{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2023,3,13]],"date-time":"2023-03-13T06:54:11Z","timestamp":1678690451487},"reference-count":40,"publisher":"Institute of Organic Chemistry & Biochemistry","issue":"5-6","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Collect. Czech. Chem. Commun."],"published-print":{"date-parts":[[2007]]},"abstract":"<jats:p>The observation that the 14-electron cation [Rh(PPh<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>]<jats:sup>+<\/jats:sup> is more electron-rich than expected, as a result of coordination of a C=C bond in one phenyl group, opened the way to a search for more examples of this behavior. We used DFT calculations and energy decomposition analysis to study this M-\u03b7<jats:sup>2<\/jats:sup>-arene interaction and to calculate its strength. For this purpose, we have chosen two formally unsaturated complexes, viz. [Mo(\u03b7<jats:sup>5<\/jats:sup>-C<jats:sub>5<\/jats:sub>H<jats:sub>5<\/jats:sub>)(CO)<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)]<jats:sup>+<\/jats:sup> (<jats:bold>1<\/jats:bold>) and [Ru(\u03b7<jats:sup>5<\/jats:sup>-C<jats:sub>5<\/jats:sub>H<jats:sub>5<\/jats:sub>)(binap)]<jats:sup>+<\/jats:sup> (<jats:bold>2<\/jats:bold>). In the former complex, the PPh<jats:sub>3<\/jats:sub> ligand can be easily moved away from the metal, destroying the Mo-\u03b7<jats:sup>2<\/jats:sup>-arene interaction, while in <jats:bold>2<\/jats:bold> this is achieved by a distortion of the Binap ligand. The experimental parameters, namely the distortion of the aryl-containing ligand, have been well reproduced by the calculated coordination geometry; the M-\u03b7<jats:sup>2<\/jats:sup>-arene interaction was estimated as 13.4 kcal mol<jats:sup>-1<\/jats:sup> for Mo and 21.4 kcal mol<jats:sup>-1<\/jats:sup> for Ru. The energy decomposition analysis revealed the formation of a covalent bond between the metal and the C=C bond, which made the global process favorable, regard- less the energy required to reorganize the geometry of the ligand in the new environment. <\/jats:p>","DOI":"10.1135\/cccc20070703","type":"journal-article","created":{"date-parts":[[2007,6,21]],"date-time":"2007-06-21T04:55:32Z","timestamp":1182401732000},"page":"703-714","source":"Crossref","is-referenced-by-count":3,"title":["Remote Metal-Arene \u03c0 Bonding in Organometallic Complexes: a DFT Study"],"prefix":"10.1135","volume":"72","author":[{"given":"Paulo J.","family":"Costa","sequence":"first","affiliation":[]},{"given":"Maria Jos\u00e9","family":"Calhorda","sequence":"additional","affiliation":[]},{"given":"Paul S.","family":"Pregosin","sequence":"additional","affiliation":[]}],"member":"111","published-online":{"date-parts":[[2007]]},"reference":[{"key":"20070703_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00322a040"},{"key":"20070703_2","doi-asserted-by":"publisher","DOI":"10.1039\/a905092b"},{"key":"20070703_3","doi-asserted-by":"publisher","DOI":"10.1021\/ja953711j"},{"key":"20070703_4a","doi-asserted-by":"publisher","DOI":"10.1039\/dt9950000049"},{"key":"20070703_4b","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(95)05687-K"},{"key":"20070703_5","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(94)84115-2"},{"key":"20070703_6","doi-asserted-by":"publisher","DOI":"10.1021\/om9707275"},{"key":"20070703_7a","doi-asserted-by":"publisher","DOI":"10.1021\/om0205344"},{"key":"20070703_7b","doi-asserted-by":"publisher","DOI":"10.1021\/om010730v"},{"key":"20070703_8a","doi-asserted-by":"publisher","DOI":"10.1021\/ja017082r"},{"key":"20070703_8b","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2005.06.072"},{"key":"20070703_9a","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3765(19990503)5:5<1452::AID-CHEM1452>3.0.CO;2-8"},{"key":"20070703_9b","doi-asserted-by":"publisher","DOI":"10.1071\/CH9950741"},{"key":"20070703_9c","doi-asserted-by":"publisher","DOI":"10.1071\/CH9901245"},{"key":"20070703_10a","doi-asserted-by":"publisher","DOI":"10.1021\/ar990080f"},{"key":"20070703_10b","doi-asserted-by":"publisher","DOI":"10.1002\/1099-0682(200208)2002:8<1907::AID-EJIC1907>3.0.CO;2-K"},{"key":"20070703_11","doi-asserted-by":"publisher","DOI":"10.1021\/om040107l"},{"key":"20070703_12","doi-asserted-by":"publisher","DOI":"10.1016\/j.crci.2006.10.008"},{"key":"20070703_13","doi-asserted-by":"publisher","DOI":"10.1021\/ic051869r"},{"key":"20070703_14","doi-asserted-by":"publisher","DOI":"10.1021\/ic50085a003"},{"key":"20070703_15","doi-asserted-by":"crossref","first-page":"395","DOI":"10.1016\/0022-328X(83)85065-7","volume":"250","author":"Green","year":"1983","journal-title":"J. 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