Side-bridged cyclam transition metal complexes bearing a phenolic ether or a phenolate pendent arm

Mewis, Ryan E and Archibald, Stephen J (2019) Side-bridged cyclam transition metal complexes bearing a phenolic ether or a phenolate pendent arm. Polyhedron, 171. pp. 578-589. ISSN 0277-5387

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Abstract

Side-bridged cyclam transition metal complexes (M = Ni(II), Cu(II) and Zn(II)) bearing a phenolic ether or phenolate pendent arm have been synthesised. For [NiL1]+ and [CuL1]+, evidence for a phenoxyl radical was obtained (quasi reversible peak at +0.74 V and +0.48 V respectively), as well as oxidation of OH, due to protonation of the phenolate, at ∼+1.24 V. The phenoxyl radical in [Ni(L1)]2+ is harder to oxidise by 0.26 V compared with the corresponding Cu(II) complex. UV–Vis data for [Ni(L1)]2+ suggests that the Ni(II) ion may be 4 or 6 coordinate whereas the Cu(II) ion in [Cu(L1)]2+ is five coordinate. The Ni(II) ion in the crystal structure of [Ni(L2)][(ClO4)2] possesses a distorted square-planar geometry in which the phenolic ether pendent arm is not involved in the coordination sphere. The cyclam ligand in this complex adopts a trans-II configuration.

Item Type:	Article
Peer-reviewed:	Yes
Date Deposited:	24 Sep 2019 09:16
Publisher:	Elsevier BV
Additional Information:	This is an Author Accepted Manuscript of a paper accepted for publication in Polyhedron, published by and copyright Elsevier.
Divisions:	Faculties > Science and Engineering
Subject terms:	Azamacrocycles, Bioinorganic, Coordination chemistry, Cyclam, Macrocyclic ligands, Science & Technology, Physical Sciences, Chemistry, Inorganic & Nuclear, Crystallography, Chemistry, Macrocyclic ligands, Azamacrocycles, Cyclam, Bioinorganic, Coordination chemistry, MACROCYCLIC LIGAND, RADICAL COMPLEXES, CHELATOR DESIGN, COPPER(II), DERIVATIVES, DEBENZYLATION, RECEPTOR, NICKEL(II), STABILITY, CLEAVAGE, 0302 Inorganic Chemistry, 0306 Physical Chemistry (incl. Structural), 0399 Other Chemical Sciences, Inorganic & Nuclear Chemistry
URI:	https://e-space.mmu.ac.uk/id/eprint/623884
DOI:	https://doi.org/10.1016/j.poly.2019.08.003
ISSN	0277-5387

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