A series of [Co(Mabiq)Cl2-n] (n = 0, 1, 2) compounds and evidence for the elusive bimetallic form

Puttock, E. V., Banerjee, P., Kaspar, M., Drennan, L., Yufit, D. S., Bill, E., Sproules, S. and Hess, C. R. (2015) A series of [Co(Mabiq)Cl2-n] (n = 0, 1, 2) compounds and evidence for the elusive bimetallic form. Inorganic Chemistry, 54(12), pp. 5864-5873. 26035475. (doi:10.1021/acs.inorgchem.5b00636)

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Abstract

The synthesis and characterization of a series of cobalt compounds, coordinated by the redox active macrocyclic biquinazoline ligand, Mabiq (2-4:6-8-bis(3,3,4,4-tetramethyldihydropyrrolo)-10-15-(2,2′-biquinazolino)-[15]-1,3,5,8,10,14-hexaene-1,3,7,9,11,14-N6), is presented. The series includes the monometallic Co(Mabiq)Cl2 (1), Co(Mabiq)Cl (2), and Co(Mabiq) (4), with formal metal oxidation states of +3 → +1. A binuclear cobaltous compound, Co2(Mabiq)Cl3 (3), also was obtained, providing the first evidence for the ability of the Mabiq ligand to coordinate two metal ions. The electronic structures of the paramagnetic 2 and 3 were examined by EPR spectroscopy and magnetic susceptibility studies. The CoII ion that resides in the N4-macrocylic cavity of 2 and 3 adopts a low spin S = 1/2 configuration. The bypirimidine functionality in 3 additionally coordinates a high-spin, S = 3/2 cobaltous ion in a tetrahedral environment. The two metal ions in 3 are weakly coupled by magnetometry. The square planar, low-valent 4 offers one of a limited number of examples of structurally characterized N4-macrocyclic CoI compounds. Spectroscopic and DFT computational data suggest that a CoII(Mabiq•) description may be a reasonable alternative to the CoI formalism for this compound.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Sproules, Dr Stephen
Authors: Puttock, E. V., Banerjee, P., Kaspar, M., Drennan, L., Yufit, D. S., Bill, E., Sproules, S., and Hess, C. R.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Inorganic Chemistry
Publisher:American Chemical Society
ISSN:0020-1669
ISSN (Online):1520-510X
Copyright Holders:Copyright © 2015 American Chemical Society
First Published:First published in Inorganic Chemistry 54(12):5864–5873
Publisher Policy:Reproduced in accordance with the copyright policy of the publisher.

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