It all adds up: Straightforward access to 2‐alkyl‐substituted 1,3‐diketones is provided by a regioselective addition of aldehydes to enones catalyzed by the ruthenium hydride catalyst [RuHCl(CO)(PPh3)3] (see scheme). The reaction involves a hydrometalation of the enone to form a metal enolate, a cross‐aldol reaction to form an alkoxymetal species, and a subsequent β‐metal hydride elimination.

Ab initio G-2 calculations have been carried out for a number of elementary reactions relevant to low-temperature silane oxidation. The calculations have been made to identify the chain-branching process which enables the spontaneous ignition of silane at room temperature. Extensive calculations have also been made for the reactions of major intermediates with hydrogen atoms and water vapor.

When primary unsaturated alcohols were treated with a catalytic amount of RuHCl(CO)(PPh3)3 in benzene under reflux, dimerization reactions took place to give alpha-hydroxymethyl ketones as major product.

Potential energy surfaces for the ground and two low-lying electronically excited states of CaNC/CaCN, are calculated using the ab initio molecular orbital (MO) configuration interaction (CI) method. The absorption and emission spectra of the system are computed by performing time-dependent quantum dynamical calculations on these surfaces. The most stable geometries for the two lowest lying 12Σ+ and 12Π electronic states correspond to the calcium isocyanide (CaNC) structure. These two states are characterized by ionic bonding and the potential energy curves along the bending coordinate are relatively isotropic. The result of our wave packet dynamics shows that the characteristics of the experimental spectra observed by the laser-induced fluorescence spectroscopy can be explained by the Renner–Teller splitting.

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