Towards the Preparation of Stable Cyclic Amino(ylide)Carbenes
Abstract
:1. Introduction
2. Results
2.1. Attempted Synthesis of CAYCs with Trialklyl Onium Groups
2.2. Computational Studies
3. Discussion and Conclusions
4. Materials and Methods
4.1. Crystal Structure Determination
4.2. Computational Studies
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Sample Availability: Samples of the compounds are not available from the authors. |
Structural Parameters | 11 | 12 | |
---|---|---|---|
bond length (Å) | C1–C2 | 1.358(4) | 1.379(2) |
C1-N1 | 1.358(4) | 1.364(1) | |
C2–P1 | 1.765(3) | 1.790(1) | |
P1–C29 | 1.830(3) | 1.679(1) | |
bond angle (°) | P1–C29–C30 | 110.9(2) | 122.20(10) |
P1–C29–C34 | 111.1(2) | 120.68(10) | |
C30–C29–C34 | 110.0(2) | 113.02(11) | |
∑ | 332.0(6) | 355.90(31) |
Onium Group | II (kJ/mol) | TSI→II (kJ/mol) | TSI→III (kJ/mol) | III (kJ/mol) | TSIII→IV (kJ/mol) | IV (kJ/mol) | |
---|---|---|---|---|---|---|---|
α-deprotonation | β-deprotonation | ||||||
SCy2 | −61.4 | 44.1 | 66.9 (concerted) | −239.9 | |||
SOCy2 | −61.7 | 50.6 | 102.7 (concerted) | −203.5 | |||
100.1eq | 107.4eq | 119.1eq | |||||
PCy3 | −59.9 | 57.5 | 134.4 (concerted) | −106.0 | |||
115.6eq | 98.9eq | 176.2eq | |||||
80.7ax | 81.2ax | 90.4ax | |||||
SMe2 | −52.2 | 54.8 | – | ||||
SOMe2 | −85.0 | 60.3 | – | ||||
PMe3 | −53.9 | 56.5 | – | ||||
StBu2 | – | 54.0 (concerted) | −236.3 | ||||
SOtBu2 | – | 35.9 (concerted) | −248.0 | ||||
PtBu3 | – | 71.1 | 40.9 | 58.5 | −185.5 | ||
SAd2 | – | 123.7 | −8.3 | ||||
SOAd2 | – | 102.4 | 7.4 | ||||
PAd3 | – | 91.6 | 91.2 | 108.4 | 47.1 | ||
S(CH2)2 | – | 38.0a | −48.6 a | −40.4 a | −275.0 | ||
S(CH2)3 | −11.9 | 65.5 | 105.0 | 75.4 | 83.0 | −238.8 | |
S(CH2)4 | −33.6 | 56.7 | 90.5 (concerted) | −180.0 |
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Steinert, H.; Schwarz, C.; Kroll, A.; Gessner, V.H. Towards the Preparation of Stable Cyclic Amino(ylide)Carbenes. Molecules 2020, 25, 796. https://doi.org/10.3390/molecules25040796
Steinert H, Schwarz C, Kroll A, Gessner VH. Towards the Preparation of Stable Cyclic Amino(ylide)Carbenes. Molecules. 2020; 25(4):796. https://doi.org/10.3390/molecules25040796
Chicago/Turabian StyleSteinert, Henning, Christopher Schwarz, Alexander Kroll, and Viktoria H. Gessner. 2020. "Towards the Preparation of Stable Cyclic Amino(ylide)Carbenes" Molecules 25, no. 4: 796. https://doi.org/10.3390/molecules25040796