{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,13]],"date-time":"2026-10-13T23:44:37Z","timestamp":1791935077854,"version":"4.3.4"},"reference-count":102,"publisher":"Wiley","issue":"30","license":[{"start":{"date-parts":[[2008,9,18]],"date-time":"2008-09-18T00:00:00Z","timestamp":1221696000000},"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":[[2008,10,20]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>New benzo[<jats:italic>h<\/jats:italic>]quinoline ligands (HCN\u2032N) containing a CHRNH<jats:sub>2<\/jats:sub> (R=H (<jats:bold>a<\/jats:bold>), Me (<jats:bold>b<\/jats:bold>), <jats:italic>t<\/jats:italic>Bu (<jats:bold>c<\/jats:bold>)) function in the 2\u2010position were prepared starting from benzo[<jats:italic>h<\/jats:italic>]quinoline <jats:italic>N<\/jats:italic>\u2010oxide (in the case of ligand <jats:bold>a<\/jats:bold>) and 2\u2010chlorobenzo[<jats:italic>h<\/jats:italic>]quinoline (for ligands <jats:bold>b<\/jats:bold> and <jats:bold>c<\/jats:bold>). These compounds were used to prepare ruthenium and osmium complexes, which are excellent catalysts for the transfer hydrogenation (TH) of ketones. The reaction of <jats:bold>a<\/jats:bold> with [RuCl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>] in 2\u2010propanol at reflux afforded the terdentate CN\u2032N complex [RuCl(CN\u2032N)(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>] (<jats:bold>1<\/jats:bold>), whereas the complexes [RuCl(CN\u2032N)(dppb)] (<jats:bold>2<\/jats:bold>\u2013<jats:bold>4<\/jats:bold>; dppb=Ph<jats:sub>2<\/jats:sub>P(CH<jats:sub>2<\/jats:sub>)<jats:sub>4<\/jats:sub>PPh<jats:sub>2<\/jats:sub>) were obtained from [RuCl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)(dppb)] with <jats:bold>a<\/jats:bold>\u2013<jats:bold>c<\/jats:bold>, respectively. Employment of (<jats:italic>R<\/jats:italic>,<jats:italic>S<\/jats:italic>)\u2010Josiphos, (<jats:italic>S<\/jats:italic>,<jats:italic>R<\/jats:italic>)\u2010Josiphos*, (<jats:italic>S<\/jats:italic>,<jats:italic>S<\/jats:italic>)\u2010Skewphos, and (<jats:italic>S<\/jats:italic>)\u2010MeO\u2010Biphep in combination with [RuCl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>] and ligand\u2005<jats:bold>a<\/jats:bold> gave the chiral derivatives [RuCl(CN\u2032N)(PP)] (<jats:bold>5<\/jats:bold>\u2013<jats:bold>8<\/jats:bold>). The osmium complex [OsCl(CN\u2032N)(dppb)] (<jats:bold>12<\/jats:bold>) was prepared by treatment of [OsCl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>] with dppb and ligand\u2005<jats:bold>a<\/jats:bold>. Reaction of the chloride <jats:bold>2<\/jats:bold> and <jats:bold>12<\/jats:bold> with NaO<jats:italic>i<\/jats:italic>Pr in 2\u2010propanol\/toluene afforded the hydride complexes [MH(CN\u2032N)(dppb)] (M=Ru <jats:bold>10<\/jats:bold>, Os <jats:bold>14<\/jats:bold>), through elimination of acetone from [M(O<jats:italic>i<\/jats:italic>Pr)(CN\u2032N)(dppb)] (M=Ru <jats:bold>9<\/jats:bold>, Os <jats:bold>13<\/jats:bold>). The species <jats:bold>9<\/jats:bold> and <jats:bold>13<\/jats:bold> easily reacted with 4,4\u2032\u2010difluorobenzophenone, via <jats:bold>10<\/jats:bold> and <jats:bold>14<\/jats:bold>, respectively, affording the corresponding isolable alkoxides [M(OR)(CN\u2032N)(dppb)] (M=Ru <jats:bold>11<\/jats:bold>, Os <jats:bold>15<\/jats:bold>). The complexes [MX(CN\u2032N)(P<jats:sub>2<\/jats:sub>)] (<jats:bold>1<\/jats:bold>\u2013<jats:bold>15<\/jats:bold>) (M=Ru, Os; X=Cl, H, OR; P=PPh<jats:sub>3<\/jats:sub> and P<jats:sub>2<\/jats:sub>=diphosphane) are efficient catalysts for the TH of carbonyl compounds with 2\u2010propanol in the presence of NaO<jats:italic>i<\/jats:italic>Pr (2\u2005mol\u2009%). Turnover frequency (TOF) values up to 1.8\u00d710<jats:sup>6<\/jats:sup>\u2005h<jats:sup>\u22121<\/jats:sup> have been achieved using 0.02\u20130.001\u2005mol\u2009% of catalyst. Much the same activity has been observed for the Ru\uf8ffCl, \uf8ffH, \uf8ffOR, and the Os\uf8ffCl derivatives, whereas the Os\uf8ffH and Os\uf8ffOR derivatives display significantly lower activity on account of their high oxygen sensitivity. The chiral Ru complexes <jats:bold>5<\/jats:bold>\u2013<jats:bold>8<\/jats:bold> catalyze the asymmetric TH of methyl\u2013aryl ketones with TOF \u224810<jats:sup>5<\/jats:sup>\u2005h<jats:sup>\u22121<\/jats:sup> at 60\u2009\u00b0C, up to 97\u2009% enatiomeric excess (<jats:italic>ee<\/jats:italic>) and remarkably high productivity (0.005\u2005mol\u2009% catalyst loading). High catalytic activity (TOF up to 2.2\u00d710<jats:sup>5<\/jats:sup>\u2005h<jats:sup>\u22121<\/jats:sup>) and enantioselectivity (up to 98\u2009%\u2005<jats:italic>ee<\/jats:italic>) have also been achieved with the in\u2010situ\u2010generated catalysts prepared from [MCl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>], (<jats:italic>S<\/jats:italic>,<jats:italic>R<\/jats:italic>)\u2010Josiphos or (<jats:italic>S<\/jats:italic>,<jats:italic>R<\/jats:italic>)\u2010Josiphos*, and the benzo[<jats:italic>h<\/jats:italic>]quinoline ligands <jats:bold>a<\/jats:bold>\u2013<jats:bold>c<\/jats:bold>.<\/jats:p>","DOI":"10.1002\/chem.200800888","type":"journal-article","created":{"date-parts":[[2008,9,18]],"date-time":"2008-09-18T13:39:23Z","timestamp":1221745163000},"page":"9148-9160","source":"Crossref","is-referenced-by-count":100,"title":["New Benzo[<i>h<\/i>]quinoline\u2010Based Ligands and their Pincer Ru and Os Complexes for Efficient Catalytic Transfer Hydrogenation of Carbonyl Compounds"],"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":"Salvatore","family":"Baldino","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Giorgio","family":"Chelucci","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Eberhardt","family":"Herdtweck","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":[[2008,10,10]]},"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","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20010105)113:1<40::AID-ANGE40>3.0.CO;2-K"},{"key":"e_1_2_6_4_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010105)40:1<40::AID-ANIE40>3.0.CO;2-5"},{"key":"e_1_2_6_5_2","unstructured":"\u00a0"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar700134q"},{"key":"e_1_2_6_7_2","first-page":"1215","volume-title":"The Handbook of Homogeneous Hydrogenation, Vol.\u20053","author":"Blacker A. J.","year":"2007"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/b515269k"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/B513396C"},{"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","unstructured":"\u00a0"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19971090333"},{"key":"e_1_2_6_12_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199702851"},{"key":"e_1_2_6_13_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_13_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_14_2","unstructured":"\u00a0"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9906610"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja991638h"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20000804)6:15<2818::AID-CHEM2818>3.0.CO;2-Q"},{"key":"e_1_2_6_18_2","unstructured":"\u00a0"},{"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\/ange.200702278"},{"key":"e_1_2_6_20_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200702278"},{"key":"e_1_2_6_21_2","unstructured":"\u00a0"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja052071"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0489387"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/om700849w"},{"key":"e_1_2_6_25_2","unstructured":"\u00a0"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200454199"},{"key":"e_1_2_6_26_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200454199"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/om049408l"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2005.07.001"},{"key":"e_1_2_6_29_2","unstructured":"\u00a0"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200502118"},{"key":"e_1_2_6_30_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200502118"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/om060408q"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200700014"},{"key":"e_1_2_6_33_2","unstructured":"\u00a0"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9943997"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/om990232a"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200701719"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200800339"},{"key":"e_1_2_6_37_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200800339"},{"key":"e_1_2_6_38_2","unstructured":"\u00a0"},{"key":"e_1_2_6_39_2","first-page":"45","volume-title":"The Handbook of Homogeneous Hydrogenation, Vol.\u20051","author":"Morris R. H.","year":"2007"},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1016\/1381-1169(94)00039-5"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200300898"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1002\/1615-4169(200207)344:5<499::AID-ADSC499>3.0.CO;2-R"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol016641w"},{"key":"e_1_2_6_44_2","first-page":"806","volume":"18","author":"Jung M. K.","year":"1997","journal-title":"Bull. Korean Chem. Soc."},{"key":"e_1_2_6_45_2","unstructured":"See for example:"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)80655-5"},{"key":"e_1_2_6_47_2","doi-asserted-by":"publisher","DOI":"10.1039\/dt9830002121"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/om034259c"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200500420"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic060066g"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/om700639a"},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1039\/b608951h"},{"key":"e_1_2_6_53_2","first-page":"1200","volume":"20","author":"Jahng Y. D.","year":"1999","journal-title":"Bull. Korean Chem. Soc."},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(20000218)112:4<759::AID-ANGE759>3.0.CO;2-K"},{"key":"e_1_2_6_54_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(20000218)39:4<743::AID-ANIE743>3.0.CO;2-I"},{"key":"e_1_2_6_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol047353d"},{"key":"e_1_2_6_56_2","unstructured":"\u00a0"},{"key":"e_1_2_6_57_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0957-4166(99)00023-3"},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm970645i"},{"key":"e_1_2_6_59_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00156a053"},{"key":"e_1_2_6_60_2","doi-asserted-by":"publisher","DOI":"10.1002\/1099-0690(200212)2002:24<4181::AID-EJOC4181>3.0.CO;2-M"},{"key":"e_1_2_6_61_2","unstructured":"\u00a0"},{"key":"e_1_2_6_62_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20020104)114:1<50::AID-ANGE50>3.0.CO;2-H"},{"key":"e_1_2_6_62_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020104)41:1<48::AID-ANIE48>3.0.CO;2-U"},{"key":"e_1_2_6_63_2","doi-asserted-by":"publisher","DOI":"10.1039\/b303006g"},{"key":"e_1_2_6_64_2","doi-asserted-by":"publisher","DOI":"10.1039\/a709014e"},{"key":"e_1_2_6_65_2","volume-title":"An Introduction to Hydrogen Bonding","author":"Jeffrey G. A.","year":"1997"},{"key":"e_1_2_6_66_2","unstructured":"The31P{1H}\u2005NMR spectrum shows the presence of a third isomer (<5\u2009%):\u03b4=64.4 (d 2J(P P)=34.5\u2005Hz) 56.1\u2005ppm (d 2J(P P)=34.5\u2005Hz)."},{"key":"e_1_2_6_67_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200701870"},{"key":"e_1_2_6_68_2","unstructured":"\u00a0"},{"key":"e_1_2_6_69_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00023a074"},{"key":"e_1_2_6_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00013a056"},{"key":"e_1_2_6_71_2","doi-asserted-by":"publisher","DOI":"10.1021\/om010745t"},{"key":"e_1_2_6_72_2","unstructured":"\u00a0"},{"key":"e_1_2_6_73_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(00)80238-6"},{"key":"e_1_2_6_74_2","volume-title":"Principles and Application of Organotransition Metal Chemistry","author":"Collman J. P.","year":"1987"},{"key":"e_1_2_6_75_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01179a012"},{"key":"e_1_2_6_76_2","unstructured":"Compound14quickly reacts with dioxygen in C6D6 leading to an uncharacterized product:1H\u2005NMR:\u03b4=\u22128.66\u2005ppm with2J(H P)=37.1 and 32.4\u2005Hz for Os\u2010H;31P{1H}\u2005NMR:\u03b4=13.7 and 4.6\u2005ppm with2J(P P)=14.4\u2005Hz."},{"key":"e_1_2_6_77_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja052862b"},{"key":"e_1_2_6_78_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200700507"},{"key":"e_1_2_6_79_2","unstructured":"\u00a0"},{"key":"e_1_2_6_80_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200700373"},{"key":"e_1_2_6_81_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20011203)7:23<5052::AID-CHEM5052>3.0.CO;2-Z"},{"key":"e_1_2_6_82_2","doi-asserted-by":"publisher","DOI":"10.1039\/a809236b"},{"key":"e_1_2_6_83_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-1902(66)80191-4"},{"key":"e_1_2_6_84_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470132579.ch33"},{"key":"e_1_2_6_85_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00174a018"},{"key":"e_1_2_6_86_2","unstructured":"\u00a0"},{"key":"e_1_2_6_87_2","unstructured":"CRYSALIS Data Collection Software and Data Processing Software for Oxford Diffraction Xcalibur devices Version 1.171 Oxford Diffraction Ltd. Oxfordshire United Kingdom 2005;"},{"key":"e_1_2_6_88_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0076-6879(97)76066-X"},{"key":"e_1_2_6_89_2","volume-title":"International Tables for Crystallography","year":"1992"},{"key":"e_1_2_6_90_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889899006020"},{"key":"e_1_2_6_91_2","unstructured":"A.\u2005L. Spek PLATON A Multipurpose Crystallographic Tool Utrecht University Utrecht (The Netherlands)2007;"},{"key":"e_1_2_6_92_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889894000221"},{"key":"e_1_2_6_93_2","unstructured":"G.\u2005M. Sheldrick SHELXL\u201097 University of G\u00f6ttingen G\u00f6ttingen (Germany)1998."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200800888","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200800888","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T15:17:08Z","timestamp":1760282228000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200800888"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2008,10,10]]},"references-count":102,"journal-issue":{"issue":"30","published-print":{"date-parts":[[2008,10,20]]}},"alternative-id":["10.1002\/chem.200800888"],"URL":"https:\/\/doi.org\/10.1002\/chem.200800888","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2008,10,10]]}}}