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The thiourea hydrogen bonds to the nitro group and stabilizes the incoming negative charge, while the amine acts a specific base to activate the nucleophile. This is an example of bifunctional catalysis. Hydrogen-bond catalysis is a type of organocatalysis that relies on use of hydrogen bonding interactions to accelerate and control organic ...
Thioureas are often found to be stronger hydrogen-bond donors (i.e., more acidic) than ureas [7] because their amino groups are more positively charged. Quantum chemical analyses revealed that this counterintuitive phenomenon, which is not explainable by the relative electronegativities of O and S, results from the effective steric size of the ...
Hydrogen bond: A hydrogen bond is a specific type of dipole-dipole interaction between a partially positive hydrogen atom and a partially negative electron donor that contain a pair of electrons such as oxygen, fluorine and nitrogen. The strength of hydrogen bond depends on the chemical nature and geometric arrangement of each group.
Researchers have since conducted increasingly detailed investigations of the triad's exact catalytic mechanism. Of particular contention in the 1990s and 2000s was whether low-barrier hydrogen bonding contributed to catalysis, [18] [19] [20] or whether ordinary hydrogen bonding is sufficient to explain the mechanism.
A true proposal of a covalent catalysis (where the barrier is lower than the corresponding barrier in solution) would require, for example, a partial covalent bond to the transition state by an enzyme group (e.g., a very strong hydrogen bond), and such effects do not contribute significantly to catalysis.
At shorter distances, the barrier between the two energy minima is low enough that the hydrogen is equally bound as a low-barrier, or single-well hydrogen bond. A Low-barrier hydrogen bond (LBHB) is a special type of hydrogen bond. LBHBs can occur when the pKa of the two heteroatoms are closely matched, which allows the hydrogen to be more ...
The term agostic is reserved to describe two-electron, three-center bonding interactions between carbon, hydrogen, and a metal. Two-electron three-center bonding is clearly implicated in the complexation of H 2, e.g., in W(CO) 3 (PCy 3) 2 H 2, which is closely related to the agostic complex shown in the figure. [8]
Other mechanistic possibilities not involving direct C–H bond cleavage by the metal include (i) generation of arylmetal species by electrophilic aromatic substitution mechanism (common for electrophilic Pd, Pt, Au, Hg species), (ii) cleavage of the C–H bond via hydrogen atom abstraction by an O- or N-centered radical, which may then go on ...