2022
DOI: 10.1002/chem.202200275
|View full text |Cite
|
Sign up to set email alerts
|

Tricyanoborane‐Functionalized Anionic N‐Heterocyclic Carbenes: Adjustment of Charge and Stereo‐Electronic Properties

Abstract: The 1-methyl-3-(tricyanoborane)imidazolin-2-ylidenate anion (2) was obtained in high yield by deprotonation of the B(CN) 3 -methylimidazole adduct 1. Regarding charge and stereo-electronic properties, anion 2 closes the gap between well-known neutral NHCs and the ditopic dianionic NHC, the 1,3-bis(tricyanoborane)imidazolin-2-ylidenate dianion (IIb). The influence of the number of N-bonded tricyanoborane moieties on the σ-donating and π-accepting properties of NHCs was assessed by quantum chemical calculations … Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
1
1
1

Citation Types

3
29
0
16

Year Published

2022
2022
2023
2023

Publication Types

Select...
6

Relationship

5
1

Authors

Journals

citations
Cited by 12 publications
(53 citation statements)
references
References 90 publications
3
29
0
16
Order By: Relevance
“…The 1 J ( 77 Se, 13 C) coupling constant of 7 of 209.9 Hz was derived from the 13 C{ 1 H} NMR spectrum (Figure 5). This coupling constant is significantly smaller than values reported for selenium adducts of related neutral and anionic NHCs [228.0 Hz for the Se adduct of IMeB(CN) 3 − ( IV ); 214.5 Hz for the Se adduct of IB(CN) 3 2− ( III ); [20] 219 Hz for the Se adduct of SIMes [32] (SIMes=1,3‐bis(mesityl)imidazolidin‐2‐ylidene)]. So, Ani‐cAAC‐B(CN) 3 should be a very potent σ‐donor in agreement to the comparably high calculated HOMO energy (Figure 4).…”
Section: Resultsmentioning
confidence: 57%
See 2 more Smart Citations
“…The 1 J ( 77 Se, 13 C) coupling constant of 7 of 209.9 Hz was derived from the 13 C{ 1 H} NMR spectrum (Figure 5). This coupling constant is significantly smaller than values reported for selenium adducts of related neutral and anionic NHCs [228.0 Hz for the Se adduct of IMeB(CN) 3 − ( IV ); 214.5 Hz for the Se adduct of IB(CN) 3 2− ( III ); [20] 219 Hz for the Se adduct of SIMes [32] (SIMes=1,3‐bis(mesityl)imidazolidin‐2‐ylidene)]. So, Ani‐cAAC‐B(CN) 3 should be a very potent σ‐donor in agreement to the comparably high calculated HOMO energy (Figure 4).…”
Section: Resultsmentioning
confidence: 57%
“…A similar behavior was observed by us for related imidazoline-2-ylidenates with one or two B(CN) 3 groups at nitrogen, previously. [20] The σ-orbital (HOMO) is significantly raised by the C 2 F 5 BF 2 group because of the reduced Lewis acidity of this group compared to B(CN) 3 , which is also reflected by the fluoride ion affinities (FIA) of 362 and 540 kJ mol À 1 of C 2 F 5 BF 2 [30] and B(CN) 3 . [15] Thus, Ani-cAAC-B(CN) 3 is predicted to be an excellent π-acceptor, while Ani-cAAC-C 2 F 5 BF 2 (6) should be a potent σdonor.…”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…B. 217.0(6) pm in 2 ${_\infty ^2 }$ [LiIMeB(CN) 3 ⋅THF] [20] . Die Bindungslängen und ‐winkel in 6 unterscheiden sich von denen in 4 .…”
Section: Ergebnisse Und Diskussionunclassified
“…During our studies on Lewis acids and Lewis acid/base adducts over the last few years 9,14,30–32 we became interested in the stereo-electronic properties of Lewis acids, which specifically include the steric properties of Lewis acids and their influence on the formation of Lewis acid/base adducts. Herein we present an easy-to-apply model we developed over the last few years to estimate the steric properties of Lewis acids without accounting for electronic factors or different electronic interaction models.…”
Section: Introductionmentioning
confidence: 99%