Preparation and spectroscopic properties of oxovanadium(IV) and dioxomolybdenum(VI) complexes with tetraaza[14]annulenes containing pyridine rings |
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| Institution: | 1. Section of Dermatology, Children’s Hospital of Philadelphia, 3401 Civic Center Boulevard, Suite 3334, Philadelphia, PA 19104, USA;2. Pediatrics and Dermatology, Perelman School of Medicine at the University of Pennsylvania, Philadelphia, PA, USA;2. Faculty of Medical Sciences, University of Groningen, The Netherlands;3. Sport and Exercise Medicine, Queen Mary University of London, UK;4. Barts Health NHS Trust, London, UK;1. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, PR China;2. International Center of Future Science, Jilin University, Changchun 130012, PR China;1. School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, China;2. Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences, Chongqing 400714, China;3. School of Civil and Environmental Engineering, Shenzhen Polytechnic, Shenzhen 518055, China;1. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Sir C.V. Raman Avenue, Bangalore 560012, India;2. Department of Biochemistry, Indian Institute of Science, Sir C.V. Raman Avenue, Bangalore 560 012, India |
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| Abstract: | The reaction of 5,14-dihydro-7,16-diethyl-(E)- or -(Z)-dipyrido b, i] 1,4,8,11 ] tetraazacyclotetradecine with vanadium(III) chloride led to the corresponding oxovanadium(IV) complexes, while reaction with tetracarbonylbis(piperidine)molybdenum(O) gave the corresponding dioxomolybdenum(VI) complexes. The oxovanadium(IV) complexes showed mass spectra with prominent parent peaks in the El mode. On the other hand the FD mass spectra for the dioxomolybdenum(VI) complexes exhibited the expected parent and parent-O peaks. A VO stretching band was observed at ca. 970 cm−1 for the oxovanadium(IV) complexes. The dioxomolybdenum(VI) complexes had strong bands at 855 and 885 cm−1 in the NaCl region, which are attributable to the MoO symmetric and asymmetric stretching modes. The absorption bands observed above 20 000 cm−1 range were attributed to the CT and π→π* transitions. Judging from the spin Hamiltonian parameters, the oxovanadium(IV) complexes are of square-planar types with an unpaired electron in the dxy orbital. The downfield shifts for the dioxomolybdenum(VI) complexes are much larger in magnitude than those observed for the corresponding oxochromium(IV) complexes. This is primarily dependent on the fact that the magnitude of the positive charge fed by molybdenum(VI) is greater than that by chromium(IV). |
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