Density Functional Theory studies on interactions of phosphoryl ligands with the Ca2+ cation: Affinity and associated parameters

Costa, Leonardo Moreira da; Carneiro, José Walkimar de M.; Paes, Lilian Weitzel Coelho; Romeiro, Gilberto A.

doi:10.1016/j.theochem.2009.06.035

Cited by 17 publications

(8 citation statements)

References 43 publications

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“…According to our previous studies, the length of the phosphoryl, imino, thiocarbonyl, and carbonyl double bond (XY) is also correlated with the strength of the metal–ligand interaction. In the metal–ligand complexes, the resonance effect of electron‐donating para ‐substituted group decreases the double‐bond character of the XY bond and shifts electron density to the coordinating ligand atom (increasing its negative charge), thus strengthening the ionic component of the metal–ligand interaction.…”

Section: Resultsmentioning

confidence: 91%

“…. The substitution energy was corrected with the ZPE and the thermal contribution (298 K) using unscaled frequencies to yield substitution enthalpy values at 298 K. The same approach has been used previously to determine the coordination energies between metal cations and ligands.

{[Ni {({normalH}_{2} O)}_{6}]}^{2 +} + L \to {[Ni {({normalH}_{2} O)}_{5}]}^{2 +} {+ H}_{2} O

…”

Section: Resultsmentioning

confidence: 99%

“…Continuing our previous investigations on the effect of substituents on the interaction between para ‐substituted ligands and metal aquacomplexes, in this work, we investigate the interaction affinity order of ligands containing O, N, and S donor atoms, for the pentaaqua nickel(II) complex. As model ligands, we studied compounds with PO (phosphoryl), CN (imino), CS (thiocarbonyl), and CO (carbonyl) functional groups.…”

Section: Introductionmentioning

confidence: 84%

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Density functional theory investigation of the binding interactions between phosphoryl, carbonyl, imino, and thiocarbonyl ligands and the pentaaqua nickel(II) complex: Coordination affinity and associated parameters

Costa

Stoyanov

Damasceno

et al. 2013

Int. J. Quantum Chem.

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Density Functional Theory (UB3LYP/6-31111G(d,p)) calculations of the affinity of the pentaaqua nickel(II) complex for a set of phosphoryl [O@P(H)(CH 3 )(PhR)], imino [HN@C(CH 3 )(PhR)], thiocarbonyl [S@C(CH 3 )(PhR)] and carbonyl [O@C(CH 3 )(PhR)] ligands were performed, where R@NH 2 , OCH 3 , OH, CH 3 , H, Cl, CN, and NO 2 is a substituent at the para-position of a phenyl ring.The affinity of the pentaaqua nickel(II) complex for these ligands was analized and quantified in terms of interaction enthalpy (DH), Gibbs free energy (DG 298 ), geometric and electronic parameters of the resultant octahedral complexes. The DH and DG 298 results show that the ligand coordination strength increases in the following order: carbonyl < thiocarbonyl < imino < phosphoryl. This coordination strength order is also observed in the analysis of the metal-ligand distances and charges on the ligand atom that interacts with the Ni(II) cation. The electronic character of the substituent R is the main parameter that affects the strength of the metal-ligand coordination. Ligands containing electron-donating groups (NH 2 , OCH 3 , OH) have more exothermic DH and DG 298 than ligands with electron-withdrawing groups (Cl, CN, NO 2 ). The metal-ligand interaction decomposed by means of the energy decomposition analysis (EDA) method shows that the electronic character of the ligand modulates all the components of the metal-ligand interaction. The absolute softness of the free ligands is correlated with the covalent contribution to the instantaneous interaction energy calculated using the EDA method.

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Section: Resultsmentioning

confidence: 91%

{[Ni {({normalH}_{2} O)}_{6}]}^{2 +} + L \to {[Ni {({normalH}_{2} O)}_{5}]}^{2 +} {+ H}_{2} O

…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 84%

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Density functional theory investigation of the binding interactions between phosphoryl, carbonyl, imino, and thiocarbonyl ligands and the pentaaqua nickel(II) complex: Coordination affinity and associated parameters

Costa

Stoyanov

Damasceno

et al. 2013

Int. J. Quantum Chem.

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“…Several studies report this methodology to determine the strength of binding of metal cations and ligands. [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][38][39][40][41][42][43][44][45][46][47] …”

Section: Resultsmentioning

confidence: 99%

“…[38][39][40][41][42][43][44][45][46][47] With the same objective, here we employ the B3LYP functional 48 to analyze the affinity of the Mg 2+ and Ca 2+ aquacations for the dithiolene ligands and to rationalize it through correlations with parameters of fundamental chemistry. Moreover, the EDA, 49-51 NBO 52 and donor-acceptor analysis methods are employed to further elucidate the character of the metal-dithiolene coordination interactions.…”

Section: +mentioning

confidence: 99%

Theoretical Study of the Interaction of 1,2-Dithiolene Ligands with the Mg2+ and Ca2+ Aquacations: Electronic, Geometric and Energetic Analysis

Melengate¹,

Stoyanov²,

Quattrociocchi³

et al. 2017

J. Braz. Chem. Soc.

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The B3LYP/6-311++G (d,p) 2+ (M = Mg or Ca) aquacations. Two series of ligands are studied: one with a phenyl ring directly bonded to the S interacting atoms and the other with a substituted ethylene (>C=C<) bonded to the two sulfide groups. These ligands present substituents with distinct induction and resonance electronic donor/acceptor effects. Fundamental characteristics, such as geometry, charges and energy of the complexed aquacations and isolated ligands, are analyzed and rationalized to correlate with the substituents effects and the metal-ligand affinity. The thermodynamic results, energy decomposition analysis (EDA) and natural bond order (NBO) show the chelate effect has an important contribution to complex stabilization and leading to an enhanced knowledge of the metal-dithiolene interaction and coordination affinity between the alkaline earth metals and sulfured ligands.

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Regiospecific Calcium‐Mediated Intermolecular Hydrophosphanylation of Butadiynes with Diphenylphosphane Oxide

et al. 2012

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Density Functional Theory studies on interactions of phosphoryl ligands with the Ca2+ cation: Affinity and associated parameters

Cited by 17 publications

References 43 publications

Density functional theory investigation of the binding interactions between phosphoryl, carbonyl, imino, and thiocarbonyl ligands and the pentaaqua nickel(II) complex: Coordination affinity and associated parameters

Density functional theory investigation of the binding interactions between phosphoryl, carbonyl, imino, and thiocarbonyl ligands and the pentaaqua nickel(II) complex: Coordination affinity and associated parameters

Theoretical Study of the Interaction of 1,2-Dithiolene Ligands with the Mg2+ and Ca2+ Aquacations: Electronic, Geometric and Energetic Analysis

Regiospecific Calcium‐Mediated Intermolecular Hydrophosphanylation of Butadiynes with Diphenylphosphane Oxide

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