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Synthesis, structural studies, kinetic stability, and oxidation catalysis of the late first row transition metal complexes of 4,10-dimethyl-1,4,7,10-tetraazabicyclo[6.5.2]pentadecane

Matz, Dallas L.; Jones, Donald G.; Roewe, Kimberly D.; Gorbet, Michael-Joseph; Zhang, Zhan; Chen, Zhuqi; Prior, Timothy J.; Archibald, Stephen J.; Yin, Guochuan; Hubin, Timothy J.


Dallas L. Matz

Donald G. Jones

Kimberly D. Roewe

Michael-Joseph Gorbet

Zhan Zhang

Zhuqi Chen

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Dr Tim Prior
Senior Lecturer in Inorganic Chemistry

Guochuan Yin

Timothy J. Hubin


© The Royal Society of Chemistry 2015. Synthetic details for 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.5.2]pentadecane, the dimethyl ethylene cross-bridged homocyclen ligand are presented for the first time. Its novel Mn 2+ , Fe 2+ , Mn 3+ , and Fe 3+ complexes have been synthesized and characterized. X-ray crystal structures were obtained for both manganese complexes, along with five additional Co 3+ , Cu 2+ , and Zn 2+ structures, the first structural characterization of complexes of this ligand. Each complex has the cis-V configuration of the cross-bridged macrocycle ring, leaving cis labile binding sites for interaction of the complex with oxidants and/or substrates. The copper(II) complex kinetic stability in 5 M HCl and at elevated temperatures was determined and compared to related complexes in the literature. The electronic properties of the manganese and iron complexes were evaluated using solid state magnetic moment determination and acetonitrile solution electronic spectroscopy, revealing high spin metal complexes in all cases. Cyclic voltammetry in acetonitrile of the divalent iron and manganese complexes revealed reversible redox processes, suggesting catalytic reactivity involving electron transfer processes are possible for both complexes. Screening of the Mn 2+ and Fe 2+ complexes for oxidation catalysis using hydrogen peroxide as the terminal oxidant showed both complexes are worthy of continued development.


Matz, D. L., Jones, D. G., Roewe, K. D., Gorbet, M., Zhang, Z., Chen, Z., …Hubin, T. J. (2015). Synthesis, structural studies, kinetic stability, and oxidation catalysis of the late first row transition metal complexes of 4,10-dimethyl-1,4,7,10-tetraazabicyclo[6.5.2]pentadecane. Dalton Transactions : an international journal of inorganic chemistry, 44(27), 12210-12224.

Journal Article Type Article
Acceptance Date Apr 1, 2015
Online Publication Date Apr 15, 2015
Publication Date Jul 21, 2015
Deposit Date Oct 26, 2018
Journal Dalton Transactions
Print ISSN 1477-9226
Electronic ISSN 1477-9234
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 44
Issue 27
Pages 12210-12224
Public URL
Publisher URL!divAbstract