Search

A dicationic diradical has been synthesized from the N,N′- trans-1,4-cyclohexylene bridged bis-NHC–CAAC dimer.

Herein, a new type of carbodicarbene (CDC) comprising two different classes of carbenes is reported; NHC and CAAC as donor substituents and compare the molecular structure and coordination to Au(I)Cl to those of NHC-only and CAAC-only analogues. The conjugate acids of these three CDCs exhibit notable redox properties. Their reactions with [NO][SbF6] were investigated. The reduction of the conjugate acid of CAAC-only based CDC with KC8 results in the formation of hydrogen abstracted/eliminated products, which proceed through a neutral radical intermediate, detected by EPR spectroscopy. In contrast, the reduction of conjugate acids of NHC-only and NHC/CAAC based CDCs led to intermolecular reductive (reversible) carbon–carbon sigma bond formation. The resulting relatively elongated carbon–carbon sigma bonds were found to be readily oxidized. They were, thus, demonstrated to be potent reducing agents, underlining their potential utility as organic electron donors and n-dopants in organic semiconductor molecules.

Here we report the synthesis of an N-heterocyclic carbene (NHC)-stabilised phosphinidene oxide by the controlled oxygenation of a phosphinidene under ambient conditions. This compound can be further oxygenated to a phosphinidene dioxide. The stoichiometric reduction of a phosphinidene oxide with KC8 resembles the pinacol coupling reaction–the reduction of a carbonyl compound. We also looked at the stoichiometric oxidation of NHC-coordinated phosphinidene, phosphinidene oxide and phosphinidene dioxide with [NO][SbF6].

We have studied the effect of N-substitution on the course of the reaction of imidazolium triflate. The reaction of N-heterocyclic carbene with N-tBu-substituted pyrrolinium triflate afforded 2-(pyrrolidin-2-yl)-imidazolium triflate, 3R. Treatment of 3R with potassium bis(trimethylsilyl)amide (KHMDS) leads to either the dealkylation product 4 or the deprotonation product, triazaalkene 5, depending on the N-substitution at the imidazolium moiety. Density functional studies using the B3LYP/TZVP setup have been employed to explore various pathways for the dealkylation reaction and the calculated energies support the dealkylation by a large energy margin compared to the deprotonatation process. Theoretical calculations revealed that dealkylation reaction is thermodynamically more favorable than deprotonation. The triazaalkene 5 could be oxidized by AgOTf to the corresponding radical cation 6 and dication 7 in-situ. While 6 and 7 could not be isolated, the formation of the former is inferred by electron paramagnetic resonance spectroscopy and its abstraction of a H-atom to afford 3Me. Similarly, the formation of the dication 7 is inferred by its ready elimination of isobutylene affording 8.

The synthesis of organic radicals is challenging due to their inherent instability. In recent years, cyclic(alkyl)(amino)carbene (CAAC)-derived 2-substituted pyrrolinium salts have been used as synthons for the synthesis of isolable carbon-based radicals. Herein, we report a direct, easy and convenient method for the synthesis of 2-aryl substituted pyrrolinium salts without using CAAC as a precursor. These cations can be reduced to the corresponding radicals. The influence of the aryl substituent at the C-2 position on radical stabilization and dimerization has been investigated. Because of the large scope of our strategy (capability to modulate different substituents at all the C- and N-centres of the pyrrolinium salts), it has the merit to be an extremely effective and productive route for generating carbon-based radicals whose stability as well as reactivity can be varied.

We have studied the effect of

The addition reactions of N-heterocyclic carbenes (NHCs) are mostly known to occur through the carbenic centre (C2), which leads to a "normal" adduct. Herein, we report the "abnormal" addition of NHCDip 1 (1,3-(2,6-iPr2 C6 H3 )-imidazole-2-ylidene) to a conjugate acid of cyclic (alkyl)(amino)carbene 2 (CAACiPr =1-iPr-3,3,5,5-Me4 -pyrrolinium triflate). Mechanistic study revealed that this reaction proceeded through the in situ formation of 1,3-(2,6-iPr2 C6 H3 )-imidazolium cation 4 and N-iPr-substituted CAAC 5 followed by the oxidative addition of compound 5 across the C4-H bond (alias backbone C-H) of compound 4. The in situ formation of compound 5 was also proven by the oxidative addition of it to the N-H group of iPrNH2 . DFT calculations also supported the mechanistic findings. A different methodology for the in situ generation of compound 5 by using TMPLi is also described.

Herein, the isolation and characterization of N-peralkyl-substituted NHCCAAC derived triazaalkenes in three oxidation states, neutral, radical cation, and dication, are reported. Cyclic voltammetry has shown the reversible electronic coupling between the first and second oxidation to be Delta E-1/2 = 0.50 V. As a proof-of-principle, to demonstrate the electron-rich nature of the triazaalkene, it was shown that it can be used as an electron donor in the reduction of an aryldiazonium salt to the corresponding arene.