{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Ballico M"],"funding":["Ministero dell'Istruzione, dell'Università e della Ricerca PRIN 2015"],"pagination":["e202201722"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC9828271"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["28(65)"],"pubmed_abstract":["The cationic achiral and chiral terpyridine diphosphine ruthenium complexes [RuCl(PP)(tpy)]Cl (PP=dppp (1), (R,R)-Skewphos (2) and (S,S)-Skewphos (3)) are easily obtained in 85-88 % yield through a one-pot synthesis from [RuCl<sub>2</sub> (PPh<sub>3</sub> )<sub>3</sub> ], the diphosphine and 2,2':6',2''-terpyridine (tpy) in 1-butanol. Treatment of 1-3 with NaPF<sub>6</sub> in methanol at RT affords quantitatively the corresponding derivatives [RuCl(PP)(tpy)]PF<sub>6</sub> (PP=dppp (1 a), (R,R)-Skewphos (2 a) and (S,S)-Skewphos (3 a)). Reaction of [RuCl<sub>2</sub> (PPh<sub>3</sub> )<sub>3</sub> ] with (S,R)-Josiphos or (R)-BINAP in toluene, followed by treatment with tpy in 1-butanol and finally with NaPF<sub>6</sub> in MeOH gives [RuCl(PP)(tpy)]PF<sub>6</sub> (PP=(S,R)-Josiphos (4 a), (R)-BINAP (5 a)) isolated in 78 % and 86 % yield, respectively. The chiral derivatives have been isolated as single stereoisomers and 3 a, 4 a have been characterized by single crystal X-ray diffraction studies. The tpy complexes with NaOiPr display high photocatalytic activity in the transfer hydrogenation (TH) of carbonyl compounds using 2-propanol as the only hydrogen donor and visible light at 30 °C, at remarkably high S/C (up to 5000) and TOF values up to 264 h<sup>-1</sup> . The chiral enantiomers 2, 2 a and 3, 3 a induce the asymmetric photocatalytic TH of acetophenone, affording (S)- and (R)-1-phenylethanol with 51 and 52 % ee, respectively, in a MeOH/2-propanol mixture."],"journal":["Chemistry (Weinheim an der Bergstrasse, Germany)"],"pubmed_title":["Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds."],"pmcid":["PMC9828271"],"funding_grant_id":["20154X9ATP_005"],"pubmed_authors":["Baratta W","Alessi D","Jandl C","Lovison D","Ballico M"],"additional_accession":[]},"is_claimable":false,"name":"Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds.","description":"The cationic achiral and chiral terpyridine diphosphine ruthenium complexes [RuCl(PP)(tpy)]Cl (PP=dppp (1), (R,R)-Skewphos (2) and (S,S)-Skewphos (3)) are easily obtained in 85-88 % yield through a one-pot synthesis from [RuCl<sub>2</sub> (PPh<sub>3</sub> )<sub>3</sub> ], the diphosphine and 2,2':6',2''-terpyridine (tpy) in 1-butanol. Treatment of 1-3 with NaPF<sub>6</sub> in methanol at RT affords quantitatively the corresponding derivatives [RuCl(PP)(tpy)]PF<sub>6</sub> (PP=dppp (1 a), (R,R)-Skewphos (2 a) and (S,S)-Skewphos (3 a)). Reaction of [RuCl<sub>2</sub> (PPh<sub>3</sub> )<sub>3</sub> ] with (S,R)-Josiphos or (R)-BINAP in toluene, followed by treatment with tpy in 1-butanol and finally with NaPF<sub>6</sub> in MeOH gives [RuCl(PP)(tpy)]PF<sub>6</sub> (PP=(S,R)-Josiphos (4 a), (R)-BINAP (5 a)) isolated in 78 % and 86 % yield, respectively. The chiral derivatives have been isolated as single stereoisomers and 3 a, 4 a have been characterized by single crystal X-ray diffraction studies. The tpy complexes with NaOiPr display high photocatalytic activity in the transfer hydrogenation (TH) of carbonyl compounds using 2-propanol as the only hydrogen donor and visible light at 30 °C, at remarkably high S/C (up to 5000) and TOF values up to 264 h<sup>-1</sup> . The chiral enantiomers 2, 2 a and 3, 3 a induce the asymmetric photocatalytic TH of acetophenone, affording (S)- and (R)-1-phenylethanol with 51 and 52 % ee, respectively, in a MeOH/2-propanol mixture.","dates":{"release":"2022-01-01T00:00:00Z","publication":"2022 Nov","modification":"2026-03-27T15:49:15.851Z","creation":"2025-04-05T10:26:28.146Z"},"accession":"S-EPMC9828271","cross_references":{"pubmed":["36001351"],"doi":["10.1002/chem.202201722"]}}