Small Molecule Activation with Intramolecular “Inverse” Frustrated Lewis Pairs
Abstract
Abstract The intramolecular “inverse” frustrated Lewis pairs (FLPs) of general formula 1‐BR 2 ‐2‐[(Me 2 N) 2 C=N]‐C 6 H 4 ( 3 – 6 ) [BR 2 =BMes 2 ( 3 ), BC 12 H 8 , ( 4 ), BBN ( 5 ), BBNO ( 6 )] were synthesized and structurally characterized by multinuclear NMR spectroscopy and X‐ray analysis. These novel types of pre‐organized FLPs, featuring strongly basic guanidino units rigidly linked to weakly Lewis acidic boryl moieties via an ortho ‐phenylene linker, are capable of activating H−H, C−H, N−H, O−H, Si−H, B−H and C=O bonds. 4 and 5 deprotonated terminal alkynes and acetylene to form the zwitterionic borates 1‐(RC≡C‐BR 2 )‐2‐[(Me 2 N) 2 C=NH]‐C 6 H 4 (R=Ph, H) and reacted with ammonia, BnNH 2 and pyrrolidine, to generate the FLP adducts 1‐(R 2 HN→BR 2 )‐2‐[(Me 2 N) 2 C=NH]‐C 6 H 4 , where the N‐H functionality is activated by intramolecular H‐bond interactions. In addition, 5 was found to rapidly add across the double bond of H 2 CO, PhCHO and PhNCO to form cyclic zwitterionic guanidinium borates in excellent yields. Likewise, 5 is capable of cleaving H 2 , HBPin and PhSiH 3more »
- Publication Date:
- Research Org.:
- Texas Tech Univ., Lubbock, TX (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); USDOE
- OSTI Identifier:
- 1775423
- Alternate Identifier(s):
- OSTI ID: 1781959
- Grant/Contract Number:
- SC0019094; 1407681
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Volume: 27; Journal Issue: 20; Journal ID: ISSN 0947-6539
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 08 HYDROGEN; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Small molecule activation; Hydrogen cleavage; Borane; C-H bond activation; Frustrated Lewis pair; N-H bond activation
Citation Formats
Manankandayalage, Chamila, Unruh, Daniel K., and Krempner, Clemens. Small Molecule Activation with Intramolecular “Inverse” Frustrated Lewis Pairs. United States: N. p., 2021.
Web. doi:10.1002/chem.202005143.
Manankandayalage, Chamila, Unruh, Daniel K., & Krempner, Clemens. Small Molecule Activation with Intramolecular “Inverse” Frustrated Lewis Pairs. United States. https://doi.org/10.1002/chem.202005143
Manankandayalage, Chamila, Unruh, Daniel K., and Krempner, Clemens. Wed .
"Small Molecule Activation with Intramolecular “Inverse” Frustrated Lewis Pairs". United States. https://doi.org/10.1002/chem.202005143. https://www.osti.gov/servlets/purl/1775423.
@article{osti_1775423,
title = {Small Molecule Activation with Intramolecular “Inverse” Frustrated Lewis Pairs},
author = {Manankandayalage, Chamila and Unruh, Daniel K. and Krempner, Clemens},
abstractNote = {Abstract The intramolecular “inverse” frustrated Lewis pairs (FLPs) of general formula 1‐BR 2 ‐2‐[(Me 2 N) 2 C=N]‐C 6 H 4 ( 3 – 6 ) [BR 2 =BMes 2 ( 3 ), BC 12 H 8 , ( 4 ), BBN ( 5 ), BBNO ( 6 )] were synthesized and structurally characterized by multinuclear NMR spectroscopy and X‐ray analysis. These novel types of pre‐organized FLPs, featuring strongly basic guanidino units rigidly linked to weakly Lewis acidic boryl moieties via an ortho ‐phenylene linker, are capable of activating H−H, C−H, N−H, O−H, Si−H, B−H and C=O bonds. 4 and 5 deprotonated terminal alkynes and acetylene to form the zwitterionic borates 1‐(RC≡C‐BR 2 )‐2‐[(Me 2 N) 2 C=NH]‐C 6 H 4 (R=Ph, H) and reacted with ammonia, BnNH 2 and pyrrolidine, to generate the FLP adducts 1‐(R 2 HN→BR 2 )‐2‐[(Me 2 N) 2 C=NH]‐C 6 H 4 , where the N‐H functionality is activated by intramolecular H‐bond interactions. In addition, 5 was found to rapidly add across the double bond of H 2 CO, PhCHO and PhNCO to form cyclic zwitterionic guanidinium borates in excellent yields. Likewise, 5 is capable of cleaving H 2 , HBPin and PhSiH 3 to form various amino boranes. Collectively, the results demonstrate that these new types of intramolecular FLPs featuring weakly Lewis acidic boryl and strongly basic guanidino moieties are as potent as conventional intramolecular FLPs with strongly Lewis acidic units in activating small molecules.},
doi = {10.1002/chem.202005143},
journal = {Chemistry - A European Journal},
number = 20,
volume = 27,
place = {United States},
year = {Wed Feb 10 00:00:00 EST 2021},
month = {Wed Feb 10 00:00:00 EST 2021}
}
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