Pentacoordinated iridium(I) complexes incorporating azopyridine chelation. Synthesis,structure and bonding |
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| Institution: | 1. Department of Chemistry, Faculty of Science and Art, Adıyaman University, 02040 Adıyaman, Turkey;2. Department of Chemistry, Faculty of Science and Art, Inönü University, 44280 Malatya, Turkey;3. Catalysis Research and Application Center, Inönü University, 44280 Malatya, Turkey;1. School of Advanced Sciences, VIT University, Vellore 632014, Tamilnadu, India;2. BIF, School of Life Sciences, University of Hyderabad, Hyderabad 500046, Telangana, India;1. G.W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA, USA;2. Department of Biomedical Engineering, Amirkabir University of Technology, Tehran, Iran;3. Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, Tehran, Iran;4. National Cell Bank, Pasture Institute of Iran, Tehran, Iran;5. Department of Chemical Engineering, Amirkabir University of Technology, Tehran, Iran;6. Department of Engineering and Technology, Golestan University, Aliabad Katool, Iran;7. School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA, USA;1. Department of Chemistry, University of Patras, 265 04 Patras, Greece;2. LAQV/REQUIMTE & Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal;3. Departament de Quimica Inorgànica i Orgànica, Secció Inorgànica and Institut de Nanociència i Nanotecnologia (IN2UB), Universitat de Barcelona, Martí Franqués 1-11, 08028 Barcelona, Spain;1. Jiangsu Province Key Laboratory for Chemistry of Low-Dimensional Materials, Huaiyin Normal University, Huaian 223300, People’s Republic of China;2. School of Physics and Electronic Electrical Engineering, Huaiyin Normal University, Huaian 223300, People’s Republic of China |
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| Abstract: | The reaction of Ir(COD)Cl]2 with 2-(arylazo)pyridine (L) in dichloromethane solution has afforded the nonelectrolytic pentacoordinated species of type Ir(L)(COD)(Cl) from which the corresponding bromides and iodides have been synthesised by metathesis (COD=1,5-cyclooctadiene). L ligands used are: 2-(phenylazo)pyridine (L1); 2-(m-tolylazo)pyridine (L2) and 2-(p-chlorophenylazo)pyridine (L3). The X-ray structures of Ir(L2)(COD)(Cl)·0.5 CH2Cl2 and Ir(L3)(COD)(I) have been determined revealing square-pyramidal geometry. The relatively short IrN(azo) lengths (∼2.00 Å) and the relatively long NN bond distance (∼1.30 Å) are consistent with significant dππ* (azo) back-bonding. The HOMO (50% Ir and 15% azo character) and LUMO (50% azo and 30% Ir character) are primarily localised in the IrL fragment and the absorption bands near 600 nm is assigned tentatively to the HOMO→LUMO transition. The stability of the pentacoordinated structures and the inertness to oxidative addition of the present complexes in contrast to the behaviour of corresponding 2,2′-bipyridine species (tetracoordinated, reactive) is rationalised in terms of π-acidity order L≫bpy. |
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