Mechanism of C-P bond formation via Pd-catalyzed decarbonylative phosphorylation of amides: insight into the chemistry of the second coordination sphere.

We report on the basis of DFT computations a plausible and detailed reaction mechanism for the first Pd-catalyzed decarbonylative phosphorylation of amides forming C-P bonds, which reveals, among other things, crucial events in the second coordination sphere, including ion pair and hydrogen bonding interactions as well as proton transfer.

Neutral nano-polygons with ultrashort Be-Be distances.

Ultrashort metal-metal distances (USMMDs, d < 1.900 Å) have been realized computationally between the main group metal beryllium. However, due to their ionic charge state and the insufficient stability of their electronic structures and/or thermodynamic stabilities, the known species with ultrashort Be-Be distances are unsuitable for synthesis in the condensed phase, which deters the applications of these interesting structures from being explored.

Computational design of species with ultrashort Be-Be distances using planar hexacoordinate carbon structures as the templates.

A current project in metal-metal bonding chemistry is to achieve ultrashort metal-metal distances (USMMDs, denoted by dM-M < 1.900 Å) between main group metal beryllium atoms. A valid way for achieving such USMMDs is the substitution of a carbon atom in a planar pentacoordinate environment with the isoelectronic Be2 moiety.