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Treatment of <jats:bold>1<\/jats:bold>\u2013<jats:bold>3<\/jats:bold> with NaPF<jats:sub>6<\/jats:sub> in methanol at RT affords quantitatively the corresponding derivatives [RuCl(PP)(tpy)]PF<jats:sub>6<\/jats:sub> (PP=dppp (<jats:bold>1\u2009a<\/jats:bold>), (<jats:italic>R<\/jats:italic>,<jats:italic>R<\/jats:italic>)\u2010Skewphos (<jats:bold>2\u2009a<\/jats:bold>) and (<jats:italic>S<\/jats:italic>,<jats:italic>S<\/jats:italic>)\u2010Skewphos (<jats:bold>3\u2009a<\/jats:bold>)). Reaction of [RuCl<jats:sub>2<\/jats:sub>(PPh<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>] with (<jats:italic>S<\/jats:italic>,<jats:italic>R<\/jats:italic>)\u2010Josiphos or (<jats:italic>R<\/jats:italic>)\u2010BINAP in toluene, followed by treatment with tpy in 1\u2010butanol and finally with NaPF<jats:sub>6<\/jats:sub> in MeOH gives [RuCl(PP)(tpy)]PF<jats:sub>6<\/jats:sub> (PP=(<jats:italic>S<\/jats:italic>,<jats:italic>R<\/jats:italic>)\u2010Josiphos (<jats:bold>4\u2009a<\/jats:bold>), (<jats:italic>R<\/jats:italic>)\u2010BINAP (<jats:bold>5\u2009a<\/jats:bold>)) isolated in 78\u2009% and 86\u2009% yield, respectively. The chiral derivatives have been isolated as single stereoisomers and <jats:bold>3\u2009a<\/jats:bold>, <jats:bold>4\u2009a<\/jats:bold> have been characterized by single crystal X\u2010ray diffraction studies. The tpy complexes with NaO<jats:italic>i<\/jats:italic>Pr display high photocatalytic activity in the transfer hydrogenation (TH) of carbonyl compounds using 2\u2010propanol as the only hydrogen donor and visible light at 30\u2009\u00b0C, at remarkably high S\/C (up to 5000) and TOF values up to 264\u2005h<jats:sup>\u22121<\/jats:sup>. The chiral enantiomers <jats:bold>2<\/jats:bold>, <jats:bold>2\u2009a<\/jats:bold> and <jats:bold>3<\/jats:bold>, <jats:bold>3\u2009a<\/jats:bold> induce the asymmetric photocatalytic TH of acetophenone, affording (<jats:italic>S<\/jats:italic>)\u2010 and (<jats:italic>R<\/jats:italic>)\u20101\u2010phenylethanol with 51 and 52\u2009% <jats:italic>ee<\/jats:italic>, respectively, in a MeOH\/2\u2010propanol mixture.<\/jats:p>","DOI":"10.1002\/chem.202201722","type":"journal-article","created":{"date-parts":[[2022,8,24]],"date-time":"2022-08-24T11:34:41Z","timestamp":1661340881000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds"],"prefix":"10.1002","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6588-8037","authenticated-orcid":false,"given":"Maurizio","family":"Ballico","sequence":"first","affiliation":[{"name":"Dipartimento di Scienze AgroAlimentari Ambientali e Animali (DI4A) Universit\u00e0 di Udine  Via Cotonificio 108 33100 Udine Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1914-806X","authenticated-orcid":false,"given":"Dario","family":"Alessi","sequence":"additional","affiliation":[{"name":"Dipartimento di Scienze AgroAlimentari Ambientali e Animali (DI4A) Universit\u00e0 di Udine  Via Cotonificio 108 33100 Udine Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christian","family":"Jandl","sequence":"additional","affiliation":[{"name":"Department of Chemistry &amp; Catalysis Research Center TUM  Lichtenbergstra\u00dfe 4 85747 Garching b. 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