{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T00:54:26Z","timestamp":1760316866126,"version":"build-2065373602"},"reference-count":95,"publisher":"Wiley","issue":"25","license":[{"start":{"date-parts":[[2009,5,6]],"date-time":"2009-05-06T00:00:00Z","timestamp":1241568000000},"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":[[2009,6,15]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:bold>Osmabenzenes can be easily synthesized<\/jats:bold> from two \u03b7<jats:sup>2<\/jats:sup>\u2010coordinated olefin osmacycles in the presence of benzonitrile by means of facile hydrogen\u2010transfer conversions (see graphic). Mechanisms for the formation of osmabenzenes are proposed based on DFT calculations.<jats:boxed-text content-type=\"graphic\" position=\"anchor\"><jats:graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" mimetype=\"image\/gif\" position=\"anchor\" specific-use=\"enlarged-web-image\" xlink:href=\"graphic\/mcontent.gif\"><jats:alt-text>magnified image<\/jats:alt-text><\/jats:graphic><\/jats:boxed-text><\/jats:p><jats:p>Treatment of HC\uf8fdCC(CH<jats:sub>3<\/jats:sub>)(OH)CH\uf8feCH<jats:sub>2<\/jats:sub> with [OsCl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>] in dichloromethane yielded the \u03b7<jats:sup>2<\/jats:sup>\u2010olefin\u2010coordinated osmacycle [Os{CH\uf8feC(PPh<jats:sub>3<\/jats:sub>)C(\uf8feCH<jats:sub>2<\/jats:sub>)\u2010\u03b7<jats:sup>2<\/jats:sup>\u2010CH\uf8feCH<jats:sub>2<\/jats:sub>}Cl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>] (<jats:bold>9<\/jats:bold>). Transformations of osmacycle <jats:bold>9<\/jats:bold> by treatment with benzonitrile under various conditions have been investigated. Reaction of <jats:bold>9<\/jats:bold> with excess benzonitrile at room temperature afforded the dicationic osmacycle [Os{CH\uf8feC(PPh<jats:sub>3<\/jats:sub>)C(\uf8feCH<jats:sub>2<\/jats:sub>)\u2010\u03b7<jats:sup>2<\/jats:sup>\u2010CH\uf8feCH<jats:sub>2<\/jats:sub>}(PhCN)<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>]Cl<jats:sub>2<\/jats:sub> (<jats:bold>11<\/jats:bold>) by ligand substitution, which reacted further to the intramolecularly coordinated \u03b7<jats:sup>2<\/jats:sup>\u2010allene complex [Os{CH\uf8feC(PPh<jats:sub>3<\/jats:sub>)C(CH<jats:sub>3<\/jats:sub>)\uf8fe(\u03b7<jats:sup>2<\/jats:sup>\u2010C\uf8feCH<jats:sub>2<\/jats:sub>)}(PhCN)<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>]Cl<jats:sub>2<\/jats:sub> (<jats:bold>12<\/jats:bold>). In contrast, heating a chloroform solution of <jats:bold>9<\/jats:bold> to the reflux temperature in the presence of excess benzonitrile generated osmabenzene [Os{CHC(PPh<jats:sub>3<\/jats:sub>)C(CH<jats:sub>3<\/jats:sub>)CHCH}(PhCN)<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>]Cl<jats:sub>2<\/jats:sub> (<jats:bold>14<\/jats:bold>). Complexes <jats:bold>11<\/jats:bold>, <jats:bold>12<\/jats:bold> and <jats:bold>14<\/jats:bold> are in fact isomers. In the absence of excess benzonitrile, the isolated dicationic <jats:bold>12<\/jats:bold> and <jats:bold>14<\/jats:bold> readily dissociate the benzonitrile ligands in solution to produce the neutral complex [Os{CH\uf8feC(PPh<jats:sub>3<\/jats:sub>)C(CH<jats:sub>3<\/jats:sub>)\uf8fe(\u03b7<jats:sup>2<\/jats:sup>\u2010C\uf8feCH<jats:sub>2<\/jats:sub>)}Cl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>] (<jats:bold>13<\/jats:bold>) and the monocationic osmabenzene [Os{CHC(PPh<jats:sub>3<\/jats:sub>)C(CH<jats:sub>3<\/jats:sub>)CHCH}Cl(PhCN)(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>]BPh<jats:sub>4<\/jats:sub> (<jats:bold>15<\/jats:bold>), respectively. Mechanisms for the formation of osmabenzene <jats:bold>14<\/jats:bold> from <jats:bold>11<\/jats:bold> and <jats:bold>12<\/jats:bold> are proposed based on DFT calculations.<\/jats:p>","DOI":"10.1002\/chem.200900214","type":"journal-article","created":{"date-parts":[[2009,5,6]],"date-time":"2009-05-06T08:09:21Z","timestamp":1241597361000},"page":"6258-6266","source":"Crossref","is-referenced-by-count":48,"title":["Osmabenzenes from Osmacycles Containing an \u03b7<sup>2<\/sup>\u2010Coordinated Olefin"],"prefix":"10.1002","volume":"15","author":[{"given":"Lei","family":"Gong","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Zhening","family":"Chen","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yumei","family":"Lin","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xumin","family":"He","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ting Bin","family":"Wen","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xin","family":"Xu","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Haiping","family":"Xia","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2009,6,5]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For recent reviews of aromatic metallacycles see:"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar700071p"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2006.11.018"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar0201512"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar020093k"},{"key":"e_1_2_6_6_2","unstructured":"Some recent work on aromatic metallacycles:"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja8048892"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/om8008712"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200703289"},{"key":"e_1_2_6_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200703289"},{"key":"e_1_2_6_10_2","unstructured":"Reviews of metallabenzenes:"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr990337n"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200504358"},{"key":"e_1_2_6_12_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200504358"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/b517928a"},{"key":"e_1_2_6_14_2","unstructured":"Examples of recent theoretical work:"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp7106044"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja068884v"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200601674"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0701367"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0443456"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja047125e"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja037983v"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja036723a"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1039\/b210622a"},{"key":"e_1_2_6_24_2","first-page":"440","volume":"16","author":"Huang Y.","year":"2003","journal-title":"Chin. 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