The cycloaddition reactions of 18 1,3-dipolar molecules to ethylene and acetylene have been reinvestigated by quantum chemical methods that are based on a second-order perturbation treatment of electron correlation. It is found that SCS-MP2 and the new perturbative B2-PLYP density functional provide accurate reaction barriers and outperform MP2 as well as standard density functionals such as B3-LYP. The new second-order based methods have the additional advantage that they perform better with increasing quality of the one-particle space, as is desired for a good quantum chemical method. The errors for the reaction enthalpies are in general larger than for the barriers when compared to CBS-QB3 literature values, which is related to strong changes in the electronic structures, but the deviations are again smaller than with MP2 or B3-LYP and are also more systematic. The results of a detailed basis set study suggest that properly polarized triple-zeta AO basis sets represent a good compromise between accuracy and computational speed. The combination of very inaccurate density functionals with small (double-zeta) basis sets, which yields good results for the initial part of the reactions due to error compensation, is not recommended.

Oxidative addition: complexes containing an anionic NHC ligand with an unsubstituted nitrogen atom within the heterocycle have been prepared by oxidative addition of 2-chloro-N-methylbenzimidazole to Ni(0) and Pt(0). The "naked" nitrogen atom of the NHC ligand reacts as a strong nucleophile.

Treatment of (silylalkynyl)benzenes with (Me3C)2GaH afforded stable cis‐addition products, for example, (Me3C)2GaC(SiMe3)C(H)C6H5 (1), while spontaneous cis/trans rearrangement was observed for sterically less shielded gallium hydrides. The corresponding trans‐di(tert‐butyl)gallium compounds (13, 14) were obtained by the reaction of C6H6−n[C(H)C(SiMe3)GaCl2]n (11, 12) with LiCMe3. In contrast, spontaneous isomerization took place upon reaction of (Me3C)2AlH with phenyltrimethylsilylethyne. In this case the cis isomer (17) was detected only at low temperature, while the trans product (18) formed quantitatively above 0 °C. Quantum‐chemical calculations showed that the trans forms are thermodynamically favored, essentially caused by a better mesomeric interaction of the CC double bonds with the phenyl groups, a smaller steric stress in the molecules, and a short bonding contact of the coordinatively unsaturated Al or Ga atoms to CH bonds of the aromatic rings. The rotation about the CC double bonds follows a zwitterionic mechanism, and the relatively small rotational barrier is further lowered by an interaction to a Lewis acidic lithium cation.

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A new quantum mechanical scheme to calculate electronic correlation energies, spin-component-scaled MP2, was tested as a tool to predict reaction energies and barriers in computational organic chemistry. Three common pericyclic reactions with known unsatisfactory MP2 descriptions were reinvestigated with the modified MP2 approach, in which the parallel and anti-parallel spin components of the correlation energy are scaled separately. The SCS-MP2 calculated reaction and activation energies of nine Diels-Alder reactions, four [3,3] sigmatropic rearrangements, and ten electrocyclization reactions are compared to those of the MP2, B3 LYP, QCISD(T), and G3 methods. For each, the SCS-MP2 results are in excellent agreement with the experimental data and compare far more favorably to G3 than both MP2 and B3 LYP. Careful evaluation of the effect of the size of the atomic orbital (AO) basis set shows that the larger expansions improve the agreement with experiment for the SCS-MP2 method, while they get worse for both MP2 and B3 LYP.