Palladium(II)-catalyzed aerobic oxidative amination of styrene with oxazolidinone proceeds with catalyst-controlled regioselectivity: (CH3CN)2PdCl2 (1) and (Et3N)2PdCl2 (2) catalyze formation of the anti-Markovnikov and Markovnikov enecarbamate products, 3 and 4, respectively. Kinetic studies and deuterium kinetic isotope effects demonstrate that these two reactions possess different rate-limit...

In the present work a quantum chemical study of a series of substituted hydrofullerenes, C(60)HR, and a series of methanofullerenes, C(60)(CHR), is presented. Their reactivity and geometrical, energetic, electronic, and magnetic properties, as well as the influence of the substituent, are discussed. As a probe of the reactivity, the acidic properties of these fullerene derivatives were predicte...

Mild deprotonation of a 2-pyridyl (py)-functionalized phosphoric triamide [PO(NHpy)(3)] in the absence of an external base was studied in the presence of various silver(I) salts. Interesting examples of octa- and hepta-nuclear Ag(I) complexes coordinated to imido and pyridyl groups were obtained when more reactive Ag(I) salts, such as AgClO(4) and AgBF(4), were used, while the less reactive AgN...

Despite extensive investigation, the precise mechanism controlling the opening of the cytoplasmic proton uptake pathway in bacteriorhodopsin (bR) has remained a mystery. From an analysis of the X-ray structure of the D96G/F171C/F219L triple mutant of bR and 60 independent molecular dynamics simulations of bR photointermediates, we report that the deprotonation of D96, a key residue in proton tr...

Ab initio, molecular orbital calculations for two different Hartree-Fock basis levels were performed on clusters in the system Al-O-H, and tested by comparing derived vibrational frequencies to the measured values for aluminum oxides and aluminum oxyhydroxide minerals. Models were chosen to reflect surface groups that may be present on aluminous minerals such as a-Al2O3 (corundum) and Al(OH)3 (...

Simple, secondary 2,4,6-triisopropyl benzoates (TIB esters) and secondary dialkyl N,N-diisopropyl carbamates have been reported to be resistant to deprotonation by strong bases. We have found that the combination of sBuLi (1.6 equiv) and TMEDA (6 equiv) in CPME at -60 °C enables deprotonation of unactivated secondary dialkyl TIB esters, but not the carbamates. These carbanions were reacted with...

Deprotonation of N,N-diisopropyl-C-ferrocenylaldiminium triflate 2 cleanly leads to the corresponding 1,2-diamino-1,2-diferrocenylethene 3, the dimer of the desired (amino)(ferrocenyl)carbene. Fulvene 6, obtained by addition of the lithium salt of tetramethylcyclopentadiene to methoxyformamidinium methylsulfate 5, reacts with dicarbonylcyclopentadienylbromoiron(II), and with a mixture of FeCl(2...

A variety of half-sandwich iron(ii) complexes with diprotic acyclic diaminocarbene ligands (pADCs) have been obtained by reaction of the cationic complexes [Fe(Cp)(CO)2(CNR)]+ and [Fe(Cp)(CO)(CNR)2]+ with methylamine, and their acid-base behaviour was studied, revealing an easy reversible deprotonation reaction of both N-H moieties of the carbene ligands. The deprotonation process is frequently...

The C–H bond deprotonation and functionalization reaction represents the most frequently used method for C–C construction also a vital mode of activation. Great developments have been made recently in catalytic formation by using weakly acidic compounds as nucleophiles. The strongly basic reagent or catalyst is key factor these reactions. If only base enough, bonds, carbanions fol...