Oxidative Coupling of Terminal Rhenium Pnictide Complexes

The isolation of rhenium(V) complexes with terminal phosphide and arsenide ligands was achieved upon decarbonylation of rhenium(III) pnictaethynolates. One‐electron oxidation of the pnictide complexes yielded Pn?Pn (Pn=P, As) coupling products, which were spectroscopically and crystallographically characterized. Computational bond analysis suggests that these complexes are best described as {Pn₂}⁰ complexes that are stabilized by donor–acceptor interactions with the metal and a pyrazole ligand.     

Manganese‐Catalyzed N‐Formylation of Amines by Methanol Liberating H2: A Catalytic and Mechanistic Study

The first example of a base metal (manganese) catalyzed acceptorless dehydrogenative coupling of methanol and amines to form formamides is reported herein. The novel pincer complex (i Pr‐PN^HP)Mn(H)(CO)₂ catalyzes the reaction under mild conditions in the absence of any additives, bases, or hydrogen acceptors. Mechanistic insight based on the observation of an intermediate and DFT calculations is also provided.     

A Terminal Iridium Oxo Complex with a Triplet Ground State

A terminal iridium oxo complex with an open‐shell (S=1) ground state was isolated upon hydrogen atom transfer (HAT) from the respective iridium(II) hydroxide. Electronic structure examinations support large spin delocalization to the oxygen atom. Selected oxo transfer reactions indicate the ambiphilic reactivity of the iridium oxo moiety. Calorimetric and computational examinations of the HAT revealed a bond dissociation free energy for the IrO?H bond that is sufficient for hydrogen atom abstraction towards C?H bonds and small contributions from entropy and spin–orbit coupling to the HAT thermochemistry.