Influence of non-covalent interactions on the coordination geometry of Ni(<scp>ii</scp>) in Ni(<scp>ii</scp>)–M(<scp>ii</scp>) complexes (M = Zn and Hg) with a salen-type N<sub>2</sub>O<sub>2</sub> Schiff base ligand and thiocyanate ion as the coligand

Das, Lakshmi Kanta; Bhunia, Pradip; Gomila, Rosa M.; Frontera, Antonio; Ghosh, Ashutosh

doi:10.1039/d2ce01632j

Cited by 5 publications

(2 citation statements)

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“…The complexes behave as monomers in solution at 23 °C, as indicated by the solution state Evans method magnetic moment measurements, and 19 F NMR in CD 3 CN shows that the triflate anion dissociates in solution (see SI). The vanadium(V/IV) redox event for V-Na, V-K, and V-Ba is reversible and shifts anodically with an increase in the cation charge, consistent with the effect on other heterobimetallic complexes in this ligand framework. − ,− ,− Computational studies were also performed, and the same trend is observed, though the simple model used in the calculations overestimates the increase in E 1/2 as the cation charge increases (see SI for computational details and Table S3 for values). The vanadium(V/IV) reduction potential for the monocations (V-Na and V-K) shifts 90–130 mV more positive than (salen)V(O) and 114–164 mV more positive than (salen-OMe)V(O).…”

Section: Resultssupporting

confidence: 56%

Charge and Solvent Effects on the Redox Behavior of Vanadyl Salen–Crown Complexes

et al. 2023

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The incorporation of charged groups proximal to a redox active transition metal center can impact the local electric field, altering redox behavior and enhancing catalysis. Vanadyl salen (salen = N,N′-ethylenebis(salicylideneaminato)) complexes functionalized with a crown ether containing a nonredox active metal cation (V-Na, V-K, V-Ba, V-La, V-Ce, and V-Nd) were synthesized. The electrochemical behavior of this series of complexes was investigated by cyclic voltammetry in solvents with varying polarity and dielectric constant (ε) (acetonitrile, ε = 37.5; N,N-dimethylformamide, ε = 36.7; and dichloromethane, ε = 8.93). The vanadium(V/IV) reduction potential shifted anodically with increasing cation charge compared to a complex lacking a proximal cation (ΔE 1/2 > 900 mV in acetonitrile and >700 mV in dichloromethane). In contrast, the reduction potential for all vanadyl salen–crown complexes measured in N,N-dimethylformamide was insensitive to the magnitude of the cationic charge, regardless of the electrolyte or counteranion used. Titration studies of N,N-dimethylformamide into acetonitrile resulted in cathodic shifting of the vanadium(V/IV) reduction potential with increasing concentration of N,N-dimethylformamide. Binding constants of N,N-dimethylformamide (log(K DMF)) for the series of crown complexes show increased binding affinity in the order of V-La > V-Ba > V-K > (salen)V(O), indicating an enhancement of Lewis acid/base interaction with increasing cationic charge. The redox behavior of (salen)V(O) and (salen-OMe)V(O) (salen-OMe = N,N′-ethylenebis(3-methoxysalicylideneamine) was also investigated and compared to the crown-containing complexes. For (salen-OMe)V(O), a weak association of triflate salt at the vanadium(IV) oxidation state was observed through cyclic voltammetry titration experiments, and cation dissociation upon oxidation to vanadium(V) was identified. These studies demonstrate the noninnocent role of solvent coordination and cation/anion effects on redox behavior and, by extension, the local electric field.

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Section: Resultssupporting

confidence: 56%

Charge and Solvent Effects on the Redox Behavior of Vanadyl Salen–Crown Complexes

et al. 2023

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“…The zones with relatively lower electron density will usually have "positive" or at least "less negative" electrostatic potential. Similar noncovalent interactions are also present in the complexes of other transition and nontransition metals, e.g., aerogen or noble gas bonding (NgB, group 18), 10 pnictogen bonding (PnB, group 15), 11 tetrel bonding (TtB, group 14), 12 triel bonding (TrB, group 13), 13 halogen bonding (HaB, group 17), 14 chalcogen bonding (ChB, group 16), 15 osme bonding (OmB, group 8), 16 spodium bonding (for group 12), 17 etc. Such names are proposed to differentiate these types of interactions from classical coordination bonds.…”

Section: ■ Introductionmentioning

confidence: 99%

On the Existence of Matere Bonds in Pentacoordinated Manganese Complexes: A Combined Experimental and Theoretical Investigation

Karmakar,

Gomila,

Frontera

et al. 2024

Crystal Growth & Design

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Four manganese(III) complexes, [MnL 1 Cl] (1), [MnL 2 Cl](2), [Mn 2 (L 2 ) 2 (N 3 ) 2 ] (3), and [Mn 2 (L 1 ) 2 (NCS) 2 ] (4) {H 2 L 1 = N,N′-bis(5chlorosalicylidene)-1,3-diaminopropane, H 2 L 2 = N,N′-bis(5-chlorosalicylidene)-2,2-dimethyl-1,3-diaminopropane} have been synthesized and characterized. The structures of the complexes were confirmed by single-crystal Xray diffraction analysis. All four complexes showed a tendency to form supramolecular dimers in the solid state. Density functional theory (DFT) calculations have been used to investigate the supramolecular assemblies observed in the solid state of these complexes and to characterize the Mn•••O interactions in terms of covalent/noncovalent nature and their importance for the formation of self-assembled dimers in complexes 1−4. QTAIM and NCIPlot calculations have been used to disclose the noncovalent nature of the Mn•••O contacts in complexes 1−4, which can be considered as matere bonds (MaBs) instead of coordination bonds. Such a type of matere bond is unprecedented in square pyramidal Mn complexes. Energetically, the MaBs exhibit values ranging from −8 to −11 kcal/mol across these complexes. Therefore, this research highlights the attractive interactions between group 7 Mn(III) derivatives and Lewis bases involving a π-hole formed opposite one of the apical coordination bonds.

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Synthesis, characterization, and structural analysis of hetero Ni(II)–Na(I) and Homo Ni(II)–Ni(II) dinuclear complexes with a flexible tridendate schiff base ligand

Narayanaswamy,

Bhargavi,

Rajasekharan

2024

Journal of Molecular Structure

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Influence of non-covalent interactions on the coordination geometry of Ni(ii) in Ni(ii)–M(ii) complexes (M = Zn and Hg) with a salen-type N₂O₂ Schiff base ligand and thiocyanate ion as the coligand

Abstract: A nickel(II)-zinc(II) complex, [(NiL)Zn(µ1,3-NCS)2]n (1) and a nickel(II)-mercury(II) complex, [{(NiL)Hg(µ1,3-SCN)(SCN)}2] (2) (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine) have been synthesized via metalloligand approach of which former is a 2D coordination polymer but...

Cited by 5 publications

References 63 publications

Charge and Solvent Effects on the Redox Behavior of Vanadyl Salen–Crown Complexes

Charge and Solvent Effects on the Redox Behavior of Vanadyl Salen–Crown Complexes

On the Existence of Matere Bonds in Pentacoordinated Manganese Complexes: A Combined Experimental and Theoretical Investigation

Synthesis, characterization, and structural analysis of hetero Ni(II)–Na(I) and Homo Ni(II)–Ni(II) dinuclear complexes with a flexible tridendate schiff base ligand

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Influence of non-covalent interactions on the coordination geometry of Ni(ii) in Ni(ii)–M(ii) complexes (M = Zn and Hg) with a salen-type N2O2 Schiff base ligand and thiocyanate ion as the coligand

Abstract: A nickel(II)-zinc(II) complex, [(NiL)Zn(µ1,3-NCS)2]n (1) and a nickel(II)-mercury(II) complex, [{(NiL)Hg(µ1,3-SCN)(SCN)}2] (2) (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine) have been synthesized via metalloligand approach of which former is a 2D coordination polymer but...

Cited by 5 publications

References 63 publications

Charge and Solvent Effects on the Redox Behavior of Vanadyl Salen–Crown Complexes

Charge and Solvent Effects on the Redox Behavior of Vanadyl Salen–Crown Complexes

On the Existence of Matere Bonds in Pentacoordinated Manganese Complexes: A Combined Experimental and Theoretical Investigation

Synthesis, characterization, and structural analysis of hetero Ni(II)–Na(I) and Homo Ni(II)–Ni(II) dinuclear complexes with a flexible tridendate schiff base ligand

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Influence of non-covalent interactions on the coordination geometry of Ni(ii) in Ni(ii)–M(ii) complexes (M = Zn and Hg) with a salen-type N₂O₂ Schiff base ligand and thiocyanate ion as the coligand