Structural variation, dynamics, and catalytic application of palladium(II) complexes of di-N-heterocyclic carbene-amine ligands

A series of palladium(II) complexes incorporating di-NHC-amine ligands has been prepared and their structural, dynamic and catalytic behaviour investigated. The complexes [trans-(k(2)-(CN)-C-tBu(Bn)CN(Bn)C-tBu)PdCl2] (12) and [trans-(kappa(2)-(CN)-C-Mes(H)C-Mes)PdCl2] (13) do not exhibit interaction between the amine nitrogen and palladium atom respectively. NMR spectroscopy between - 40 and 25 degrees C shows that the di-NHC-amine ligand is flexible expressing C-s symmetry and for 13 rotation of the mesityl groups is prevented. In the related C-1 complex [(kappa(3)-(CN)-C-tBu(H)C-tBu)PdCl][CI] (14) coordination of NHC moieties and amine nitrogen atom is observed between -40 and 25 degrees C. Reaction between 12 - 14 and two equivalents of AgBF4 in acetonitrile gives the analogous complexes [trans-(kappa(2)-(CN)-C-tBu(Bn)C-tBu)PdCl2] (12) and [trans-(kappa(CN)-C-2Mes(H)C-Mes)PdCl2] (13) do not exhibit interaction between the amine nitrogen and palladium atom respectively. NMR spectroscopy between -40 ans 25 degrees C shows the di-NHC-amine ligand is flexible expressing C-s symmetry and for 13 rotation of the mesityl groups is prevented. In the related C-1 complex [kappa(3)-(CN)-C-tBu(H)C-tBu)PdCI][CI] (14) coordination of NHC moieties and amine nitrogen atom is observed between -40 and 25 degrees C.Reaction between 12-14 and two equivalents of AgBF4 in acetonitrile gives the analogous complexes [trans-(kappa(2)-(CN)-C-tBu(H)(CPd)-Pd-tBu(MeCN)(2)][BF4](2) (15), [trans-(kappa(CN)-C-2Mes(H)C-Mes)Pd(MeCN)(2)[BF4](2 (16)) and [(kappa(3)-(CN)-C-tBu(H)C-tBu)Pd(MeCN)][BF4](2) (17) indicating that ligand structure determines amine coordination. The single crystal X-ray structures of 12, 17 and two ligand imidazolium salt precursors C-tBu(H)N(Bn)C(H) (tBu)][CI](2) (2) and [C-tBu(H) N(H)C(H)(tBu)][BPh4](2) (4) have been determined. Complexes 12-14 and 15-17 have been shown to be active precatalysts for Heck and hydroamination reactions respectively

Cross-Dehydrogenative Couplings between Indoles and β-Keto Esters : Ligand-Assisted Ligand Tautomerization and Dehydrogenation via a Proton-Assisted Electron Transfer to Pd(II)

Cross-dehydrogenative coupling reactions between -ketoesters and electron-rich arenes, such as indoles, proceed with high regiochemical fidelity with a range of -ketoesters and indoles. The mechanism of the reaction between a prototypical -ketoester, ethyl 2-oxocyclopentanonecarboxylate and N-methylindole, has been studied experimentally by monitoring the temporal course of the reaction by 1H NMR, kinetic isotope effect studies, and control experiments. DFT calculations have been carried out using a dispersion-corrected range-separated hybrid functional (B97X-D) to explore the basic elementary steps of the catalytic cycle. The experimental results indicate that the reaction proceeds via two catalytic cycles. Cycle A, the dehydrogenation cycle, produces an enone intermediate. The dehydrogenation is assisted by N-methylindole, which acts as a ligand for Pd(II). The compu-tational studies agree with this conclusion, and identify the turnover-limiting step of the dehydrogenation step, which involves a change in the coordination mode of the -keto ester ligand from an O,O’-chelate to an C-bound Pd enolate. This ligand tautom-erization event is assisted by the -bound indole ligand. Subsequent scission of the ’-C–H bond takes place via a proton-assisted electron transfer mechanism, where Pd(II) acts as an electron sink and the trifluoroacetate ligand acts as a proton acceptor, to pro-duce the Pd(0) complex of the enone intermediate. The coupling is completed in cycle B, where the enone is coupled with indole. Pd(TFA)2 and TFA-catalyzed pathways were examined experimentally and computationally for this cycle, and both were found to be viable routes for the coupling step