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- W2009703386 abstract "The study of Cu·dipy·LL systems, where LL is a ligand coordinating through two oxygen atoms and has a delocalized π-electron cloud, has shown that KCu·dipyCu·dipy·LLKCuCu·LL [1, 2]. This is because in Cu(dipy)2+, Cu(II) has more class ‘A’ character and hence has greater affinity for the oxygen atoms in the secondary ligand. Further, in case of π-bonding ligands it can be seen that there is a better match between the π-orbitals of Cu·dipy and LL rather than in Cu·LL [3]. In other words theπ-delocalization between dipyridyl and the secondary ligand is stabilized through the metal ion. The effect is more pronounced in the case of ligands coordinating through oxygen atoms (OO) because of the additional pair of electrons on the oxygen atoms. In order to further confirm this fact, the study of the formation constants of complexes of the type Cu·A·L, where A = dipyridyl, o-phenanthroline, 2,2′-pyridyl benzimidazoline, 2,2′-pyridyl imidazoline and L = acetoacetanilidide, acetoacet-o-anisidide, acetoacet-o-toluidide, benzoatoacetanilide have been carried out. Though the β-ketoanilides have higher KH values, they form less stable complexes than β-diketones [4]. This shows that π-delocalization is less in metal β ketoanilide (Cu·L) rings. However, the ternary complexes Cu·A·L are very stable. Δ log[KCu·ACu·L-KCuCu·L] is positive though in Cu·β-diketone complexes Δ log K is zero. This must be because of the lone pair of electron over the anilide nitrogen, which gets delocalized over the β-ketoanilide ring. Due to increased electron density in the ring, Cu dπ orbitals do not match in energy with the β-ketoanilide pπ-orbitals in the binary Cu·L complex. In the mixed ligand complex Cu·A·L, however, mutual stabilization due to π-delocalization is more pronounced and hence there is greater stabilization. The extent of stabilization of the mixed ligand complex should depend on the π-delocalization in Cu·A. The order of π-delocalization can be expected to be Cu· dipyridyl > Cu·o-phenanthroline > Cu·2,2′-pyridyl benzimidazoline > Cu·2,2′-pyridyl imidazoline. The formation constants of the mixed ligand complexes Cu·A·L are in the same order." @default.
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- W2009703386 modified "2023-09-26" @default.
- W2009703386 title "π Interaction in mixed ligand complexes" @default.
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- W2009703386 doi "https://doi.org/10.1016/s0020-1693(00)92216-3" @default.
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