Copper (II)-mediated oxidative dehydrogenation of amine ligands

[Display omitted] •O. D. of a polyamine Cu(II) compound led to imine and amine Cu(I) complexes.•Cu(II) carried out oxidative dehydrogenation (O.D.) with no external base nor oxidant.•Crystal structures of imine hexa and amine pentadentate Cu(II) complexes are presented.•Polyamine Cu(II) complex unde...

Full description

Saved in:
Bibliographic Details
Published in:Inorganica Chimica Acta 2018-09, Vol.481, p.189-196
Main Authors: Sarmiento-Pavía, Pedro D., Flores-Álamo, Marcos, Solano-Peralta, Alejandro, Kroneck, Peter M.H., Sosa-Torres, Martha E.
Format: Article
Language:English
Subjects:
Alcohol
Chemical compounds
Copper
Copper(I)
Copper(II)
Crystallography
Dehydrogenation
Infrared radiation
Ligands
Mono-imine
Nitrogen atoms
NMR
Nuclear magnetic resonance
Oxidation
Oxidative dehydrogenation
Pentadentate amine
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:[Display omitted] •O. D. of a polyamine Cu(II) compound led to imine and amine Cu(I) complexes.•Cu(II) carried out oxidative dehydrogenation (O.D.) with no external base nor oxidant.•Crystal structures of imine hexa and amine pentadentate Cu(II) complexes are presented.•Polyamine Cu(II) complex underwent a disproportionation reaction. The process of oxidative dehydrogenation of the pentadentate amine ligand 2,10-bis-(2′-pyridyl)-3,6,9-triazaundecane (L1am) mediated by Cu(II) in the absence of an external oxidant led to the Cu(I) mono-imine complex, [CuIL1im](BPh4). This complex was quite sensitive towards air oxidation, leading to the corresponding Cu(II) mono-imine complex. The complexes were characterized by C, H, N analysis, IR, NMR, and cyclic voltammetry. The structures of the Cu(II) mono-imine complexes, [CuIIL1im(X)](BPh4)2 (X = CH3COCH3, CH3SOCH3, or CH3CN), and of the Cu(II) amine complex [CuIIL1am](BPh4)(NO3), were solved by X-ray crystallography. These complexes carried each a Cu(II)N5 site, with five nitrogen atoms provided by either L1im (2 sp3 amino N, 1 sp2 imino N, 2 sp2 pyridine N), or L1am (3 sp3 amino N, 2 sp2 pyridine N). The Cu(II) promoted oxidative dehydrogenation of amine ligand L1am did not require an external base in contrast to related Fe(III)/Fe(II) systems.
ISSN:0020-1693
1873-3255
DOI:10.1016/j.ica.2017.10.019