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

Grapperhaus, Craig A.; Bill, Eckhard; Weyhermüller, Thomas; Neese, Frank; Wieghardt, Karl

doi:10.1021/ic001370r

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

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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 [Mn^VN(cyclam−acetato)]PF₆. A Combined Experimental and DFT Study. Inorganic Chemistry, 40(17), 4191-4198. doi:10.1021/ic001370r.

Cite as: https://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 [Mn^IIICl(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 [Mn^VN(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 Mn^V⋮N unit. Structural and spectroscopic parameters were successfully calculated and compared to experiment. A pictorial description of the bonding has been developed.