50102a001"},{"key":"e_1_2_6_53_2","unstructured":"R. Ahlrichs M. B\u00e4r H.\u2010P. Baron R. Bauernschmitt S. B\u00f6cker M. Ehrig K. Eichkorn S. Elliott F. Furche F. Haase M. H\u00e4ser C. H\u00e4ttig H. Horn C. Huber U. Huniar M. Kattannek A. K\u00f6hn C. K\u00f6lmel M. Kollwitz K. May C. Ochsenfeld H. \u00d6hm A. Sch\u00e4fer U. Schneider O. Treutler K. Tsereteli B. Unterreiner M. von\u2005Arnim F. Weigend P. Weis H. Weiss Turbomole Version 5 January2002. Theoretical Chemistry Group University of Karlsruhe;"},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.469408"},{"key":"e_1_2_6_55_2","unstructured":"Turbomole basis\u2010set library Turbomole Version 5 see (a);"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.463096"},{"key":"e_1_2_6_57_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF01114537"},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.467146"},{"key":"e_1_2_6_59_2","unstructured":"\u00a0"},{"key":"e_1_2_6_60_2","unstructured":"PQS version 2.4 2001 Parallel Quantum Solutions Fayetteville Arkansas USA (the Baker optimizer is available separately from PQS upon request);"},{"key":"e_1_2_6_61_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.540070402"},{"key":"e_1_2_6_62_2","unstructured":"\u00a0"},{"key":"e_1_2_6_63_2","first-page":"785","volume":"37","author":"Lee C.","year":"1988","journal-title":"J. Chem. Phys. J. Chem. Phys."},{"key":"e_1_2_6_64_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.464304"},{"key":"e_1_2_6_65_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.464913"},{"key":"e_1_2_6_66_2","unstructured":"All calculations were performed by using the Turbomole functional \u201cb3\u2010lyp\u201d which is not identical to the Gaussian \u201cB3\u2009LYP\u201d functional."},{"key":"e_1_2_6_67_2","unstructured":"Some references and reviews on DFT approaches to EPR parameters:"},{"key":"e_1_2_6_68_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.474590"},{"key":"e_1_2_6_69_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.475889"},{"key":"e_1_2_6_70_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1367-5931(02)00006-6"},{"key":"e_1_2_6_71_2","doi-asserted-by":"publisher","DOI":"10.1002\/9783527620548.ch9c"},{"key":"e_1_2_6_72_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00091a029"},{"key":"e_1_2_6_73_2","unstructured":"\u00a0"},{"key":"e_1_2_6_74_2","doi-asserted-by":"publisher","DOI":"10.1016\/0301-0104(73)80059-X"},{"key":"e_1_2_6_75_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.454603"},{"key":"e_1_2_6_76_2","doi-asserted-by":"publisher","DOI":"10.1016\/0021-9991(92)90277-6"},{"key":"e_1_2_6_77_2","doi-asserted-by":"publisher","DOI":"10.1007\/s002140050021"},{"key":"e_1_2_6_78_2","unstructured":"\u00a0"},{"key":"e_1_2_6_79_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevA.38.3098"},{"key":"e_1_2_6_80_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.33.8822"},{"key":"e_1_2_6_81_2","doi-asserted-by":"publisher","DOI":"10.1023\/A:1008193805436"},{"key":"e_1_2_6_82_2","unstructured":"G.\u2005M. Sheldrick SADABS Bruker AXS Madison WI 1997."},{"key":"e_1_2_6_83_2","unstructured":"G.\u2005M. Sheldrick SHELXL\u201097 Program for Crystal Structure Refinement University of G\u00f6ttingen G\u00f6ttingen Germany 1997."},{"key":"e_1_2_6_84_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889899006020"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200801615","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200801615","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T19:05:54Z","timestamp":1760295954000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200801615"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2008,12]]},"references-count":87,"journal-issue":{"issue":"35","published-print":{"date-parts":[[2008,12,8]]}},"alternative-id":["10.1002\/chem.200801615"],"URL":"https:\/\/doi.org\/10.1002\/chem.200801615","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2008,12]]}}}