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Electronic Structure and Hydrogen Bonding in a Dicobalt(III) Werner Complex

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Abstract

The bonding of the O-O group in the dicobalt cation 1a [(NH3)6Co2(μ-O2)(μ-OH)(μ-NH2)]3+ was studied by DFT methods (ADF program) and the bridging O2 ligand was characterized as superoxide(O2−). In this complex, three bridging ligands connect the two cobalt atoms, forcing a cis conformation of the Co-O-O-Co atoms. A comparison was made with [(NH3)10Co2(μ-O2)]5+, 2a, where a trans arrangement is observed. Superoxide binds more strongly to the dicobalt(III) fragment in 2a than in 1a, both as a result of weaker Pauli repulsion and stronger covalent interaction. It was found that in 1a the electronic structure with one unpaired electron, where cobalt is formally Co(III), d6, and O2 carries one negative charge gives rise to the most stable structure, compared to possibilities with three and five unpaired electrons. The hydrogen bonds in the crystal were analyzed and the interactions between one water molecule or one nitrate ion studied in more detail.

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Authors and Affiliations

  1. Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016, Lisboa, Portugal

    Nuno A. G. Bandeira & Maria José Calhorda

  2. ITQB, Av. da República, EAN, Apart. 127, 2781-901, Oeiras, Portugal

    Maria José Calhorda

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  1. Nuno A. G. Bandeira
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  2. Maria José Calhorda
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Correspondence to Maria José Calhorda.

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Bandeira, N.A.G., Calhorda, M.J. Electronic Structure and Hydrogen Bonding in a Dicobalt(III) Werner Complex. Struct Chem 16, 265–271 (2005). https://doi.org/10.1007/s11224-005-4457-6

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  • DOI: https://doi.org/10.1007/s11224-005-4457-6

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