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Changing the chemical and physical properties of high valent heterobimetallic bis-([small mu ]-oxido) Cu-Ni complexes by ligand effects
Citation key C6DT02391F
Author Kafentzi, Maria-Chrysanthi and Orio, Maylis and Reglier, Marius and Yao, Shenglai and Kuhlmann, Uwe and Hildebrandt, Peter and Driess, Matthias and Simaan, A. Jalila and Ray, Kallol
Pages 15994-16000
Year 2016
DOI 10.1039/C6DT02391F
Journal Dalton Trans.
Volume 45
Publisher The Royal Society of Chemistry
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 [small beta]-diketiminate ligand (L = [HC-(CMeNC6H3(iPr)2)2]) with the Cu(i) complexes. In contrast to the oxo groups in known high-valent [M2([small 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[prime or minute],N[prime or minute],N[prime or minute]-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([small 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([small mu ]-O)2Cu]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.
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