612-00-0Relevant articles and documents
Adams et al.
, p. 930 (1978)
Mechanistic insight on the hydrogenation of conjugated alkenes with H 2 catalyzed by early main-group metal catalysts
Zeng, Guixiang,Li, Shuhua
, p. 3361 - 3369 (2010)
Density functional theory calculations have been performed to investigate the molecular mechanism of the hydrogenation reactions of 1,1-diphenylethylene and myrcene catalyzed by the actual calcium hydride catalyst, CaH(dipp-nacnac)(thf) (dipp-nacnac = CH{
Complexes between lithium cation and diphenylalkanes in the gas phase: The pincer effect
Gal, Jean-Francois,Maria, Pierre-Charles,Mo, Otilia,Yanez, Manuel,Kuck, Dietmar
, p. 7676 - 7683 (2006)
The gas-phase lithium cation basicities (LCB values, Gibbs free energies of binding) of α,ω)-diphenylal-kanes Ph-(CH2) n-Ph (n = 2, 3, or 7) and 1,1-diphenylethane Ph-CH(Me)-Ph were investigated by means of Fourier-transform ion cyclotron resonance (FTICR) mass spectrometry. Their structures, and those of the corresponding Li+ complexes were optimized at the B3LYP/6-31G(d) level and their relative stabilities calculated at the B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d) level. Whereas the most stable conformers of the free diphenylalkanes were found to adopt a completely stretched aliphatic chain connecting the two benzene rings, the most stable Li+ complexes correspond to conformers in which the alkali metal cation interacts simultaneously with both benzene rings through the folding of the aliphatic chain ("pincer effect"). This chelation brings about a significant enhancement of the Li+ binding enthalpies (LBE values), which were calculated to be approximately 75 kJ mor-1 higher than those evaluated for conventional (singly coordinated) π complexes in which the metal cation interacts with only one of the benzene rings. The increase of the corresponding lithium cation basicities, however, (Gibbs free energies of Li+ binding, LCB values) was calculated to be smaller by approximately 15 kJ mol-1 as the pincer effect is entropically disfavored. The good agreement between the calculated LCB values, assuming a statistical distribution of the different conformers present in the gas phase, and the experimental LCB values measured by means of FTICR mass spectrometry are considered indirect evidence of the existence of the pincer effect.
A facile and versatile electro-reductive system for hydrodefunctionalization under ambient conditions
Huang, Binbin,Guo, Lin,Xia, Wujiong
, p. 2095 - 2103 (2021/03/26)
A general electrochemical system for reductive hydrodefunctionalization is described, employing the inexpensive and easily available triethylamine (Et3N) as a sacrificial reductant. This protocol is characterized by facile operation, sustainable conditions, and exceptionally wide substrate scope covering the cleavage of C-halogen, N-S, N-C, O-S, O-C, C-C and C-N bonds. Notably, the selectivity and capability of reduction can be conveniently switched by simple incorporation or removal of an alcohol as a co-solvent.
Hydrolysis of B2pin2 over Pd/C Catalyst: High Efficiency, Mechanism, and in situ Tandem Reaction
Li, Ning,Shen, Jialu,Liu, Xiang
supporting information, p. 2797 - 2800 (2021/02/16)
A facile and effective synthesis of H2 or D2 from Pd/C catalyzed hydrolysis of B2pin2 has first been developed. Among them, B2pin2 is frequently used for borylation reaction, and has rarely been used for hydrogen evolution. The kinetic isotope effects (KIEs) and tandem reaction for diphenylacetylene and norbornene hydrogenation have confirmed both two H atoms of H2 gas are provided from H2O. This is contrary to other boron compounds hydrolysis (including NH3BH3, NaBH4), which generates H2 with only one H atom provided by water and the other one by boron compounds. Note that the hydrolysis of B2pin2 in D2O also provides an easy and useful synthesis of D2.