naa a22 4500 51073345X CHVBK 20180411083001.0 cr unu---uuuuu 180411e20130101xx s 000 0 eng 10.1007/s12039-012-0342-1 doi (NATIONALLICENCE)springer-10.1007/s12039-012-0342-1 Osmium and cobalt complexes incorporating facially coordinated N,N,O donor azo-imine ligands: Redox and catalytic properties [Elektronische Daten] [POULAMI PATTANAYAK, DEBPRASAD PATRA, JAHAR PRATIHAR, ANDREW BURROWS, MARY MAHON, SURAJIT CHATTOPADHYAY] Reactions of 1-{[2-(arylazo)phenyl]iminomethyl}-2-phenol, HL [where H represents the dissociable phenolic protons of ligands and aryl groups of HL are C6H5 (HL1), p-CH3C6H5 (HL2), p-ClC6H5 (HL3)] with Os(H)(CO)(Br)(PPh3)3 in toluene and with Co(ClO4)3.6H2O in methanol afforded new facially coordinated complexes of composition [(L)Os(CO)(Br)(PPh3)] and [(L)2Co]ClO4. The anionic ligand (L) − , binds the metal in tridentate (N, N, O) manner in [(L)Os(CO)(Br)(PPh3)] and [(L)2Co]ClO4 complexes. All the Os(II) and Co(III) complexes are diamagnetic and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. The cyclic voltammograms exhibited one quasi reversible oxidative response near 0.10V vs SCE for [(L)Os(CO)(Br)(PPh3)] and [(L)2Co]ClO4 complexes displayed serial reductive responses within − 0.06 to − 1.61V vs SCE. Single point DFT calculation was carried out to examine the nature of redox orbitals. Conversion of ketones to corresponding alcohols has been studied using [(L)Os(CO)(Br)(PPh3)] as catalyst. Graphical Abstract New complexes of Os(II) and Co(III) have been synthesized where the tridentate ligands are held in facial manner about the metal centre. Redox properties of the metal complexes have been studied and nature of the redox orbitals were examined on the basis of DFT calculations. Catalytic transformation of secondary ketones to corresponding alcohols using the newly synthesized Os(II) complexes as catalyst have been outlined. Indian Academy of Sciences, 2013 2-(Arylazo)-1-N-salicylidene phenylamine nationallicence face capped Os(II) nationallicence Co(III) nationallicence DFT nationallicence redox nationallicence hydrogen transfer reaction nationallicence PATTANAYAK POULAMI Department of Chemistry, University of Kalyani, 741235, Kalyani, India aut PATRA DEBPRASAD Department of Chemistry, University of Kalyani, 741235, Kalyani, India aut PRATIHAR JAHAR Department of Chemistry, University of Kalyani, 741235, Kalyani, India aut BURROWS ANDREW Department of Inorganic Chemistry, University of Bath, Claverton Down, BA27AY, Bath, UK aut MAHON MARY Department of Inorganic Chemistry, University of Bath, Claverton Down, BA27AY, Bath, UK aut CHATTOPADHYAY SURAJIT Department of Chemistry, University of Kalyani, 741235, Kalyani, India aut Journal of Chemical Sciences Springer-Verlag 125/1(2013-01-01), 51-62 0974-3626 125:1<51 2013 125 12039 https://doi.org/10.1007/s12039-012-0342-1 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s12039-012-0342-1 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- PATTANAYAK POULAMI Department of Chemistry, University of Kalyani, 741235, Kalyani, India aut NATIONALLICENCE 700 1- PATRA DEBPRASAD Department of Chemistry, University of Kalyani, 741235, Kalyani, India aut NATIONALLICENCE 700 1- PRATIHAR JAHAR Department of Chemistry, University of Kalyani, 741235, Kalyani, India aut NATIONALLICENCE 700 1- BURROWS ANDREW Department of Inorganic Chemistry, University of Bath, Claverton Down, BA27AY, Bath, UK aut NATIONALLICENCE 700 1- MAHON MARY Department of Inorganic Chemistry, University of Bath, Claverton Down, BA27AY, Bath, UK aut NATIONALLICENCE 700 1- CHATTOPADHYAY SURAJIT Department of Chemistry, University of Kalyani, 741235, Kalyani, India aut NATIONALLICENCE 773 0- Journal of Chemical Sciences Springer-Verlag 125/1(2013-01-01), 51-62 0974-3626 125:1<51 2013 125 12039 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer