title: Linkage and redox isomerism in ruthenium complexes of catecholate, semiquinone, and o-acylphenolate ligands derived from 1,2-dihydroxy-9,10-anthracenedione (alizarin) and related species: syntheses, characterizations, and photophysics.
abstract: The complexes Ru(CO)2L2(AL-2H) (AL = alizarin; L = PPh3, PCyc3, PBu3, P(m-NaSO3C6H4)3), Ru(CO)(dppe)(PBu3)(AL-2H), and RuH(CO)L2(AL-H) (L = PPh3, PCyc3), and Ru(CO)2L2(AR-2H) (AR = anthrarobin; L = PBu3) were prepared by reactions of Ru3(CO)12, L, and AL, and the complexes RuH(CO)(PPh3)2(AL-H), RuH(CO)(PPh3)2(QN-H) (QN = quinizarin), and RuH(CO)(PPh3)2(LQN-H) (LQN = leucoquinizarin) are prepared by reactions of RuH2(CO)(PPh3)3 with AL or QN. The AL-2H and AR-2H ligands act as 1,2-catecholates, whereas the AL-H, QN-H, LQN-H ligands are 1,9-o-acylphenolate ligands. RuH(CO)(PPh3)2(AL-H) is characterized by X-ray crystallography. The electrochemistry of these complexes is examined, and the semiquinone complexes [Ru(CO)2L2(AL-2H)]+ (L = PPh3, PCyc3, PBu3) and [Ru(CO)(dppe)(PBu3)(AL-2H)]+ are generated by chemical oxidation and were characterized by EPR and IR spectroscopy. The photophysical properties are also reported.
authors.affiliation: Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14260-3000, USA.
authors.forename: M R
authors.initials: MR
authors.lastname: Churchill
authors.forename: K M
authors.initials: KM
authors.lastname: Keil
authors.forename: F V
authors.initials: FV
authors.lastname: Bright
authors.forename: S
authors.initials: S
authors.lastname: Pandey
authors.forename: G A
authors.initials: GA
authors.lastname: Baker
authors.forename: J B
authors.initials: JB
authors.lastname: Keister
mesh_terms: D000880:Anthraquinones / Q000138:chemical synthesis* / Q000737:chemistry*; D002396:Catechols / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007536:Isomerism; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D010636:Phenols / Q000138:chemical synthesis / Q000737:chemistry*; D010777:Photochemistry; D011809:Quinones / Q000138:chemical synthesis / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013329:Structure-Activity Relationship
chemical_list: D000880:Anthraquinones; D002396:Catechols; D008024:Ligands; D009942:Organometallic Compounds; D010636:Phenols; D011809:Quinones; C010078:alizarin; D012428:Ruthenium