2018
DOI: 10.1002/chem.201705992
|View full text |Cite
|
Sign up to set email alerts
|

Further Development of Weakly Coordinating Cations: Fluorinated Bis(triarylphosphoranylidene)iminium Salts

Abstract: So far unknown bis(triarylphosphoranylidene)iminium cations [PPN] with one fluorine atom in para ([PPN-1 ] ), two in meta ([PPN-2 ] ), or three in para and meta positions of the phenyl rings ([PPN-3 ] ) were obtained by a newly developed one-pot reaction. These halogenated [PPN] cations were characterized by IR and Raman spectroscopy in comparison with quantum-chemical calculations, ESI mass spectrometry, NMR spectroscopy, and single-crystal X-ray diffraction. To assess their quality as weakly coordinating cat… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
1
1
1

Citation Types

0
11
0

Year Published

2018
2018
2022
2022

Publication Types

Select...
7

Relationship

1
6

Authors

Journals

citations
Cited by 10 publications
(11 citation statements)
references
References 50 publications
0
11
0
Order By: Relevance
“…Thus, bulky cations with high charge distribution also favor ion separation, which may stabilize reactive anions leading to higher reactivity in catalytic applications. [48,49] The higher reactivity of 2 b compared to 2 a in the insertion of benzaldehyde into the BÀ H bond may possibly be explained similarly. The cation in 2 b is significantly more sterically demanding due to the additional CF 3 groups in the imino phenolate ligands.…”
Section: Hydrosilylation Of Aldehydes Catalyzed By 2 a And 2 Bmentioning
confidence: 99%
“…Thus, bulky cations with high charge distribution also favor ion separation, which may stabilize reactive anions leading to higher reactivity in catalytic applications. [48,49] The higher reactivity of 2 b compared to 2 a in the insertion of benzaldehyde into the BÀ H bond may possibly be explained similarly. The cation in 2 b is significantly more sterically demanding due to the additional CF 3 groups in the imino phenolate ligands.…”
Section: Hydrosilylation Of Aldehydes Catalyzed By 2 a And 2 Bmentioning
confidence: 99%
“…Even less F-substituted arylxenon derivatives (Aryl = 2,6-F 2 C 6 H 3 , 2-FC 6 H 4 , 4-FC 6 H 4 ) were found to be stable at temperatures slightly below 0 • C, when inert tetrafluoroborate [BF 4 ] − was used as a counterion (Naumann et al, 1993). In our case, we should look for bulky weakly coordinating cations ["weakly coordinating cations" is a rather recent concept complementary to the much older concept of "weakly coordinating anions"; see, for example (Price et al, 2009;Fischer et al, 2014;Moritz et al, 2015;Mann et al, 2018)], which do not contain any nucleophilic site that can attack the B-NG bond. Preferentially, we need to find a chemically inert, symmetric, bulky, and rigid cationic species that will be able to reliably separate [B 12 X 11 NG] − anions from each other in the solid phase.…”
Section: On the Way To Bulk Salts Of The Anionic Ng Derivativesmentioning
confidence: 99%
“…As already mentioned [(C 6 H 5 ) 3 PBr][Br 7 ] was obtained by the reaction of triphenylphosphine with 5 equivalents of elemental bromine in the eutectic mixture of ionic liquids [C 10 MPyr]Br (C 10 MPyr = N-decyl-N-methylpyrrolidinium) and [C 4 MPyr][OTf ] (C 4 MPyr = N-butyl-N-methylpyrrolidinium; OTf = triflate). [11] In a similar approach but without using ionic liquids as a solvent we performed our reactions in neat bromine.…”
Section: Polybromide Dianion [Br 14 ] 2-stabilized By [(C 6 H 5 ) 3 Pmentioning
confidence: 99%
“…Besides, the amount of bromine, the structural motif depends especially on the employed cation. [10] This class of fluorinated weakly coordinating cations has not yet been used for the preparation of polyhalide systems. [7,8] Therefore the size of the polybromide anion and its properties can be drastically influenced by the cation.…”
Section: Introductionmentioning
confidence: 99%