Journal
INORGANICA CHIMICA ACTA
Volume 535, Issue -, Pages -Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2022.120845
Keywords
N,N '-bis(salicylaldehydo)propylenediimine; N,N '-bis(salicylaldehydo)tetramethylene-diimine; Nickel(II) and copper(II) complexes with Schiff-bases; Dissociation enthalpies; Formation enthalpies; Sublimation enthalpies
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Funding
- FCT, Lisbon, Portugal [UIDB/00081/2020]
- FCT/MCTES [CEECIND/01161/2017]
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This study makes a new contribution to understanding the relationship between metal-ligand bonding and the reactivity of metallic complexes. The energetic characterization of two transition metal complexes was carried out through experimental measurements and quantum chemical calculations, and compared with similar complexes.
This work constitutes a new contribution for understanding the relationship between the metal-ligand bonding and, indirectly, the inherent reactivity of metallic complexes with tetradentate N2O2 Schiff base ligands, being reported the energetic characterization of two transition metal complexes - (N,AT c -bis(salicylaldehydo)tetramethylenediiminate)nickel(II) and (N,N' -bis(salicylaldehydo)propylenediiminate)copper(II). The standard molar enthalpies of formation of these complexes were determined by solution-reaction calorimetry measurements. Their standard molar enthalpies of sublimation, at T = 298.15 K, were obtained by an effusion method. From these studies, the gas-phase enthalpies of formation of Ni(II) and Cu(II) complexes, at T = 298.15 K, were derived. Differences between the metal-ligand and mean hydrogen-ligand bond dissociation enthalpies were derived and discussed in structural terms, in comparison with identical parameters for complexes of the same metals with analogous tetradentate Schiff bases. High-level quantum chemical calculations have also been conducted, complementing the results obtained experimentally.
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