Synthesis, spectroscopic characterization, crystal structure and thermal analyses of two zinc(II) complexes with methanolysis of 2-pyridinecarbonitrile as a chelating ligand

Amani, Vahid; Ahmadi, Roya; Naseh, Mohamad; Ebadi, Amin

doi:10.1007/s13738-016-1013-9

Cited by 17 publications

(6 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The methanolysis of the initial 2-cyanopyridine takes place upon coordination with the Mn(II) ion as a chelating bidentate ligand through the two nitrogen atoms of the pyridine ring and the carbonitrile group. As observed previously, the coordination of 2-cyanopyridine to some divalent metal ions activates the CN triple bond and makes it much more amenable toward nucleophilic attack by CH 3 OH molecules [32][33][34] Figure S2). The IR spectrum for 2 also confirms the methanolysis reaction of the 2-cyanopyridine to give the O-methyl picolinimidate ligand.…”

Section: Preparation and Characterization Of Biomimetic Modelsupporting

confidence: 53%

Modeling the OEC with Two New Biomimetic Models: Preparations, Structural Characterization, and Water Photolysis Studies of a Ba–Mn Box Type Complex and a Mn4N6 Planar-Diamond Cluster

et al. 2018

View full text Add to dashboard Cite

The oxygen-evolving complex (OEC) is the native enzyme that catalyzes the oxidation of water in natural photosynthesis. Two new classes of manganese cluster complexes of formula Ba2Mn2L12(H3L1)2(CH3OH)4 1 and Mn4L26Cl2 2 were prepared (H4L1 = N,N′-(ethane-1,2-diyl)bis(2-hydroxybenzamide); L2 = methyl picolinimidate) and characterized by standard techniques including microanalysis, IR spectroscopy, ESI spectrometry, and magnetic susceptibility measurements. X-ray diffraction studies of these complexes revealed (i) a box-type structure for 1 formed by two redox-active manganese(III) ions and two barium(II) ions connected by two bridging bisamido-bisphenoxy ligand molecules; and (ii) a planar-diamond array for Mn4N6 cluster 2 where the picolinimidates act as chelating ligands through the two nitrogen atoms. The ability of 1 and 2 to split water has been studied by means of water photolysis experiments. In these experiments, the oxygen evolution was measured in aqueous media in the presence of p-benzoquinone (acting as the hydrogen acceptor), the reduction of which was followed by UV-spectroscopy. The relevant photolytic activity found for 1 is in contrast to the inactivity of 2 in the photolytic experiments. This different behavior is discussed on the basis of the structure of the biomimetic models and the proposed reaction mechanism for this process supported by DFT calculations.

show abstract

Section: Preparation and Characterization Of Biomimetic Modelsupporting

confidence: 53%

Modeling the OEC with Two New Biomimetic Models: Preparations, Structural Characterization, and Water Photolysis Studies of a Ba–Mn Box Type Complex and a Mn4N6 Planar-Diamond Cluster

et al. 2018

View full text Add to dashboard Cite

show abstract

“…Following different survey on Drug delivery and nanostructures, [ 22–52 ] here DFT–SCRF calculations are applied to probe energetic, geometric, and stability characters of the reaction between 1,3‐diene ( I ) with dienophile ( C 20 ) in order to give the suggested drug delivery ( I a ). This cycloaddition is take placed through formation of a cyclohexene ring with boat conformation and C 1 symmetry in gas phase and in solution, which is often taken as one of prototype pericyclic concerted reactions.…”

Section: Resultsmentioning

confidence: 99%

Stereoselective cycloaddition of biologically active thioindoline with the smallest nanocage in gas phase versus solution via density functional theory

Asnaashariisfahani

Azizi

Heravi

et al. 2022

J of Physical Organic Chem

View full text Add to dashboard Cite

A fine speculation of enantioselectivity prior to the expensive experimental endeavors is truly one of the ultimate goals of the computational organic chemists. In this survey, we have predicted stereo specificity for hetero Diels–Alder (DA) cycloaddition of (E)‐3‐benzylidene‐indoline‐2‐thione (I) with C20 to give (Ia) as drug delivery in the gas phase and in solution, at density functional theory (DFT)–self‐consistent reaction field (SCRF). The enthalpy difference between liquid (l) and gas (g) phases (∆Hl‐g), as well as activation energy (Eexo≠, Eendo≠) of Ia cycloadduct, appears proportional to the dielectric constant of solvent (ε). In contrast to the above trends, kinetic stability based on ∆EL‐H of Ia, develops in opposite to that of ε. The more stability of Ia is attributed to its H―bonding, and dipole–dipole interaction in water. The energy barrier of exo transition states (TS) is low; hence, cycloaddition is recommended to be of synthetically interest for preparation of asymmetric nano compound. Moreover, the π‐π aromatic stacking among the substituted phenyl ring and C20 (πsubstituted phenyl ring ↔ πC20) has significant effect on destabilization of endo TS. This DA reaction have polar nature according to one‐step mechanism, that comprises an initial hetero‐DA reaction yielding Ia, which experiences a subsequent [3,3] sigmatropic shift to yield the expected formal cycloadduct. This is a consequence of more polar nature of reaction, due to lower nucleophilicity (N), higher electrophilicity (ω), higher maximum electronic charge (ΔNmax), more polarity (μ), and more global electron density transfer (GEDT) of Ia in polar solvents (especially in water) in comparison to gas phase. This polar character is given by the electrophilic character of the C20 dienophile (ω = 5.29 eV) and nucleophilic character of the 1,3‐diene molecule (I) (N = 3.70 eV). Additionally, molecular mechanism of the considered reaction is substantially different from the DA reactions between simple 1,3‐diene and dienophiles.

show abstract

“…Among them, excellent results were obtained for this transformation with CaCl 2 , whereas MeCN was found to be the most effective solvent among the other common organic solvents tested (DMA, DMF, NMP, DMSO, MeCN, DCM, toluene, and 1,4-dioxane). 36 Evaluation of the substrate scope clearly demonstrated that the reaction was tolerant to a variety of primary and secondary aliphatic alcohols ( Scheme 21 ). However, tertiary alcohols provided complicated mixtures.…”

Section: Dehydroxylative Trifluoromethylselenylationmentioning

confidence: 99%

Recent trends in dehydroxylative trifluoro-methylation, -methoxylation, -methylthiolation, and -methylselenylation of alcohols

et al. 2021

Self Cite

View full text Add to dashboard Cite

show abstract

Synthesis, spectroscopic characterization, crystal structure and thermal analyses of two zinc(II) complexes with methanolysis of 2-pyridinecarbonitrile as a chelating ligand

Cited by 17 publications

References 43 publications

Modeling the OEC with Two New Biomimetic Models: Preparations, Structural Characterization, and Water Photolysis Studies of a Ba–Mn Box Type Complex and a Mn4N6 Planar-Diamond Cluster

Modeling the OEC with Two New Biomimetic Models: Preparations, Structural Characterization, and Water Photolysis Studies of a Ba–Mn Box Type Complex and a Mn4N6 Planar-Diamond Cluster

Stereoselective cycloaddition of biologically active thioindoline with the smallest nanocage in gas phase versus solution via density functional theory

Recent trends in dehydroxylative trifluoro-methylation, -methoxylation, -methylthiolation, and -methylselenylation of alcohols

Contact Info

Product

Resources

About