Linkage isomerism in transition-metal complexes of mixed (arylcarboxamido)(arylimino)pyridine ligands

David W. Boyce, Debra J Salmon, William B Tolman

Research output: Contribution to journalArticle

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Abstract

The synthesis of a series of asymmetric mixed 2,6-disubstituted (arylcarboxamido)(arylimino)pyridine ligands and their coordination chemistry toward a series of divalent first-row transition metals (Cu, Co, and Zn) have been explored. Complexes featuring both anionic N,N,N″-carboxamido and neutral O,N,N-carboxamide coordination have been prepared and characterized by X-ray crystallography, cyclic voltammetry, and UV-visible and EPR spectroscopy. Specifically, RLM(X) (M = Cu; X = Cl-, OAc-) and RL(H)MX2 (M = Cu, Co, Zn; X = Cl-, SbF 6 -) complexes that feature N,N,N″- or O,N,N-coordination are presented. Base-induced linkage isomerization from O,N,N-carboxamide to N,N,N″-carboxamido coordination is also confirmed by multiple forms of spectroscopy.

Original languageEnglish (US)
Pages (from-to)5788-5796
Number of pages9
JournalInorganic Chemistry
Volume53
Issue number11
DOIs
StatePublished - Jun 2 2014

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Coordination Complexes
linkages
Transition metals
pyridines
transition metals
Spectroscopy
Ligands
ligands
X ray crystallography
Isomerization
Cyclic voltammetry
Paramagnetic resonance
spectroscopy
isomerization
crystallography
chemistry
pyridine
synthesis
x rays

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Linkage isomerism in transition-metal complexes of mixed (arylcarboxamido)(arylimino)pyridine ligands. / Boyce, David W.; Salmon, Debra J; Tolman, William B.

In: Inorganic Chemistry, Vol. 53, No. 11, 02.06.2014, p. 5788-5796.

Research output: Contribution to journalArticle

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N2 - The synthesis of a series of asymmetric mixed 2,6-disubstituted (arylcarboxamido)(arylimino)pyridine ligands and their coordination chemistry toward a series of divalent first-row transition metals (Cu, Co, and Zn) have been explored. Complexes featuring both anionic N,N,N″-carboxamido and neutral O,N,N-carboxamide coordination have been prepared and characterized by X-ray crystallography, cyclic voltammetry, and UV-visible and EPR spectroscopy. Specifically, RLM(X) (M = Cu; X = Cl-, OAc-) and RL(H)MX2 (M = Cu, Co, Zn; X = Cl-, SbF 6 -) complexes that feature N,N,N″- or O,N,N-coordination are presented. Base-induced linkage isomerization from O,N,N-carboxamide to N,N,N″-carboxamido coordination is also confirmed by multiple forms of spectroscopy.

AB - The synthesis of a series of asymmetric mixed 2,6-disubstituted (arylcarboxamido)(arylimino)pyridine ligands and their coordination chemistry toward a series of divalent first-row transition metals (Cu, Co, and Zn) have been explored. Complexes featuring both anionic N,N,N″-carboxamido and neutral O,N,N-carboxamide coordination have been prepared and characterized by X-ray crystallography, cyclic voltammetry, and UV-visible and EPR spectroscopy. Specifically, RLM(X) (M = Cu; X = Cl-, OAc-) and RL(H)MX2 (M = Cu, Co, Zn; X = Cl-, SbF 6 -) complexes that feature N,N,N″- or O,N,N-coordination are presented. Base-induced linkage isomerization from O,N,N-carboxamide to N,N,N″-carboxamido coordination is also confirmed by multiple forms of spectroscopy.

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