Issue 3, 2007

A cadmium hydroxide complex of a N3S-donor ligand containing two hydrogen bond donors: synthesis, characterization, and CO2 reactivity

Abstract

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/π 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 ΔH° = +31(2) kJ mol−1 and ΔS° = +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).

Graphical abstract: A cadmium hydroxide complex of a N3S-donor ligand containing two hydrogen bond donors: synthesis, characterization, and CO2 reactivity

Supplementary files

Article information

Article type
Paper
Submitted
04 Gwen. 2006
Accepted
14 Du 2006
First published
29 Du 2006

Dalton Trans., 2007, 351-357

A cadmium hydroxide complex of a N3S-donor ligand containing two hydrogen bond donors: synthesis, characterization, and CO2 reactivity

R. A. Allred, S. A. Huefner, K. Rudzka, A. M. Arif and L. M. Berreau, Dalton Trans., 2007, 351 DOI: 10.1039/B612748G

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