Changing the chemical and physical properties of high valent heterobimetallic bis-(μ-oxido) Cu-Ni complexes by ligand effects

10Citations
Citations of this article
17Readers
Mendeley users who have this article in their library.

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 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.

References Powered by Scopus

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density

94430Citations
N/AReaders
Get full text

Density-functional exchange-energy approximation with correct asymptotic behavior

48911Citations
N/AReaders
Get full text

Density-functional approximation for the correlation energy of the inhomogeneous electron gas

18109Citations
N/AReaders
Get full text

Cited by Powered by Scopus

Amphoteric reactivity of metal–oxygen complexes in oxidation reactions

87Citations
N/AReaders
Get full text

Hydrogen atom transfer by a high-valent nickel-chloride complex

55Citations
N/AReaders
Get full text

From Enzymes to Functional Materials—Towards Activation of Small Molecules

51Citations
N/AReaders
Get full text

Register to see more suggestions

Mendeley helps you to discover research relevant for your work.

Already have an account?

Cite

CITATION STYLE

APA

Kafentzi, M. C., Orio, M., Réglier, M., Yao, S., Kuhlmann, U., Hildebrandt, P., … Ray, K. (2016). Changing the chemical and physical properties of high valent heterobimetallic bis-(μ-oxido) Cu-Ni complexes by ligand effects. Dalton Transactions, 45(40), 15994–16000. https://doi.org/10.1039/c6dt02391f

Readers' Seniority

Tooltip

PhD / Post grad / Masters / Doc 6

75%

Professor / Associate Prof. 1

13%

Researcher 1

13%

Readers' Discipline

Tooltip

Chemistry 7

88%

Engineering 1

13%

Save time finding and organizing research with Mendeley

Sign up for free