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Theoretical modelling of tripodal CuN3 and CuN4 cuprous complexes interacting with O2, CO or CH3CN

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Abstract

Dioxygen binding at copper enzymatic sites is a fundamental aspect of the catalytic activity observed in many biological systems such as the monooxygenases, especially peptidylglycine α-hydroxylating monooxygenase (PHM), in which two mononuclear CuI sites are involved. Biomimetic models have been developed: dipods, tripods, and, more recently, functionalized calixarenes. The modelling of calixarene systems, although not unreachable for theory yet, requires, however, a number of preliminary investigations to ensure proper calibrations if relevant description of the metal–ligand interaction at the hybrid quantum mechanical/molecular mechanics levels of theory is the aim. In this paper, we report quantum chemistry investigations on a coherent series of representative cuprous tripodal species characterized by (1) monodentate ligands [Cu(ImH)3]+ (where ImH is imidazole), [Cu(MeNH2)3]+ and [Cu(MeNH2)4]+ , (2) neutral tripodal ligands [CuCH(ImH)3]+, [Cu(tren)]+ [where tren is tris(2-aminoethyl)amine], and [Cu(trenMe3)]+ [where trenMe3 is tris(2-methylaminoethyl)amine] and (3) a hydrido-tris(pyrazolyl)borate [CuBH(Pyra)3]. The structures of these complexes, the coordination mode (η 2 side-on or η 1 end-on) of O2 to CuI and the charge transfer from the metal to dioxygen have been computed. For some systems, the coordination by CH3CN and CO is also reported. Beyond results relative to structural properties, an interesting feature is that it is possible to build from computational results only a set of abacuses linking the ν(16O–16O) vibrational frequency of the coordinated O2 molecule to the O–O bond length or to the net charge of the O2 moiety. Such abacuses may help experimentalists in distinguishing between the four possible ways of binding O2 to CuN3 and CuN4 cuprous centres, namely (1) end-on triplet states, (2) side-on triplet states, (3) end-on singlet states and (4) side-on singlet states. These abacuses are extended to three tripods obtained by the substitution of one nitrogen atom by either a phosphorus or a sulphur atom. Moreover, it is shown that any factor favouring pyramidalization at copper favours charge transfer and thus coordination of the incoming O2 moiety. All these allow insight into the coordination mode of O2 and into the charge transfer from CuI in site CuM of PHM.

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Acknowledgements

The geometry optimizations and the numerical vibrational calculations reported in this paper were performed at IDRIS (Orsay, France) and CINES (Montpellier, France) national supercomputing centres. The analytical vibrational calculations were performed at the CCRE of the University Pierre et Marie Curie (Paris, France). The CASSCF and CASMP2 calculations were run at the CRIHAN (Saint-Etienne-du-Rouvray, France) regional supercomputing centre thanks to a dedicated CPU grant.

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Authors and Affiliations

  1. Laboratoire de Chimie Théorique, UMR 7616 CNRS, Université Pierre et Marie Curie, Paris 6, Case courrier 137-4, place Jussieu, 75252, Paris Cedex 05, France

    Aurélien de la Lande, Hélène Gérard & Olivier Parisel

  2. Departament de Ciències Experimentals, Universitat Jaume I, Box 224, 12080, Castelló, Spain

    Vicent Moliner

  3. Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR 8601 CNRS, Université René Descartes, Paris 5, 45, rue des Saints-Pères, 75270, Paris Cedex 06, France

    Guillaume Izzet & Olivia Reinaud

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  1. Aurélien de la Lande
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Correspondence to Olivier Parisel.

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de la Lande, A., Gérard, H., Moliner, V. et al. Theoretical modelling of tripodal CuN3 and CuN4 cuprous complexes interacting with O2, CO or CH3CN. J Biol Inorg Chem 11, 593–608 (2006). https://doi.org/10.1007/s00775-006-0107-8

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  • DOI: https://doi.org/10.1007/s00775-006-0107-8

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