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Structural and Electrochemical Studies of Copper(I) Complexes with Diethoxyphosphoryl‐1,10‐phenanthrolines
Author(s) -
Mitrofanov Alexander,
Manowong Machima,
Rousselin Yoann,
Brandès Stéphane,
Guilard Roger,
BessmertnykhLemeune Alla,
Chen Ping,
Kadish Karl M.,
Goulioukitaliya,
Beletskaya Irina
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402161
Subject(s) - chemistry , phenanthroline , triphenylphosphine , copper , substituent , ligand (biochemistry) , bromide , denticity , steric effects , electrochemistry , chelation , coordination complex , coordination sphere , trifluoromethanesulfonate , bite angle , inorganic chemistry , metal , medicinal chemistry , stereochemistry , organic chemistry , catalysis , biochemistry , receptor , electrode
Two series of copper(I) complexes with diethoxyphosphoryl‐substituted 1,10‐phenanthroline ligands were synthesized and characterized in the solid state and in solution. The first comprised mixed‐ligand Cu I complexes with phenanthroline and triphenylphosphine. The second series includes bis‐chelates with two phenanthroline ligands. According to the X‐ray data for the six complexes, the ditopic phenanthroline ligands exhibit bidentate coordination to the copper(I) atom through two nitrogen atoms in both series. Solution equilibria involving different phenanthroline copper(I) species were studied by 1 H and 31 P NMR spectroscopy, electrochemistry, and spectroelectrochemistry. The solution speciation of these labile complexes is different for these two series and depends on the nature of solvent and the location of the phosphorus substituent on the phenanthroline backbone. Coordinating solvents can replace a bromide, triphenylphosphine, and even a phenanthroline ligand in the inner coordination sphere of the metal center. Copper(I) complexes with α‐substituted phenanthrolines easily dissociate even in noncoordinating solvents such as CH 2 Cl 2 and CHCl 3 . Ligand‐exchange reactions leading to less sterically hindered species were observed under the utilized solution conditions. The coordination mode of the phenanthroline chelators does not change under any of the utilized solution conditions, and binding of the phosphoryl group to the metal center was never observed by spectroscopic or spectroelectrochemical methods.