For studying both hydrogen bond and dipole-dipole interactions between methanol molecules (self-association) the geometry of clusters of increasing numbers of methanol molecules (n = 1,2,3) were optimized and also their vibrational frequencies were calculated with quantum chemical methods. Beside these B3LYP/6-311G** calculations, PCM calculations were also done for all systems with PCM at the ...

Accurate infrared spectra of the two hydroxycarbene isomers are computed by diagonalizing the Watson Hamiltonian including up to four mode couplings using full dimensional potential energy and dipole moment surfaces calculated at the CCSD(T)/cc-pVTZ (frozen core) and CCSD6-311G(**) (all electrons correlated) levels, respectively. Anharmonic corrections are found to be very important for these e...

Herein, we report the first examples of the synthesis of pyrroloindolines by means of (3 + 2) dearomative annulation reactions between 3-substituted indoles and highly reactive azaoxyallyl cations. Computational studies using density functional theory (DFT) (B3LYP-D3/6-311G**++) support a stepwise reaction pathway in which initial C-C bond formation takes place at C3 of indole, followed by ring...

Ab initio calculations of the potential energy surface for the C3(1Sigmag+)+C2H2(1Sigmag+) reaction have been performed at the RCCSD(T)/cc-pVQZ//B3LYP/6-311G(d,p) + ZPE[B3LYP/6-311G(d,p)] level with extrapolation to the complete basis set limit for key intermediates and products. These calculations have been followed by statistical calculations of reaction rate constants and product branching r...

The isomerization of silylallene to seven of its isomers has been studied using ab initio molecular orbital theory. The energetics were obtained using quadratically convergent configuration interaction (QCISD(T)) with the 6-311G(d,p) basis set, at geometries optimized by second-order perturbation theory (MP2) with the 6-31G(d) basis set. Test calculations using multiconfiguration wave functions...

The synthesis of Mn2LAc+, Zn2LAc+, and H4L2+ is described, where L is a tetrakis-Schiff base macrocycle formed using 4-tert-butyl-2,6-diformylphenol and 2,2′-diamino-N-methyldiethylamine resulting in an N6O2 coordination environment. In Mn2LAc+ and Zn2LAc+, the two metal centers are bridged by an acetate ligand. [Mn2LAc](ClO4)·(DMF)0.5, [Mn2LAc](ClO4)·(ACN)0.5, and [Zn2LAc](PF6) crystallized in...

A set of highly preorganized pyrazolate-bridged dimanganese complexes L(Mn)MnX have been prepared and structurally characterized. They can be described as hybrid organometallic/Werner-type systems that consist of a low-spin CpMn(I)(CO)2 subunit (Mn1) and a proximate tripodal tetradentate {N4} binding pocket accommodating a high-spin Mn(II) ion (Mn2), with Mn...Mn distances of approximately 4.3 ...