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Small Molecule Activation with Intramolecular 'Inverse' Frustrated Lewis Pairs
- Source :
- Chemistry – A European Journal. 27:6263-6273
- Publication Year :
- 2021
- Publisher :
- Wiley, 2021.
-
Abstract
- The intramolecular "inverse" frustrated Lewis pairs (FLPs) of general formula 1-BR2 -2-[(Me2 N)2 C=N]-C6 H4 (3-6) [BR2 =BMes2 (3), BC12 H8 , (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-BR2 )-2-[(Me2 N)2 C=NH]-C6 H4 (R=Ph, H) and reacted with ammonia, BnNH2 and pyrrolidine, to generate the FLP adducts 1-(R2 HN→BR2 )-2-[(Me2 N)2 C=NH]-C6 H4 , 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 H2 CO, PhCHO and PhNCO to form cyclic zwitterionic guanidinium borates in excellent yields. Likewise, 5 is capable of cleaving H2 , HBPin and PhSiH3 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.
- Subjects :
- chemistry.chemical_classification
Double bond
010405 organic chemistry
Stereochemistry
Chemistry
Organic Chemistry
Boranes
General Chemistry
Nuclear magnetic resonance spectroscopy
Borane
010402 general chemistry
01 natural sciences
Catalysis
Frustrated Lewis pair
Pyrrolidine
0104 chemical sciences
Adduct
chemistry.chemical_compound
Intramolecular force
Subjects
Details
- ISSN :
- 15213765 and 09476539
- Volume :
- 27
- Database :
- OpenAIRE
- Journal :
- Chemistry – A European Journal
- Accession number :
- edsair.doi.dedup.....b5dfc91c36d2f091bde233f76b3d85d7