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• W2028011509 abstract "Abstract Two tripodal ligands containing two pyridyl and one 4‐(benzimidazol‐2‐yl)‐2‐ tert ‐butylphenol (HL H ) and one 2‐ tert ‐butyl‐4‐( N ‐methylbenzimidazol‐2‐yl)phenol (HL Me ) unit have been synthesized. They possess a N 3 O donor set that is known to stabilize phenoxyl radicals more efficiently than the corresponding N 2 O 2 donor unit. Reaction of one molar equiv. of Cu(ClO 4 ) 2 · 6H 2 O with HL H or HL Me affords the zwitterionic benzimidazolium phenolate complexes [Cu II (HL H )] 2+ and [Cu II (HL Me )] 2+ via a proton transfer reaction coupled to copper(II) coordination. Addition of HClO 4 to [Cu II (HL H )] 2+ and [Cu II (HL Me )] 2+ results in the formation of the benzimidazolium phenol complexes [Cu II (H 2 L H )] 3+ and [Cu II (H 2 L Me )] 2+ , while addition of NEt 3 affords the benzimidazol‐phenolate complexes [Cu II (L H )] 2+ and [Cu II (L Me )] 2+ , respectively. The phenol’s p K a is remarkably low due to the strong withdrawing effect of the benzimidazolium substituent. X‐ray crystallographic analysis of the copper(II) complexes shows that deprotonation of the axial phenol forces the metal to move out of the square plane towards the oxygen atom, and one (or two) Cu–N pyridine equatorial bond length increases. The copper(II) phenoxyl species [Cu II (HL H )] · 3+ and [Cu II (HL Me )] · 3+ were prepared electrochemically, or by addition of two molar equiv. of copper(II) to HL H or HL Me . Under these conditions, radical formation has never been observed for tripodal ligands containing two pyridyl and one 2,4‐di‐ tert ‐butylphenol group. This difference is explained in terms of the proton transfer mechanism and redox potentials. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)" @default.
• W2028011509 created "2016-06-24" @default.
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• W2028011509 date "2006-09-01" @default.
• W2028011509 modified "2023-10-13" @default.
• W2028011509 title "Galactose Oxidase Models: Creation and Modification of Proton Transfer Coupled to Copper(II) Coordination Processes in Pro‐Phenoxyl Ligands" @default.
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• W2028011509 doi "https://doi.org/10.1002/ejic.200600286" @default.
• W2028011509 hasPublicationYear "2006" @default.
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