{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,4]],"date-time":"2026-09-04T21:07:08Z","timestamp":1788556028778,"version":"build-2803163510"},"reference-count":78,"publisher":"Wiley","issue":"8","license":[{"start":{"date-parts":[[2007,12,28]],"date-time":"2007-12-28T00:00:00Z","timestamp":1198800000000},"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":[[2008,3,7]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The osmium compound <jats:italic>trans<\/jats:italic>,<jats:italic>cis<\/jats:italic>\u2010[OsCl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>(Pyme)] (<jats:bold>1<\/jats:bold>) (Pyme=1\u2010(pyridin\u20102\u2010yl)methanamine), obtained from [OsCl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>] and Pyme, thermally isomerizes to <jats:italic>cis<\/jats:italic>,<jats:italic>cis<\/jats:italic>\u2010[OsCl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>(Pyme)] (<jats:bold>2<\/jats:bold>) in mesitylene at 150\u2009\u00b0C. Reaction of [OsCl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>] with Ph<jats:sub>2<\/jats:sub>P(CH<jats:sub>2<\/jats:sub>)<jats:sub>4<\/jats:sub>PPh<jats:sub>2<\/jats:sub> (dppb) and Pyme in mesitylene (150\u2009\u00b0C, 4\u2005h) leads to a mixture of <jats:italic>trans<\/jats:italic>\u2010[OsCl<jats:sub>2<\/jats:sub>(dppb)(Pyme)] (<jats:bold>3<\/jats:bold>) and <jats:italic>cis<\/jats:italic>\u2010[OsCl<jats:sub>2<\/jats:sub>(dppb)(Pyme)] (<jats:bold>4<\/jats:bold>) in about an 1:3 molar ratio. The complex <jats:italic>trans<\/jats:italic>\u2010[OsCl<jats:sub>2<\/jats:sub>(dppb)(Pyet)] (<jats:bold>5<\/jats:bold>) (Pyet=2\u2010(pyridin\u20102\u2010yl)ethanamine) is formed by reaction of [OsCl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>] with dppb and Pyet in toluene at reflux. Compounds <jats:bold>1<\/jats:bold>, <jats:bold>2<\/jats:bold>, <jats:bold>5<\/jats:bold> and the mixture of isomers <jats:bold>3<\/jats:bold>\/<jats:bold>4<\/jats:bold> efficiently catalyze the transfer hydrogenation (TH) of different ketones in refluxing 2\u2010propanol and in the presence of NaO<jats:italic>i<\/jats:italic>Pr (2.0\u2005mol\u2009%). Interestingly, <jats:bold>3<\/jats:bold>\/<jats:bold>4<\/jats:bold> has been proven to reduce different ketones (even bulky) by means of TH with a remarkably high turnover frequency (TOF up to 5.7\u00d710<jats:sup>5<\/jats:sup>\u2005h<jats:sup>\u22121<\/jats:sup>) and at very low loading (0.05\u20130.001 mol\u2009%). The system <jats:bold>3<\/jats:bold>\/<jats:bold>4<\/jats:bold> also efficiently catalyzes the hydrogenation of many ketones (H<jats:sub>2<\/jats:sub>, 5.0\u2005atm) in ethanol with KO<jats:italic>t<\/jats:italic>Bu (2.0\u2005mol\u2009%) at 70\u2009\u00b0C (TOF up to 1.5\u00d710<jats:sup>4<\/jats:sup>\u2005h<jats:sup>\u22121<\/jats:sup>). The in\u2010situ\u2010generated catalysts prepared by the reaction of [OsCl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>] with Josiphos diphosphanes and (\u00b1)\u20101\u2010alkyl\u2010substituted Pyme ligands, promote the enantioselective TH of different ketones with 91\u201396\u2009%\u2005<jats:italic>ee<\/jats:italic> (<jats:italic>ee<\/jats:italic>=enantiomeric excess) and with a TOF of up to 1.9\u00d710<jats:sup>4<\/jats:sup>\u2005h<jats:sup>\u22121<\/jats:sup> at 60\u2009\u00b0C.<\/jats:p>","DOI":"10.1002\/chem.200701719","type":"journal-article","created":{"date-parts":[[2007,12,28]],"date-time":"2007-12-28T11:22:16Z","timestamp":1198840936000},"page":"2557-2563","source":"Crossref","is-referenced-by-count":75,"title":["Osmium Pyme Complexes for Fast Hydrogenation and Asymmetric Transfer Hydrogenation of Ketones"],"prefix":"10.1002","volume":"14","author":[{"given":"Walter","family":"Baratta","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Maurizio","family":"Ballico","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alessandro","family":"Del\u2005Zotto","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Katia","family":"Siega","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Santo","family":"Magnolia","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pierluigi","family":"Rigo","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2008,2,28]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","volume-title":"The Handbook of Homogeneous Hydrogenation, Vols.\u20051\u20133","year":"2007"},{"key":"e_1_2_6_3_2","volume-title":"Asymmetric Catalysis on Industrial Scale","year":"2004"},{"key":"e_1_2_6_4_2","volume-title":"Comprehensive Asymmetric Catalysis","year":"2004"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/0471721506"},{"key":"e_1_2_6_6_2","unstructured":"\u00a0"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/b515269k"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/B513396C"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/B513564H"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2004.04.007"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19980619)110:12<1792::AID-ANGE1792>3.0.CO;2-9"},{"key":"e_1_2_6_11_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19980703)37:12<1703::AID-ANIE1703>3.0.CO;2-I"},{"key":"e_1_2_6_12_2","unstructured":"\u00a0"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/cc9960000233"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19971090333"},{"key":"e_1_2_6_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199702851"},{"key":"e_1_2_6_15_2","unstructured":"\u00a0"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200454199"},{"key":"e_1_2_6_16_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200454199"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/om049408l"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2005.07.001"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0491701"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200702278"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja052071"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200304884"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0620989"},{"key":"e_1_2_6_24_2","unstructured":"\u00a0"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/om990210o"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200505246"},{"key":"e_1_2_6_27_2","unstructured":"\u00a0"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00390a043"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0957-4166(00)82111-4"},{"key":"e_1_2_6_30_2","unstructured":"\u00a0"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00127a027"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja002177z"},{"key":"e_1_2_6_33_2","unstructured":"\u00a0"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja071159f"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2006.09.058"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1002\/asia.200600105"},{"key":"e_1_2_6_37_2","first-page":"1745","volume":"62","author":"Chen J. 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