title: Changing the chemical and physical properties of high valent heterobimetallic bis-(μ-oxido) Cu-Ni complexes by ligand effects.
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 LNiIIsuperoxo precursor bearing a β-diketiminate ligand (L = [HC-(CMeNC6H3(iPr)2)2]) with the Cu(i) complexes. In contrast to the oxo groups in known high-valent [M2(μ-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(μ-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(μ-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.
authors: Aix Marseille Univ, CNRS, Centrale Marseille, iSm2, Marseille, France. jalila.simaan@univ-amu.fr.
authors: Maria-Chrysanthi
authors: MC
authors: Kafentzi
authors: Aix Marseille Univ, CNRS, Centrale Marseille, iSm2, Marseille, France. jalila.simaan@univ-amu.fr.
authors: Maylis
authors: M
authors: Orio
authors: Aix Marseille Univ, CNRS, Centrale Marseille, iSm2, Marseille, France. jalila.simaan@univ-amu.fr.
authors: Marius
authors: M
authors: Réglier
authors: Department of Chemistry, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany. matthias.driess@tu-berlin.de.
authors: Shenglai
authors: S
authors: Yao
authors: Department of Chemistry, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany. matthias.driess@tu-berlin.de.
authors: Uwe
authors: U
authors: Kuhlmann
authors: Department of Chemistry, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany. matthias.driess@tu-berlin.de.
authors: Peter
authors: P
authors: Hildebrandt
authors: Department of Chemistry, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany. matthias.driess@tu-berlin.de.
authors: Matthias
authors: M
authors: Driess
authors: Aix Marseille Univ, CNRS, Centrale Marseille, iSm2, Marseille, France. jalila.simaan@univ-amu.fr.
authors: A Jalila
authors: AJ
authors: Simaan
authors: Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Germany. kallol.ray@chemie.hu-berlin.de.
authors: Kallol
authors: K
authors: Ray