The intramolecular alpha-arylation of aldehydes via organo-SOMO catalysis was investigated using density functional theory (B3LYP and M06-2X functionals). The geometries, spin densities, Mulliken charges, and molecular orbitals of the reacting enamine radical cations were analyzed, and the nature of the resulting cyclized radical cation intermediates was characterized. In agreement with experim...

Catalytic dehydrogenation of ammonia-borane (NH(3)·BH(3), AB) and dimethylamine borane (NHMe(2)·BH(3), DMAB) by the Pd(II) complex [((tBu)PCP)Pd(H(2)O)]PF(6) [(tBu)PCP = 2,6-C(6)H(3)(CH(2)P(t)Bu(2))(2)] leads to oligomerization and formation of spent fuels of general formula cyclo-[BH(2)-NR(2)](n) (n = 2,3; R = H, Me) as reaction byproducts, while one equivalent of H(2) is released per amine-bo...

Amidines are special nitrogen analogues of the carboxylic acid, containing two N of different functionality. One is formally single bonded like-amino nitrogen (N) and the other is a formally double-bonded imino nitrogen (N), where protonation occurs first. The pKa’s of amidines vary from neutral to slightly acidic (pKa ranges from 4.4 to 14) depending on their substitution pattern. Amidines are...

The enolization of simple carbonyl compounds is a key reaction for many chemical and biochemical processes. Numerous theoretical experimental studies have been done to probe aspects the mechanism this reaction. In work, effect small water clusters, (H2O)n, n = 1–9, on enol content acetone has investigated by using density functional theory calculations at M06 level in gas solution phases. indic...