Mixed-valence, tetranuclear cobalt(iii,iv) complexes: preparation and properties of [Co4O4(O2CR)2(bpy)4]3+ salts

Dimitrou, Katerina; Brown, Angelica D.; Concolino, Thomas E.; Rheingold, Arnold L.; Christou, George

doi:10.1039/b102008k

Cited by 71 publications

(55 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…There are four crystallographically independent diagonal Co-Co internuclear distances; three are long (d > 2.82 ) and one is short [Co(1)-Co(2), 2.6759(11) ], giving the cluster a decidedly distorted geometry very similar to the analogous carboxylate-bound clusters. [29,30,33] The CoÀO distances within the core are all 1.90 or slightly less, again very similar to the aforementioned carboxylate-bridged clusters. The ClO 4 À counterions are non-coordinating and do not show any readily apparent interaction with the [Co 4 O 4 ] 4 + core or either of the Re I centres.…”

Section: Resultssupporting

confidence: 56%

“…The cobalt-oxo cubane [Co 4 O 4 (CO 2 Py) 2 (bpy) 4 ](ClO 4 ) 2 (1, CO 2 Py = 4-carboxypyridine) was obtained from isonicotinic acid and [Co 4 O 4 (CO 2 Me) 2 (bpy) 4 ](ClO 4 ) 2 by using methods adapted from those reported by Christou [33] (see the Experimental Section and the Supporting Information for synthetic details and full characterisation). Complexation of this functionalised cubane with the rhenium-based photosensitiser [Re(phen)(CO) 3 -(CH 3 CN)]PF 6 [34] (phen = 1,10-phenanthroline) affords a cobaltoxo cubane core ligated by Re I phenanthroline photocentres (2).…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Photo‐active Cobalt Cubane Model of an Oxygen‐Evolving Catalyst

et al. 2013

View full text Add to dashboard Cite

A dyad complex has been constructed as a soluble molecular model of a heterogeneous cobalt-based oxygen-evolving catalyst (Co-OEC). To this end, the Co(4)O(4) core of a cobalt-oxo cubane was covalently appended to Re(I) photosensitisers. The resulting adduct was characterised both in the solid state (by X-ray diffraction) and in solution using a variety of techniques. In particular, the covalent attachment of the Re(I) moieties to the Co(4)O(4) core promotes emission quenching of the Re(I) photocentres, with implications for the energy and electron transduction process of Co-OEC-like catalysts.

show abstract

Section: Resultssupporting

confidence: 56%

Section: Resultsmentioning

confidence: 99%

Photo‐active Cobalt Cubane Model of an Oxygen‐Evolving Catalyst

et al. 2013

View full text Add to dashboard Cite

show abstract

mentioning

confidence: 97%

“…Furthermore, the Co 4 cubane core can be oxidized to 3Co(III) and Co(IV) form and more stable than the Mn(III) Mn(IV) species that are intermediates in the O 2 evolution process [4,5]. To our knowledge, the crystal structure of a few complexes containing Co 4 cubane core, [Co 4 O 4 (O 2 CMe) 2 (bpy) 4 ](ClO 4 ) 2 [5], [Co 4 O 4 (C 7 H 8 N) 4 ] AE 5CHCl 3 [6], [ [11], etc, had been reported. Vanadates have been intensively studied owing to the ability of vanadium atoms adopting a variety of co-ordination geometries and oxidation states [12].…”

mentioning

confidence: 99%

“…The analogous complexes containing Co 4 , Zn 4 , Cd 4 and Ni 4 cubane cores had been reported [3,4]. Furthermore, the Co 4 cubane core can be oxidized to 3Co(III) and Co(IV) form and more stable than the Mn(III) Mn(IV) species that are intermediates in the O 2 evolution process [4,5]. To our knowledge, the crystal structure of a few complexes containing Co 4 cubane core, [Co 4 O 4 (O 2 CMe) 2 (bpy) 4 ](ClO 4 ) 2 [5], [Co 4 O 4 (C 7 H 8 N) 4 ] AE 5CHCl 3 [6], [ [11], etc, had been reported.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Hydrothermal synthesis and characterization of a novel crystal containing [Co4O4]4+ cubane core: [Co4O4(dpaH)4(CH3COO)2]2V4O12·5H2O

Zhang

You

Zhu

et al. 2006

Inorganic Chemistry Communications

View full text Add to dashboard Cite

Cobalt: Inorganic & Coordination ChemistryBased in part on the article Cobalt: Inorganic & Coordination Chemistry by David A. Buckingham which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Blackman

2005

Encyclopedia of Inorganic Chemistry

View full text Add to dashboard Cite

This article provides a summary of the important and interesting aspects of the inorganic and coordination chemistry of cobalt. A brief history of the element, detailing its discovery and historical uses, is given, and some general information concerning the properties of elemental cobalt is detailed. The general chemistry of cobalt is then outlined, including an overview of the common oxidation states found in inorganic compounds and complexes, a discussion of the stereochemistry, spectra and magnetism of cobalt complexes, and an outline of some analytical methods used for cobalt. The inorganic chemistry of simple cobalt salts is then described, and the coordination chemistry of cobalt, which constitutes the majority of the article, is then outlined in some detail. Coordination complexes of cobalt are detailed according to the oxidation state of the metal ion, with complexes ranging from Co(−I) to Co(V) discussed. Brief descriptions of the chemistry of each oxidation state are given, and specific examples are then outlined according to the nature of the ligand donor atom(s), with extensive references to both the primary literature and to review articles given. Thus, Co(I), Co(0), and Co(−I) complexes containing aliphatic, aromatic, and macrocyclic amine ligands, as well as Schiff‐base, porphyrin, and P‐donor ligands are discussed, while Co(II) complexes of carboxylate, heterocyclic, and oxygen‐derived ligands are summarized. Co(III) ammine and amine complexes are described in detail, while Co(III) complexes containing O‐donor ligands are also discussed. The few known Co(IV) and Co(V) complexes are outlined.

show abstract

Mixed-valence, tetranuclear cobalt(iii,iv) complexes: preparation and properties of [Co4O4(O2CR)2(bpy)4]3+ salts

Cited by 71 publications

References 15 publications

Photo‐active Cobalt Cubane Model of an Oxygen‐Evolving Catalyst

Photo‐active Cobalt Cubane Model of an Oxygen‐Evolving Catalyst

Hydrothermal synthesis and characterization of a novel crystal containing [Co4O4]4+ cubane core: [Co4O4(dpaH)4(CH3COO)2]2V4O12·5H2O

Cobalt: Inorganic & Coordination ChemistryBased in part on the article Cobalt: Inorganic & Coordination Chemistry by David A. Buckingham which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Contact Info

Product

Resources

About