2016
DOI: 10.1039/c6dt02807a
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The electronic and solvatochromic properties of [Co(L)(bipyridine)2]+(L = o-catecholato, o-benzenedithiolato) species: a combined experimental and computational study

Abstract: Complexes of Co(iii) containing mixed chelating diimine and o-quinone ligand sets are of fundamental interest on account of their fascinating magnetic and electronic properties. Whilst complexes of this type containing one diimine and two o-quinone ligands have been studied extensively, those with the reverse stoichiometry (two diimines and one o-quinone) are much rarer. Herein, we describe a ready route to the synthesis of the complex [Co(o-catecholate) (2,2'-bipyridine)] (1), and also report the synthesis of… Show more

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Cited by 15 publications
(19 citation statements)
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References 59 publications
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“…The highest occupied orbitals (HOMO) are ligand‐based; specifically, the π 3 orbital of the bdt ligand (Figure ) . This supports the assignment of the oxidation of [ 1 ] 2+ (see Figure and associated discussion) as being ligand‐centered, and that the process is irreversible; a bdt radical anion ligand is incapable of bridging two Co III ions, as was also observed with the monocobalt complex …”
Section: Resultssupporting
confidence: 80%
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“…The highest occupied orbitals (HOMO) are ligand‐based; specifically, the π 3 orbital of the bdt ligand (Figure ) . This supports the assignment of the oxidation of [ 1 ] 2+ (see Figure and associated discussion) as being ligand‐centered, and that the process is irreversible; a bdt radical anion ligand is incapable of bridging two Co III ions, as was also observed with the monocobalt complex …”
Section: Resultssupporting
confidence: 80%
“…Cyclic voltammetry was performed on complex [ 1 ] 2+ in acetonitrile containing 1 m tetrabutylammonium hexafluorophosphate (TBA‐PF 6 ) as the supporting electrolyte (see Figure ). This evinced an irreversible oxidative process peaking at around +0.7 V (vs. ferrocenium/ferrocene), which we attribute to oxidation of the benzenedithiolate ligands by analogy to the behavior observed for the monomeric species [Co III (bdt)(Me 2 bpy) 2 ] + in this solvent system (see below) . In terms of reductive electrochemistry, the sample displayed an irreversible wave at –1.4 V, followed by a more reversible wave at around –1.8 V, with this latter value agreeing well with the position of the couple for the reduction of free Me 2 bpy in acetonitrile as determined by Saji and Aoyagui .…”
Section: Resultssupporting
confidence: 54%
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