caa a22 4500 605511152 CHVBK 20210128100649.0 cr unu---uuuuu 210128e20150901xx s 000 0 eng 10.1007/s00894-015-2759-1 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2759-1 Theoretical and experimental studies of phenol oxidation by ruthenium complex with N,N,N- tris(benzimidazol - 2yl-methyl)amine [Elektronische Daten] [J. Hernandez, Antonio Silva, Pandiyan Thangarasu, Rafael Najera, Alfonso Moreno, M. Ledesma, Julian Cruz-Borbolla, Narinder Singh] The ruthenium complex with (N,N,N-tris(benzimidazol-2yl-methyl)amine, L1) was prepared, and characterized. Fukui data were used to localize the reactive sites on the ligand. The structural and electronic properties of the complex were analyzed by DFT in different oxidation states in order to evaluate its oxidant properties for phenol oxidation. The results show that the hard Ru(IV) cation bonds preferentially with a hard base (Namine = amine nitrogen, or axial chloride ion), and soft Ru(II) with a soft base (Nbzim = benzimidazole nitrogen or axial triphenyl phosphine). Furthermore, the Jahn-Teller effect causes an elongation of the axial bond in the octahedral structure. The bonding nature and the orbital contribution to the electronic transitions of the complex were studied. The experimental UV-visible bands were interpreted by using TD-DFT studies. The complex oxidizes phenol to benzoquinone in the presence of H2O2 and the intermediate was detected by HPLC and 13C NMR. A possible mechanism and rate law are proposed for the oxidation. The adduct formation of phenol with [Ru(O)L1]2+ or [Ru(OH)L1]+ is theoretically analyzed to show that [Ru(OH)L1-OPh]+ could produce the phenol radical. Graphical Abstract Phenol oxidation by ruthenium complex Springer-Verlag Berlin Heidelberg, 2015 Benzoquinone formation nationallicence DFT nationallicence TD-DFT nationallicence Fukui indexes nationallicence Phenol oxidation nationallicence Ruthenium complex nationallicence Hernandez J. Centro Tecnológico, Facultad de Estudios Superiores Aragón (FES-Aragón), Universidad Nacional Autónoma de México (UNAM), CP 57130, México, Estado de México, Mexico aut Silva Antonio Facultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México D.F., 04510, México, Mexico aut Thangarasu Pandiyan Facultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México D.F., 04510, México, Mexico aut Najera Rafael Facultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México D.F., 04510, México, Mexico aut Moreno Alfonso Facultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México D.F., 04510, México, Mexico aut Ledesma M. Instituto de Ingeniera, Universidad Nacional Autónoma de México, Ciudad Universitaria, 04510, México D.F, Mexico aut Cruz-Borbolla Julian Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, km. 4.5 Carretera Pachuca-Tulancingo, Col. Carboneras, C.P. 42184, Hidalgo, Mexico aut Singh Narinder Department of Chemistry, Indian Institute of Technology (IIT), Ropar, Punjab, India aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/9(2015-09-01), 1-16 1610-2940 21:9<1 2015 21 894 https://doi.org/10.1007/s00894-015-2759-1 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2759-1 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Hernandez J. Centro Tecnológico, Facultad de Estudios Superiores Aragón (FES-Aragón), Universidad Nacional Autónoma de México (UNAM), CP 57130, México, Estado de México, Mexico aut NATIONALLICENCE 700 1- Silva Antonio Facultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México D.F., 04510, México, Mexico aut NATIONALLICENCE 700 1- Thangarasu Pandiyan Facultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México D.F., 04510, México, Mexico aut NATIONALLICENCE 700 1- Najera Rafael Facultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México D.F., 04510, México, Mexico aut NATIONALLICENCE 700 1- Moreno Alfonso Facultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México D.F., 04510, México, Mexico aut NATIONALLICENCE 700 1- Ledesma M. Instituto de Ingeniera, Universidad Nacional Autónoma de México, Ciudad Universitaria, 04510, México D.F, Mexico aut NATIONALLICENCE 700 1- Cruz-Borbolla Julian Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, km. 4.5 Carretera Pachuca-Tulancingo, Col. Carboneras, C.P. 42184, Hidalgo, Mexico aut NATIONALLICENCE 700 1- Singh Narinder Department of Chemistry, Indian Institute of Technology (IIT), Ropar, Punjab, India aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/9(2015-09-01), 1-16 1610-2940 21:9<1 2015 21 894