ABSTRACT
Multi-metallic cooperative catalysis has gained a lot of interest in organic synthesis over the past few years exploring various organic transformations. Of all the myriad chemical transformations, multi-metallic cooperative catalysis offers exceptional chemo-, stereo- and regio-selectivities. In recent years, hetero-multi-metallic catalysis has not only been used to synthesise only simpler organic molecules but rather more complex molecules like heteroarenes which include a variety of commercially important molecules. The current review, in this context, emphasises the synthesis of 5- and 6-membered as well as condensed heteroarenes, covering the literature over the last decade. The discussion focusses on the combinations in cooperative catalytic systems in strategies used to achieve selectivity and also highlights the mode of action for the cooperative catalysis leading to the synthesis of a few commercially and biologically relevant heteroarenes. Finally, the review concludes with a brief outlook on the future scope and opportunities in the field of cooperative catalyses and their prospects for providing state-of-the-art solutions for synthetically challenging organic transformations.
ABSTRACT
The osmotic coefficient measurements for binary aqueous solutions of 2,2,2-cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8] hexacosane) in the concentration range of ~0.009 to ~0.24 mol·kg(-1) and in ternary aqueous solutions containing a fixed concentration of 2,2,2-cryptand of ~0.1 mol·kg(-1) with varying concentration of KBr (~0.06 to ~0.16 mol·kg(-1)) have been reported at 298.15 K. The diamine gets hydrolyzed in aqueous solutions and needs proper approach to obtain meaningful thermodynamic properties. The measured osmotic coefficient values are corrected for hydrolysis and are used to determine the solvent activity and mean ionic activity coefficients of solute as a function of concentration. Strong ion-pair formation is observed, and the ion-pair dissociation constant for the species [CrptH](+)[OH(-)] is reported. The excess and mixing thermodynamic properties (Gibbs free energy, enthalpy, and entropy changes) have been obtained using the activity data from this study and the heat data reported in the literature. Further, the data are utilized to compute the partial molal entropies of solvent and solute at finite as well as infinite dilution of 2,2,2-cryptand in water. The concentration dependent non-linear enthalpy-entropy compensation effect has been observed for the studied system, and the compensation temperature along with entropic parameter are reported. Using solute activity coefficient data in ternary solutions, the transfer Gibbs free energies for transfer of the cryptand from water to aqueous KBr as well as transfer of KBr from water to aqueous cryptand were obtained and utilized to obtain the salting constant (ks) and thermodynamic equilibrium constant (log K) values for the complex (2,2,2-cryptand:K(+)) at 298.15 K. The value of log K = 5.8 ± 0.1 obtained in this work is found to be in good agreement with that reported by Lehn and Sauvage. The standard molar entropy for complexation is also estimated for the 2,2,2-cryptand-KBr complex in aqueous medium.
