Other information on the differences between peroxides and ketals ---------------------------S2 Lack of stabilization on sulphonyl compounds------------------------------------------------------S2 PES relaxed scan for both COCO dihedrals in dimethoxy-methane simultaneously--------S3 PES relaxed dihedral scans for fluoroperoxides-----------------------------------------------------S3 More detail...

By reaction of 1,4-dipotassio-1,1,4,4-tetrakis(trimethylsilyl)tetramethyltetrasilane with PbBr(2) in the presence of triethylphosphine a base adduct of a cyclic disilylated plumbylene could be obtained. Phosphine abstraction with B(C(6)F(5))(3) led to formation of a base-free plumbylene dimer, which features an unexpected single donor-acceptor PbPb bond. The results of density functional comput...

The structure, bonding and reactivity of 2-adamantylidene and its heavier group-14 analogues, 2X (X10H14, X = C-Sn), have been studied at the M06/def2-TZVPP//BP86/def2-TZVPP level of theory. 2-Adamantylidene and its heavier analogues, 2X, have a singlet ground state, where the carbene and silylene bridges in 2C and 2Si are bent similarly to the foiled-type carbenes. The bending of the carbene a...

The molecular dynamics of the triplet-state Zimmerman di-π-methane rearrangement of dibenzobarrelene were computed with B3LYP and M06-2X density functionals. All productive quasiclassical trajectories involve sequential formation and cleavage of C-C bonds and an intermediate with lifetimes ranging from 13 to 1160 fs. Both dynamically concerted and stepwise trajectories are found. The average li...

Alkaline hydrolysis of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), as one of the most promising methods for nitrocompound remediation, was investigated computationally at the PCM(Pauling)/M06-2X/6-311++G(d,p) level of theory. Computational simulation shows that RDX hydrolysis is a highly exothermic multistep process involving initial deprotonation and nitrite elimination, cycle cleavage, fur...

Relative populations of three energy-lowest IPR (isolated-pentagon-rule) isomers Eu@C 88 are computed using the Gibbs energy based on characteristics from density functional theory and MP2 calculations (M06-2X/3-21G∼SDD entropy term, MP2=FU/6-31G*∼SDD or B2PLYPD=FU/6-31 + G*∼SDD energetics). The predict coexistence isomers, in agreement with extraction a polar solvent, offer possible explanatio...

Opioids such as morphine are important pain-relieving drugs but also carry a risk of harmful side effects including addiction. Morphine is active in both healthy and inflamed tissue, however, decreasing the pKa biochemically-active amine group can promote selective binding more acidic conditions tissue reduce associated with opioids. Herein, we explore impact fluorination on fluoromorphine deri...

Abstract The tautomeric equilibrium of sildenafil molecule was theoretically studied using B3LYP and M06-2X density functional theory (DFT) methods in connection with aug-cc-pVDZ correlation consistent basis set. Calculations were performed for gas phase water solution conditions modelled by polarizable continuum model (PCM). Three forms are possible. Two keto forms: A — where the proton more d...