title: Asymmetric oxidation of vinyl- and ethynyl terthiophene ligands in triruthenium complexes.
abstract: A series of ruthenium(ii) complexes [{RuCl(CO)(PMe3)3(-CH[double bond, length as m-dash]CH-)}nX], (: n = 3, X = 3,3''-dimethyl-2,2':3',2''-terthiophene; : n = 2, X = 2,2'-bithiophene; : n = 2, X = 2,3-bis(3-methylthiophen-2-yl)benzothiophene) and [{Cp*(dppe)2Ru(-C[triple bond, length as m-dash]C-)}3X], (X = 3,3''-dimethyl-2,2':3',2''-terthiophene), were prepared and characterized by (1)H, (13)C and (31)P NMR. Their redox, spectroscopic and bonding properties were studied with a range of spectro-electrochemical methods in combination with density functional theory calculations. The first two anodic steps observed for and are largely localized on the lateral frameworks of the molecular triangle, the direct conjugation between them being precluded due to the photostable open form of the dithienyl ethene moiety. The third anodic step is then mainly localized on the centerpiece of the triangular structure, affecting both bithiophene laterals. The experimental IR and UV-vis-NIR spectroelectrochemical data and, largely, also DFT calculations account for this explanation, being further supported by direct comparison with the anodic behavior of reference diruthenium complexes and .
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China. chshliu@mail.ccnu.edu.cn.
authors.forename: Jing
authors.initials: J
authors.lastname: Zhang
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China. chshliu@mail.ccnu.edu.cn.
authors.forename: Chao-Fang
authors.initials: CF
authors.lastname: Sun
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China. chshliu@mail.ccnu.edu.cn.
authors.forename: Ming-Xing
authors.initials: MX
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD, UK. f.hartl@reading.ac.uk.
authors.forename: František
authors.initials: F
authors.lastname: Hartl
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China. chshliu@mail.ccnu.edu.cn.
authors.forename: Jun
authors.initials: J
authors.lastname: Yin
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China. chshliu@mail.ccnu.edu.cn.
authors.forename: Guang-Ao
authors.initials: GA
authors.lastname: Yu
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China. chshliu@mail.ccnu.edu.cn.
authors.forename: Li
authors.initials: L
authors.lastname: Rao
authors.affiliation: Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China. chshliu@mail.ccnu.edu.cn.
authors.forename: Sheng Hua
authors.initials: SH
authors.lastname: Liu