“…Similarly, we observed that the signals corresponding to the meta and para protons in Ph 4 C ((CD 3 ) 2 CO; at ~7.29 and ~7.21 ppm, respectively) appeared up-field compared to the signals corresponding to Ph 4 Si (meta and para protons appear at ~7.44 and ~7.48 ppm, respectively; Supplementary Fig. 1 ) 31 . Fig.…”
The phenyl (Ph) group is a representative substituent in the field of organic chemistry as benzene (the parent molecule) is of fundamental importance. Simple Ph-substituted compounds of common chemical elements are well known. However, extensive structural characterization of tetraphenylammonium (Ph4N+) salts has not been reported. Herein, the synthesis of Ph4N+ salts and their characterization data including the 1H and 13C nuclear magnetic resonance (NMR) spectra and the single-crystal X-ray structure have been presented. An intermolecular radical coupling reaction between an aryl radical and a triarylammoniumyl radical cation was conducted to synthesize the target moieties. The Ph4N+ salts described herein are the simplest tetraarylammonium (Ar4N+) salts known. The results reported herein can potentially help access the otherwise inaccessible non-bridged Ar4N+ salts, a new class of rigid and sterically hindered organic cations.
“…Similarly, we observed that the signals corresponding to the meta and para protons in Ph 4 C ((CD 3 ) 2 CO; at ~7.29 and ~7.21 ppm, respectively) appeared up-field compared to the signals corresponding to Ph 4 Si (meta and para protons appear at ~7.44 and ~7.48 ppm, respectively; Supplementary Fig. 1 ) 31 . Fig.…”
The phenyl (Ph) group is a representative substituent in the field of organic chemistry as benzene (the parent molecule) is of fundamental importance. Simple Ph-substituted compounds of common chemical elements are well known. However, extensive structural characterization of tetraphenylammonium (Ph4N+) salts has not been reported. Herein, the synthesis of Ph4N+ salts and their characterization data including the 1H and 13C nuclear magnetic resonance (NMR) spectra and the single-crystal X-ray structure have been presented. An intermolecular radical coupling reaction between an aryl radical and a triarylammoniumyl radical cation was conducted to synthesize the target moieties. The Ph4N+ salts described herein are the simplest tetraarylammonium (Ar4N+) salts known. The results reported herein can potentially help access the otherwise inaccessible non-bridged Ar4N+ salts, a new class of rigid and sterically hindered organic cations.
The phenyl (Ph) group is a representative substituent in the field of organic chemistry as benzene (the parent molecule) is of fundamental importance. Simple Ph-substituted compounds of common chemical elements are well known. However, extensive structural characterization of tetraphenylammonium (Ph4N+) salts has not been reported. Herein, the synthesis of Ph4N+ salts and their characterization data including the 1H- and 13C-nuclear magnetic resonance (NMR) spectra and the single-crystal X-ray structure have been presented. An intermolecular radical coupling reaction between an aryl radical and a triarylammoniumyl radical cation was conducted to synthesize the target moieties. The Ph4N+ salts described herein are the simplest tetraarylammonium (Ar4N+) salts known. The results reported herein can potentially help access the otherwise inaccessible non-bridged Ar4N+ salts, a new class of rigid and sterically hindered organic cations.
“…Vinyl triphenyl germane was prepared according to a modified procedure that was previously reported. 27 Triphenylgermanium chloride (3.0 g, 8.8 mmol) was dissolved in 20 mL of THF. Vinylmagnesium chloride in THF (8.3 mL, 13.2 mmol, 1.5 equiv) was added dropwise to solution while stirring.…”
Section: ■ Experimental Sectionmentioning
confidence: 99%
“…Vinyl triphenyl germane was prepared according to a modified procedure that was previously reported . Triphenylgermanium chloride (3.0 g, 8.8 mmol) was dissolved in 20 mL of THF.…”
Section: Synthesis Characterization
and Reactionsmentioning
A series of Ni(0) compounds supported by electronically similar N-heterocyclic carbene (NHC) ancillary ligands with a range of %V bur were used as catalysts for aryl C− H bond silylation, germylation, and stannylation. The NHC steric bulk strongly influenced the selectivity of C−H functionalization to give new carbon−heteroatom bonds versus alkene hydroarylation, despite little structural change in the resting state of the catalysts. Studies were performed by reacting C 6 F 5 H and H 2 CCHER 3 (ER 3 = SnBu 3 , GePh 3 , SiMe 3 ) using catalytic amounts of Ni(COD) 2 and NHC ligands IPr, IMes, IBn, and i Pr 2 Im. Catalytic C−H stannylation to give C 6 F 5 SnBu 3 was facile with all ligands. The catalytic C−H germylation reaction was more difficult than stannylation but was demonstrated using H 2 CCHGePh 3 to give C 6 F 5 GePh 3 for all but the largest NHC. The bulkiest NHC, IPr, gave a 96:4 ratio of the hydroarylation product C 6 F 5 CH 2 CH 2 GePh 3 versus C 6 F 5 GePh 3 . The C−H silylation reactions required the highest temperatures and gave selective silylation product C 6 F 5 SiMe 3 only for the smallest IBn and i Pr 2 Im NHC ligands. Using the larger IMes carbene resulted in a 66:34 mixture of silylation and hydroarylation products, and the largest NHC, IPr, gave exclusive conversion to the hydroarylation product, C 6 F 5 CH 2 CH 2 SiMe 3 . DFT calculations are provided that give insight into the mechanism and key reaction steps, such as the relative difficulty of the critical β-Sn, Ge, and Si elimination steps.
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