Investigating Tetrel based Neutral Frustrated Lewis Pairs for Hydrogen Activation DOI Creative Commons
Pallavi Sarkar, Shubhajit Das, Swapan K. Pati

et al.

Published: June 28, 2021

Tetrel Lewis acids are a prospective alternative to commonly employed neutral boranes in frustrated pair (FLP) chemistry. While cationic tetrylium acids, being isolobal and iso(valence)electronic, natural replacement boranes, tetrel allude as less trivial options due the absence of formally empty p orbital on acceptor centre. Recently series intramolecular geminal FLPs (C2F5)3E-CH2-P(tBu)2 (E= Si, Ge, Sn) featuring atoms site, were reported for activation small molecules including H2. In this work, through density functional theory computations, we elucidate general mechanistic picture H2 by family FLPs. Our findings reveal that atom derives required acidity utilizing antibonding orbitals its adjacent bonds with individual contributions depending identity donor atoms. By varying acid base attached substituents, unravel their interplay energetics activation. We find switching site from P N significantly affects synchronous nature bond breaking/formations along reaction pathway result, N-bearing have more favourable profile than those P. results quantitatively discussed detail within framework Activation Strain Model reactivity Energy Decomposition Analysis method. Finally, reductive elimination decomposition route pertinent plausible extension catalytic hydrogenation these is also examined

Language: Английский

Recent Advances in Group 14 and 15 Lewis Acids for Frustrated Lewis Pair Chemistry DOI
Pallavi Sarkar, Shubhajit Das, Swapan K. Pati

et al.

Chemistry - An Asian Journal, Journal Year: 2022, Volume and Issue: 17(10)

Published: March 23, 2022

Frustrated Lewis pairs (FLP) which rely on the cooperative action of acids and bases, played a prominent role in advancement main-group catalysis. While early days FLP chemistry witnessed dominance boranes, there is growing body reports alternative derived from groups 14 15. This short review focuses discovery such non-boron candidates reported since 2015.

Language: Английский

Citations

13
Dynamic Covalent Optical Chirality Sensing with a Sterically Encumbered Aminoborane DOI Creative Commons
Zeus A. De los Santos, Ciarán C. Lynch, Christian Wolf

et al.

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(61)

Published: July 7, 2022

A sterically encumbered aminoborane sensor is introduced and used for quantitative stereochemical analysis of monoalcohols, diols amino alcohols. The small-molecule probe exhibits a rigid ortho-substituted arene scaffold with proximate boron binding site triarylamine circular dichroism (CD) reporter unit which proved to be crucial the observed chiroptical signal induction. Coordination chiral target molecule produces strong Cotton effects UV changes that are readily correlated its absolute configuration, enantiomeric composition concentration achieve comprehensive within 5 % error margin. sensing method was successfully applied in chromatography-free less than one milligram crude asymmetric reaction mixture advantages this approach, amenable high-throughput experimentation equipment automation, over traditional methods discussed.

Language: Английский

Citations

11
The Reactivity of Isomeric Nitrenium Lewis Acids with Phosphines, Carbenes, and Phosphide DOI

Diya Zhu,

Zheng‐Wang Qu, Jiliang Zhou

et al.

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 27(8), P. 2861 - 2867

Published: Nov. 2, 2020

Alkylation of spiro[fluorene-9,3'-indazole] at N(1) and N(2) with tBuCl affords the nitrenium cations [C

Language: Английский

Citations

15
Assessing Combinations of B(C6F5)3 and N2‐Derived Molybdenum Nitrido Complexes for Heterolytic Bond Activation DOI Creative Commons

Anaïs Coffinet,

David Specklin, Quentin Le Dé

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(26)

Published: Feb. 20, 2023

Two different dinitrogen-derived molybdenum nitrido complexes varying by their geometry, ligand spheres and oxidations states were shown to engage N in dative bonding with the strong Lewis acid B(C6 F5 )3 . The stable adducts assessed for frustrated pair-type heterolytic E-H bond splitting of hydrosilanes (E=Si) HB(C6 )2 Whereas Si-H activation was achieved, substitute a quantitative or equilibrated fashion, depending on nature complex. No B-H observed. Thermodynamics these reactions, computed DFT, are agreement experimental outcomes.

Language: Английский

Citations

4
Nitrenium Salts in Intramolecular Lewis Pairs DOI Creative Commons
Idan Avigdori, Kuldeep Singh,

Alla Pogoreltsev

et al.

Zeitschrift für anorganische und allgemeine Chemie, Journal Year: 2022, Volume and Issue: 649(4)

Published: Nov. 29, 2022

Abstract Herein we present the synthesis, full characterization and systematic investigation of intramolecular Lewis pairs incorporating acidic N‐heterocyclic nitrenium salts linked to phosphine bases. Intramolecular adducts frustrated (FLPs) were obtained, depending on different modification molecular structure. Several aryl alkyl groups utilized as substituents core naphthotriazinium components, which by an chain variable length. Whereas intermolecular adduct with a relatively weak donor (Ph 2 PMe) was not observed, corresponding version PR) detected both in dissociated pair form coordinated simultaneously. Additionally, one set modifications led unique rearrangement core, resulting fused heterocycle. The mechanism this analyzed computationally.

Language: Английский

Citations

4
Triazenolysis of Alkenes: Aza-version of Ozonolysis DOI Creative Commons
Alexander N. Koronatov, Pavel А. Sakharov,

Alexander Kaushansky

et al.

Published: Oct. 10, 2023

Numerous applications of alkenes exist due to their abundance and versatility in chemical transformations. In this study, we present a unique novel transformation alkenes, the aza-version canonical ozonolysis reaction, which termed as triazenolysis. This process offers non-trivial previously unfeasible synthetic disconnection, allowing cleavage C=C double bond into two new C-N bonds reductive manner. We carefully examined applicability finding that diverse cyclic are suitable for developed process. Furthermore, an example acyclic alkene, illustrating potential expanding triazenolysis other counterparts. Through DFT calculations, explored mechanism key step demonstrated significance Lewis acid catalysis achieving desired transformation.

Language: Английский

Citations

2
New generation of nitrenium salts: catalytic hydrosilylation of imines and a mechanism of action of nitrogen Lewis acids DOI Creative Commons
Kuldeep Singh, Idan Avigdori,

Alexander Kaushansky

et al.

Published: March 29, 2022

Nitrogen Lewis acids (NLAs) are emerging as a powerful tool in strong bond activation and catalysis. Till now, N,N-dialkyl-nitrenium salts were known utilized chemical transformations. In this article, we report on the synthesis characterization of new generation nitrenium-based – N,N-diaryl-substituted naphthotriazinium salts, which open door to libraries stereoelectronically modifiable catalysts. We exemplify potency these acidic catalysts gram-scale hydrosilylation various ketimines aldimines yields up 99% catalyst loading low 0.1mol%. Notably, dialkyl-nitrenium proved inefficient reaction. Based our experimental theoretical studies, elucidated, for first time, mechanistic action nitrenium such reduction-type reactions, demonstrating unique hydridic behavior N-H bonds triazanes.

Language: Английский

Citations

0
Investigating Tetrel based Neutral Frustrated Lewis Pairs for Hydrogen Activation DOI Creative Commons
Pallavi Sarkar, Shubhajit Das, Swapan K. Pati

et al.

Published: June 28, 2021

Tetrel Lewis acids are a prospective alternative to commonly employed neutral boranes in frustrated pair (FLP) chemistry. While cationic tetrylium acids, being isolobal and iso(valence)electronic, natural replacement boranes, tetrel allude as less trivial options due the absence of formally empty p orbital on acceptor centre. Recently series intramolecular geminal FLPs (C2F5)3E-CH2-P(tBu)2 (E= Si, Ge, Sn) featuring atoms site, were reported for activation small molecules including H2. In this work, through density functional theory computations, we elucidate general mechanistic picture H2 by family FLPs. Our findings reveal that atom derives required acidity utilizing antibonding orbitals its adjacent bonds with individual contributions depending identity donor atoms. By varying acid base attached substituents, unravel their interplay energetics activation. We find switching site from P N significantly affects synchronous nature bond breaking/formations along reaction pathway result, N-bearing have more favourable profile than those P. results quantitatively discussed detail within framework Activation Strain Model reactivity Energy Decomposition Analysis method. Finally, reductive elimination decomposition route pertinent plausible extension catalytic hydrogenation these is also examined

Language: Английский

Citations

0
Investigating Tetrel based Neutral Frustrated Lewis Pairs for Hydrogen Activation DOI Creative Commons
Pallavi Sarkar, Shubhajit Das, Swapan K. Pati

et al.

Published: June 28, 2021

Tetrel Lewis acids are a prospective alternative to commonly employed neutral boranes in frustrated pair (FLP) chemistry. While cationic tetrylium acids, being isolobal and iso(valence)electronic, natural replacement boranes, tetrel allude as less trivial options due the absence of formally empty p orbital on acceptor centre. Recently series intramolecular geminal FLPs (C2F5)3E-CH2-P(tBu)2 (E= Si, Ge, Sn) featuring atoms site, were reported for activation small molecules including H2. In this work, through density functional theory computations, we elucidate general mechanistic picture H2 by family FLPs. Our findings reveal that atom derives required acidity utilizing antibonding orbitals its adjacent bonds with individual contributions depending identity donor atoms. By varying acid base attached substituents, unravel their interplay energetics activation. We find switching site from P N significantly affects synchronous nature bond breaking/formations along reaction pathway result, N-bearing have more favourable profile than those P. results quantitatively discussed detail within framework Activation Strain Model reactivity Energy Decomposition Analysis method. Finally, reductive elimination decomposition route pertinent plausible extension catalytic hydrogenation these is also examined

Language: Английский

Citations

0