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Title: Effects of denticity and ligand rigidity on reactivity of copper complexes with cumyl hydroperoxide

Abstract

Cu(II) complexes bearing N2/Py2 tetradentate ligands consisting of two pyridyl arms and a flexible ethyldiamine backbone, [(BPMEN)Cu(ClO4)2] (1), with rigid cyclohexyl backbone [(BPMCN)Cu(ClO4)2] (2), and substituted with bispyrrolidyl [(PDP)Cu(ClO4)2] (3), and Cu(II) complex bearing N2/Py3 pentadentate ligand, [(TPMEN)Cu(ClO4)2] (4), were synthesized and structurally characterized. Reactivity of 1–4 with cumyl hydroperoxide was investigated to study the effects of ligand rigidity and denticity on the mechanism of O–O bond cleavage. Results presented herein illustrate that 1–3 favors homolysis, however 4 showed little to almost no impact on O–O bond cleavage.

Authors:
; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1473686
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Inorganica Chimica Acta
Additional Journal Information:
Journal Volume: 483; Journal Issue: C; Journal ID: ISSN 0020-1693
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
O-O bond cleavage mechanism; complex characterization; copper coordination chemistry; cumyl hydroperoxide; oxidation reactions

Citation Formats

Pella, Bruce J., Niklas, Jens, Poluektov, Oleg G., and Mukherjee, Anusree. Effects of denticity and ligand rigidity on reactivity of copper complexes with cumyl hydroperoxide. United States: N. p., 2018. Web. doi:10.1016/j.ica.2018.07.035.
Pella, Bruce J., Niklas, Jens, Poluektov, Oleg G., & Mukherjee, Anusree. Effects of denticity and ligand rigidity on reactivity of copper complexes with cumyl hydroperoxide. United States. doi:10.1016/j.ica.2018.07.035.
Pella, Bruce J., Niklas, Jens, Poluektov, Oleg G., and Mukherjee, Anusree. Thu . "Effects of denticity and ligand rigidity on reactivity of copper complexes with cumyl hydroperoxide". United States. doi:10.1016/j.ica.2018.07.035. https://www.osti.gov/servlets/purl/1473686.
@article{osti_1473686,
title = {Effects of denticity and ligand rigidity on reactivity of copper complexes with cumyl hydroperoxide},
author = {Pella, Bruce J. and Niklas, Jens and Poluektov, Oleg G. and Mukherjee, Anusree},
abstractNote = {Cu(II) complexes bearing N2/Py2 tetradentate ligands consisting of two pyridyl arms and a flexible ethyldiamine backbone, [(BPMEN)Cu(ClO4)2] (1), with rigid cyclohexyl backbone [(BPMCN)Cu(ClO4)2] (2), and substituted with bispyrrolidyl [(PDP)Cu(ClO4)2] (3), and Cu(II) complex bearing N2/Py3 pentadentate ligand, [(TPMEN)Cu(ClO4)2] (4), were synthesized and structurally characterized. Reactivity of 1–4 with cumyl hydroperoxide was investigated to study the effects of ligand rigidity and denticity on the mechanism of O–O bond cleavage. Results presented herein illustrate that 1–3 favors homolysis, however 4 showed little to almost no impact on O–O bond cleavage.},
doi = {10.1016/j.ica.2018.07.035},
journal = {Inorganica Chimica Acta},
number = C,
volume = 483,
place = {United States},
year = {2018},
month = {11}
}

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