A5072658283- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Crystallography and molecular interactions
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Fluorine in Organic Chemistry
- Catalytic Cross-Coupling Reactions
- Asymmetric Hydrogenation and Catalysis
- Cyclopropane Reaction Mechanisms
- Carbon dioxide utilization in catalysis
- Organometallic Complex Synthesis and Catalysis
- Organoboron and organosilicon chemistry
- Synthetic Organic Chemistry Methods
University of Bath
2015-2020
A series of two-coordinate copper tert-butoxide complexes bearing five-, six-, and seven-membered ring N-heterocyclic carbenes, prepared by protonolysis (NHC)CuMes with tBuOH, have been used as catalytic precursors in the semihydrogenation alkynes silanes/tBuOH hydroboration HBPin. Both processes proceed high regioselectivity show enhancements six- carbenes.
Abstract The efficient and highly selective room temperature hydrodefluorination (HDF) of fluoroarenes by the trans‐[Ru(IMe 4 ) H 2 ] catalyst, 3 , is reported. Mechanistic studies show acts directly in catalysis without any ligand dissociation DFT calculations indicate a concerted nucleophilic attack mechanism. fully account for observed selectivities which corroborate earlier predictions regarding selectivity HDF.
Relativistic DFT calculations rationalise hydride NMR chemical shifts in a range of Ru complexes.
The all-trans isomer of Ru(IMe4)2(PPh3)2H2 (ttt-4; IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) reacts with C6F6 at 70 °C to afford the hydride fluoride complex Ru(IMe4)2(PPh3)2HF (ttt-6). At room temperature, ttt-6 Et3SiH give a mixture products, one which is assigned as silyl trihydride Ru(IMe4)2(PPh3)(SiEt3)H3 (8) by comparison isolated and structurally characterized analogue Ru(IMe4)2(PPh3)(SiPh3)H3 (9). As ttt-4 was re-formed cleanly upon heating Et3SiH, it tested in catalytic...
Multiple catalytic hydrodefluorination steps take place with the<italic>trans</italic>-dihydride complex [Ru(IEt<sub>2</sub>Me<sub>2</sub>)<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>H<sub>2</sub>] (<bold>1</bold>), taking C<sub>6</sub>F<sub>6</sub>to tri-, di- and mono-fluorobenzenes.
The major product of the reaction between Ru(IMe4)2(PPh3)2H2 (1; IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) and P(C6F5)3 (PCF) is five-coordinate complex Ru(IMe4)2(PF2{C6F5})(C6F5)H (2), which formed via a series C–F/P–C bond cleavage P–F formation steps. In contrast, hydrodefluorination all six ortho C–F bonds in PCF occurs with Ru(PPh3)4H2 to afford Ru(PPh3)3HF (3). NaBArF4 abstracted fluoride ligand 3 give [Ru({η6-C6H5}PPh2)(PPh3)2H][BArF4], while B2pin2 reacted C6D6 yield mixture...
The efficient and highly selective room temperature hydrodefluorination (HDF) of fluoroarenes by the trans-[Ru(IMe4)4H2] catalyst, 3, is reported. Mechanistic studies show 3 acts directly in catalysis without any ligand dissociation DFT calculations indicate a concerted nucleophilic attack mechanism. fully account for observed selectivities which corroborate earlier predictions regarding selectivity HDF.
C-O bond activation of DPEphos occurs upon mild heating in the presence [Ru(NHC)