Journalartikel

Autorenliste: Hoffmann, A; Wern, M; Hoppe, T; Witte, M; Haase, R; Liebhauser, P; Glatthaar, J; Herres-Pawlis, S; Schindler, S

Jahr der Veröffentlichung: 2016

Seiten: 4744-4751

Zeitschrift: European Journal of Inorganic Chemistry

Bandnummer: 2016

Heftnummer: 29

ISSN: 1434-1948

DOI Link: https://doi.org/10.1002/ejic.201600906

Verlag: Wiley-VCH Verlag

Abstract: 
Mono- and bis(guanidine) ligands stabilise bis-mu-oxido dicopper(III) complexes. Here, the formation of these complexes has been investigated in detail by means of low-temperature stopped-flow techniques for the monoguanidine 2-[3-(dimethylamino)propyl]-1,1,3,3-tetramethylguanidine (TMGdmap) and the related bis(guanidine) 1,3-bis(N,N,N',N'-tetramethylguanidino)propane (btmgp). Low-temperature IR studies in solution support the formation of bis-mu-oxido complexes. For both systems, no intermediates on the pathways to the bis-mu-oxido complexes could be detected; this has been explained through extensive DFT calculations. In the first step, the oxygen reduction during the binding to the copper(I) complex to form a superoxido species was studied. In the second step, the full path from superoxido through trans-mu-peroxido to side-on peroxido and finally bis-mu-oxido was modelled for singlet and triplet states. Hereby, a clear picture of the detailed reaction mechanism, which directly correlates with the observed activation enthalpies and reaction orders, was gained. The superoxido formation is rate-determining as pseudo-first order in copper(I) although the bis-mu-oxido formation is observed. The results illustrate the strength of density functional theory for the prediction of the reactivity of real-life systems.

Harvard-Zitierstil: Hoffmann, A., Wern, M., Hoppe, T., Witte, M., Haase, R., Liebhauser, P., et al. (2016) Hand in Hand: Experimental and Theoretical Investigations into the Reactions of Copper(I) Mono- and Bis(guanidine) Complexes with Dioxygen, European Journal of Inorganic Chemistry, 2016(29), pp. 4744-4751. https://doi.org/10.1002/ejic.201600906

APA-Zitierstil: Hoffmann, A., Wern, M., Hoppe, T., Witte, M., Haase, R., Liebhauser, P., Glatthaar, J., Herres-Pawlis, S., & Schindler, S. (2016). Hand in Hand: Experimental and Theoretical Investigations into the Reactions of Copper(I) Mono- and Bis(guanidine) Complexes with Dioxygen. European Journal of Inorganic Chemistry. 2016(29), 4744-4751. https://doi.org/10.1002/ejic.201600906