Side-On Bound Beryllium Dinitrogen Complex: A Precursor for Complete Conversion of Dinitrogen to Ammonia Mediated by -Heterocyclic Carbene.

The complete conversion of dinitrogen to ammonia mediated by a side-on N-bound carbene-beryllium complex, [NHC-Be(η-N)] has been studied considering both the symmetric and unsymmetric pathways. -heterocyclic carbenes complexed with Be(η-N) moieties were considered substrates in our study. We found that two mechanistic pathways were possible for the reduction of dinitrogen to form ammonia.

Beryllium carbonyl Be(CO) ( = 1-4) complex: a p-orbital analogy of Dewar-Chatt-Duncanson model.

Transition metal-carbonyl bonds are rationalized by M ← CO σ donation and M → CO π back donation where the d orbital of the transition metal is involved. This bonding model provided by Dewar, Chatt and Duncanson (DCD) has rationalized many transition metal-ligand bonds. The involvement of p orbital in such a DCD model can be intriguing.

Enhancing Precatalyst Performance and Robustness through Aromaticity: Insights from Iridaheteroaromatics.

Despite the inherent stability-enhancing benefits of dπ-pπ conjugation-induced aromaticity, metallaaromatic catalysts remain underutilized in this context, despite their reactivity with organic functionalities in stoichiometric reactions. We present a strategy for synthesizing a diverse range of iridaheteroaromatics, (L^L)Ir(Cp*)I, including iridapyridylidene-indole, iridapyridene-indole, and iridaimidazole, via in situ deprotonation/metalation reactions utilizing [Cp*IrCl] and the respective ligands. These catalysts exhibit enhanced σ-donor and π-acceptor properties, intrinsic σ-π continuum attributes, and versatile binding sites, contributing to stability through enhanced dπ-pπ conjugation-induced aromaticity.

Pushing The Extreme of Multicentre Bonding: Planar Pentacoordinate Hydride.

Planar hypercoordination has sparkled interest among the researchers from last few decades. Most of the elements in the Periodic Table have shown this remarkable structural feature. However, the smallest element, hydrogen, is missing in the list.

Highly Luminescent Eu-Incorporated Zr-MOFs as Fluorescence Sensors for Detection of Hazardous Organic Compounds in Water and Fruit Samples.

Considering the risk of toxic organic compounds to both human health and the environment, highly luminescent Eu-incorporated amino-functionalized zirconium metal-organic frameworks, namely, Eu/MOF and Eu@MOF were synthesized via the solvothermal method. The synthesized luminescent europium-incorporated MOFs act as outstanding sensor materials for diphenylamine and dinitrobenzene detection in water and fruit samples. The synergistic effect of Eu metal ions and amino-functionalized MOFs enhances the luminescent properties of the MOFs improving the fluorescence sensing ability toward the analytes.

Manganese Complex Catalyzed Sequential Multi-component Reaction: Enroute to a Quinoline-Derived Azafluorenes.

The development of innovative synthetic strategies for constructing complex molecular structures is the heart of organic chemistry. This significance of novel reactions or reaction sequences would further enhance if they permitted the synthesis of new classes of structural motifs, which have not been previously created. The research on the synthesis of heterocyclic compounds is one of the most active topics in organic chemistry due to the widespread application of N-heterocycles in life and material science.

Sequential organo and metal catalyzed reaction between 3-pyrrolyloxindoles and linear nitroenynes: access to cyclic aza-spirooxindoles.

An asymmetric Michael addition/hydroarylation reaction sequence, catalyzed by a sequential catalytic system consisting of a squaramide and a combination of silver and gold salts, provides a new series of cyclic aza-spirooxindole derivatives in excellent yields (up to 94%) and high diastero- and enantioselectivities (up to 7 : 1 dr, up to >99% ee). Computational study has also been performed.

Palladium-Catalyzed Annulative Coupling of Spirovinylcyclopropyl Oxindoles with -Quinone Methides.

Pd-catalyzed annulative coupling of spirovinylcyclopropyl oxindoles with -quinone methides has been accomplished cascade carbon-carbon bond formation to afford -spirooxindole scaffolds. The mild reaction conditions, diastereoselectivity, functional group diversity, post-synthetic transformations, and mechanistic studies using DFT calculations are the important practical features.

Cobalt-Catalyzed Stereospecific C-N/C-O Bond Formation of Oxiranes with Diaziridines.

Co-catalyzed stereospecific C-N and C-O bond formation of oxiranes with diaziridines has been accomplished to furnish tetrahydro-[1,3,4]-oxadiazines at room temperature. Optically active oxiranes can be coupled with high optical purities (>96% ee). Stereoselectivity, functional group tolerance, mechanistic studies using DFT, and natural product modification are the important practical features.

Heterogeneous iron catalyst for C(1)-H functionalization of 2-naphthols with primary aromatic alcohols.

An iron oxide nanocatalyst supported on a potassium exchanged zeolite-Y (FeO-KY) is an efficient and reusable catalyst that promotes the selective α-H functionalization of 2-naphthols with various aromatic primary alcohols. The reaction occurs at 110 °C in dichloroethane and requires 6 h for completion. The product yields were found to vary with respect to the nature of the substituents.

An study of the selective adsorption and separation of CO from a flue gas mixture (CH, CO, N) by ZnLi clusters.

Due to the increasing concentration of CO in the atmosphere and its negative effect on the environment, selective adsorption of CO from flue gas has become significantly important. In this study, we have considered a Zn-doped lithium cluster, ZnLi cluster, featuring a planar pentacoordinate Zn centre, as a potential candidate for selective CO capture and separation from a flue gas mixture (CH, CO, N). The binding energy calculation and non-covalent interaction study showed that CO molecules bind relatively strongly as compared to N and CH molecules.

Ultra-high reversible hydrogen storage capacity of the LiB cluster: a quantum chemical study.

Quantum chemical calculations have been carried out to investigate the hydrogen adsorption characteristics of the LiB cluster. Calculations reveal that the cluster can adsorb a maximum of thirteen H molecules reaching a considerably high gravimetric density of 34.66 wt%.

Inorganic Bergman Cyclization: An Appeal From Theory.

The scope of Bergman cyclization is expanded computationally by exploring the cyclization in inorganic B, N substituted derivative. This substitution has introduced polarity into the transition state, which resulted in dramatic lowering of the activation barrier. Natural charge distribution throughout the reaction profile has ascertained this hypothesis.

Can an alkalide act as a perfect Lewis base?

The Lewis basic character of alkali metals forming donor-acceptor complexes is a very rare phenomenon. No Lewis adduct with an alkalide as the Lewis basic centre has ever been reported. Herein, we theoretically designed EXH (E = Li, Na, K; X = Be, Mg, Ca) clusters which represent the first true example of Lewis adducts with alkalides as the two-electron donor basic sites.