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Dalton Trans., 2007, 351 - 357, DOI: 10.1039/b612748g
A cadmium hydroxide complex of a N3S-donor ligand containing two hydrogen bond donors: synthesis, characterization, and CO2 reactivity
Russell A. Allred, Sara A. Huefner, Katarzyna Rudzka, Atta M. Arif and Lisa M. Berreau
Treatment of the ebnpa (N-2-(ethylthio)ethyl-N,N-bis((6-neopentylamino-2-pyridyl)methyl)amine) ligand with a molar equivalent amount of Cd(ClO4)2·5H2O in CH3CN followed by the addition of [Me4N]OH·5H2O yielded the cadmium hydroxide complex [(ebnpaCd)2(µ-OH)2](ClO4)2 ( 1). Complex 1 has a binuclear cation in the solid-state with secondary hydrogen-bonding and CH/
interactions involving the ebnpa ligand. In acetonitrile, 1 forms a binuclear/mononuclear equilibrium mixture. The formation of a mononuclear species has been confirmed by conductance measurements of 1 at low concentrations. Variable temperature studies of the binuclear/mononuclear equilibrium provided the standard enthalpy and entropy associated with the formation of the monomer as 
H° = +31(2) kJ mol–1 and S° = +108(8) J mol–1 K–1, respectively. Enhanced secondary hydrogen-bonding interactions involving the terminal Cd–OH moiety may help to stabilize the mononuclear complex. Treatment of 1 with CO2 in acetonitrile results in the formation of a binuclear cadmium carbonate complex, [(ebnpaCd)2(µ-CO3)](ClO4)2 ( 2).
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