A5030851922- Organoboron and organosilicon chemistry
- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Boron Compounds in Chemistry
- Organometallic Complex Synthesis and Catalysis
- Boron and Carbon Nanomaterials Research
- Synthesis and characterization of novel inorganic/organometallic compounds
- Hydrogen Storage and Materials
- Crystallography and molecular interactions
- Catalytic Processes in Materials Science
- Fluorine in Organic Chemistry
- Graphene research and applications
- Radioactive element chemistry and processing
- Inorganic Chemistry and Materials
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Magnetism in coordination complexes
- Molecular Junctions and Nanostructures
- MXene and MAX Phase Materials
- Membrane-based Ion Separation Techniques
- Luminescence and Fluorescent Materials
- Ammonia Synthesis and Nitrogen Reduction
- 2D Materials and Applications
- Nanopore and Nanochannel Transport Studies
- Machine Learning in Materials Science
- Asymmetric Hydrogenation and Catalysis
Indian Institute of Science Bangalore
2017-2025
Bangalore University
2019
The development of a fully ab initio theory for the chemical vapor deposition (CVD) synthesis two-dimensional (2D) materials is prominent challenge in computational chemistry and science. Here, quantum-mechanical density functional calculations are used to discover mechanisms underlying nucleation growth monolayer 2H molybdenum disulfide (MoS2) during organometallic CVD. Starting with hexacarbonyl (Mo(CO)6) hydrogen sulfide (H2S) as molecular precursors, we elucidate processes such...
The reaction of [(Cp*Mo)2 (μ-Cl)2 B2 H6 ] (1) with CO at room temperature led to the formation highly fluxional species [{Cp*Mo(CO)2 }2 {μ-η2 :η2 -B2 H4 }] (2). Compound 2, best our knowledge, is first example a bimetallic diborane(4) conforming singly bridged Cs structure. Theoretical studies show that 2 mimics Cotton dimolybdenum-alkyne complex [{CpMo(CO)2 C2 H2 ]. In an attempt replace two hydrogen atoms in 2e [W(CO)4 fragment, W(CO)4 (3) was isolated upon treatment [W(CO)5 ⋅thf]. 3 shows...
The room-temperature reaction of [Cp*TaCl4 ] with LiBH4 ⋅THF followed by addition S2 CPPh3 results in pentahydridodiborate species [(Cp*Ta)2 (μ,η2 :η2 -B2 H5 )(μ-H)(κ2 ,μ-S2 CH2 )2 (1), a classical [B2 ]- ion stabilized the binuclear tantalum template. Theoretical studies and bonding analysis established that unusual stability 1 is mainly due to stabilization sp2 -B center electron donation from tantalum. Reactions replace hydrogens attached diborane moiety 2 e {M(CO)4 } fragment (M=Mo or W)...
Heteropolar two-dimensional materials, including hexagonal boron nitride (hBN), are promising candidates for seawater desalination and osmotic power harvesting, but previous simulation studies have considered bare, unterminated nanopores in molecular dynamics (MD) simulations. There is presently a lack of force fields to describe functionalized nanoporous hBN aqueous media. To address this gap, we conduct density functional theory (DFT)-based ab initio MD simulations surrounded by water...
Abstract The electronic structure of (η 5 ‐Cp) 2 Zr(NH ‐BB‐NH ) ( 3 b suggests that it could be a candidate for having boron–boron triple bond in the cyclic system; however, computational studies shows is very high energy isomer on its potential surface. Replacement amines with tricoordinate nucleophilic boron groups Zr[B(PH ‐BB‐B(PH ] c reduces relative dramatically. B≡B arises through donation two electrons from metal fragment, ZrCp , to in‐plane π‐bonding orbital central B–B unit. Strong...
The synthesis and characterization of metal-free fluoroborylene [(Me-cAAC)<sub>2</sub>BF] (<bold>1</bold>) is reported.
Abstract The reaction of [(Cp*Mo) 2 (μ‐Cl) B H 6 ] ( 1 ) with CO at room temperature led to the formation highly fluxional species [{Cp*Mo(CO) } {μ‐η :η ‐B 4 }] ). Compound 2, best our knowledge, is first example a bimetallic diborane(4) conforming singly bridged C s structure. Theoretical studies show that mimics Cotton dimolybdenum–alkyne complex [{CpMo(CO) ]. In an attempt replace two hydrogen atoms in 2e [W(CO) fragment, W(CO) 3 was isolated upon treatment 5 ⋅thf]. shows intriguing...
Abstract The room‐temperature reaction of [Cp*TaCl 4 ] with LiBH ⋅THF followed by addition S 2 CPPh 3 results in pentahydridodiborate species [(Cp*Ta) (μ,η :η ‐B H 5 )(μ‐H)(κ ,μ‐S CH ) ( 1 ), a classical [B − ion stabilized the binuclear tantalum template. Theoretical studies and bonding analysis established that unusual stability is mainly due to stabilization sp center electron donation from tantalum. Reactions replace hydrogens attached diborane moiety e {M(CO) } fragment (M=Mo or W)...
Abstract During the Search for a relationship between boranes and allotropes of elemental boron, several chemical problems came up: mechanism 1,2‐shift in vinyl cations, relative stability polyhedral boranes, carboranes, pyramidal Non‐planar 2π aromaticity, pseudo π* sequential dehydrogenation polycondensation design stuffed boron fullerenes C−C bond making breaking processes belong to this group. A common thread that runs through these projects is use frontier molecular orbitals design,...
A detailed DFT study involving 50 intermediates, 26 transition states, a range of spin multiplicities and 3 MECPs explains the products (and their distribution) reaction cyclohexyl isocyanide with Cr–Cr quintuple-bonded complex [LCr]2 (L = N,N′-bis(2,6-diisopropylphenyl-1,4-diazadiene). Using methyl as prototypical N,N′-bis(2,6-dimethyl-1,4-diazadiene) system, mechanistic pathways for formation diamagnetic [LCr(MeNC)4] (2b) paramagnetic [L2Cr2[C4(NMe)4](MeNC)2] (3b) [L2Cr2[C6(NMe)6]] (4b) an...
The inherent tendency of BR fragments to undergo coupling is utilized predict M2B10H10 and M2@B10H8 complexes (where M = Mn Fe). Electronic structure analysis Mn2B10H10 (7) shows that the metal d-orbitals stabilize interlocked boron wheel structure, forming an unprecedented geometrical pattern with Möbius aromaticity. two additional electrons in Fe2@B10H10 (8) a twisted [10]boraannulene structure. removal 2H from 7 8 leads planar structures Mn2@B10H8 (11) Fe2@B10H8 (10), respectively....
A detailed molecular orbital analysis of the metal-bis(borylene) complex [Fe(CO)3 {B(Dur)B(N(SiMe3 )2 )}] (Dur=2,3,5,6-tetramethylphenyl) (1 a) serves as a focal point recent developments in this area chemistry, such B-B coupling and catenation reactions. There is strong π delocalization between Fe(CO)3 (B-Dur)(B-N(SiMe3 ) units; short distance 1 due to delocalization. The π-donor ligand N(SiMe3 on boron provides decisive stability a. LUMO has σ-bonding character. Hence facilitated by...
A theoretical analysis of [L]M(μ-CCR)2M[L] and [L]M(μ-RC4R)M[L], where M represents the selected elements from main group, transition metals, lanthanides actinides, shows how central (μ-CCR)2 (μ-RC4R) units reorganize as traverses across periodic table. In this context metal actinide complexes are similar in nature, while lanthanide group show similarity. The ground state electronic configuration thus oxidation control these striking differences. An effective way to stabilize (iii) thorium a...
A theoretical analysis of reductive coupling isocyanide and CO mediated by a Cr–Cr quintuple bonded complex B–B multiple complexes shows how the difference in donor–acceptor capability ligands controls product distributions. In case CO, is unable to show C–C due high π- back bonding possibility reaction follows singlet potential energy surface throughout, whereas, isocyanide, less allows reactions undergo spin transition gives series products with different multiplicities. Similarly,...
Closo-carborane anions are prominent, whereas the cations of same less abundant in literature. As these ions have similar size and weakly coordinating, ionic liquids two could important applications many areas chemistry. In view limited number polyhedral carborane available, we revisited rearrangement dicarboranyl methyl cation (7-CH2 7,9-nido-C2 B9 H10+ ) using ab initio molecular dynamics calculations with metadynamics. Our simulations confirmed concerted mechanism rearrangement. We...