Please use this identifier to cite or link to this item: http://dx.doi.org/10.14279/depositonce-6231
Main Title: Changing the chemical and physical properties of high valent heterobimetallic bis-(mu-oxido) Cu-Ni complexes by ligand effects
Author(s): Kafentzi, Maria-Chrysanthi
Orio, Maylis
Réglier, Marius
Yao, Shenglai
Kuhlmann, Uwe
Hildebrandt, Peter
Drieß, Matthias
Simaan, A. Jalila
Ray, Kallol
Type: Article
Language Code: en
Abstract: Two new heterobimetallic [LNiO2Cu(RPY2)](+) (RPY2 = N-substituted bis 2-pyridyl(ethylamine) ligands with R = indane, 3a or R = Me, 3b) complexes have been spectroscopically trapped at low temperatures. They were prepared by reacting the mononuclear side-on LNiII superoxo precursor bearing a beta-diketiminate ligand (L = [HC-(CMeNC6H3(iPr)(2))(2)]) with the Cu(I) complexes. In contrast to the oxo groups in known high-valent [M-2(mu-O)(2)](n+) (M = Fe, Co, Ni, Cu) cores that display electrophilic reactivities, 3a and 3b display rather nucleophilic oxo cores active in aldehyde deformylation reactions. However, the spectroscopic and reactivity properties of 3a/3b are found to be distinct relative to that of the previously reported [LNiO2Cu(MeAN)](+) complex containing a more basic (nucleophilic) N, N, N', N', N'-pentamethyl-dipropylenetriamine (MeAN) ligand at the copper centre. The geometry and electronic properties of the copper ligands affect the electron density of the oxygen atoms of the heterodinuclear {Ni(mu-O)(2)} core and 3a/3b undergo slower nucleophilic and faster electrophilic reactions than the previously reported [LNiO2Cu(MeAN)](+) intermediate. The present study therefore demonstrates the tuning of the electrophilicity/ nucleophilicity of the oxygen atoms of the heterobimetallic [Ni(mu-O)(2)Cu](2+) cores by controlling the electron donation from the ancillary ligands, and underlines the significance of subtle electronic changes in the physical and chemical properties of the biologically relevant heterobimetallic metal-dioxygen intermediates.
URI: https://depositonce.tu-berlin.de//handle/11303/6892
http://dx.doi.org/10.14279/depositonce-6231
Issue Date: 2016
Date Available: 24-Oct-2017
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Sponsor/Funder: DFG, EXC 314, Unifying Concepts in Catalysis
Creative Commons License: https://creativecommons.org/licenses/by/3.0/
Journal Title: Dalton transactions
Publisher: Royal Society of Chemistry
Publisher Place: Cambridge
Volume: 45
Issue: 40
Publisher DOI: 10.1039/c6dt02391f
Page Start: 15994
Page End: 16000
EISSN: 1477-9234
ISSN: 1477-9226
Appears in Collections:Fachgebiet Metallorganische Chemie und Anorganische Materialien » Publications
Fachgebiet Physikalische Chemie / Biophysikalische Chemie » Publications

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