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Molecular and Electronic Structure of [MnVN(cyclam−acetato)]PF6. A Combined Experimental and DFT Study

MPS-Authors

Grapperhaus,  Craig A.
Research Department Wieghardt, Max Planck Institute for Radiation Chemistry, Max Planck Society;

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Bill,  Eckhard
Research Department Wieghardt, Max Planck Institute for Radiation Chemistry, Max Planck Society;

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Weyhermüller,  Thomas
Research Department Wieghardt, Max Planck Institute for Radiation Chemistry, Max Planck Society;

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Wieghardt,  Karl
Research Department Wieghardt, Max Planck Institute for Radiation Chemistry, Max Planck Society;

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Citation

Grapperhaus, C. A., Bill, E., Weyhermüller, T., Neese, F., & Wieghardt, K. (2001). Molecular and Electronic Structure of [MnVN(cyclam−acetato)]PF6. A Combined Experimental and DFT Study. Inorganic Chemistry, 40(17), 4191-4198. doi:10.1021/ic001370r.


Cite as: http://hdl.handle.net/21.11116/0000-0007-F285-1
Abstract
From the reaction of Li(cyclam−acetate), MnCl2·4H2O, and KPF6 in methanol brown microcrystals of [MnIIICl(cyclam−acetato)]PF6 (1) were obtained in the presence of air (cyclam−acetic acid = 1,4,8,11-tetraazacyclotetradecane-1-acetic acid). The reaction of 1 in aqueous NH3 solution with NaOCl produced blue crystals of [MnVN(cyclam−acetato)]PF6 (2). Complexes 1 and 2 were characterized by single-crystal X-ray crystallography, IR and Raman, electronic absorption, and 1H, 13C, and 15N NMR spectroscopies. Their magnetochemistry as well as their electrochemistry have been investigated. The complexes [MnN(cyclam−acetato)]+/2+ were studied by theoretical calculations at the DFT and semiempirical levels in order to obtain more insight into the ground and excited states of the MnV⋮N unit. Structural and spectroscopic parameters were successfully calculated and compared to experiment. A pictorial description of the bonding has been developed.