A Series of [Co(Mabiq)Cl2–n] (n = 0, 1, 2) Compounds and Evidence for the Elusive Bimetallic Form
datasetposted on 15.06.2015, 00:00 authored by Emma V. Puttock, Priyabrata Banerjee, Manuel Kaspar, Liam Drennen, Dmitry S. Yufit, Eckhard Bill, Stephen Sproules, Corinna R. Hess
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)--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 electron paramagnetic resonance 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 density functional theory computational data suggest that a CoII(Mabiq•) description may be a reasonable alternative to the CoI formalism for this compound.