Ir(IV) Sulfoxide-Pincer Complexes by Three-Electron Oxidative Additions of Br and I. Unprecedented Trap-Free Reductive Elimination of I from a formal d Metal.

Oxidative addition of 1.5 equiv of bromine or iodine to a Ir(I) sulfoxide pincer complex affords the corresponding Ir(IV) tris-bromido or tris-iodido complexes, respectively. The unprecedented trap-free reductive elimination of iodine from the Ir(IV)-iodido complex is induced by coordination of ligands or donor solvents.

Early Main Group Metal Catalysts for Imine Hydrosilylation.

The efficient catalytic reduction of imines with phenylsilane is achieved by using the potassium, calcium and strontium based catalysts [(DMAT)K (THF)] , (DMAT) Ca⋅(THF) and (DMAT) Sr⋅(THF) (DMAT=2-dimethylamino-α-trimethylsilylbenzyl). Eight different aldimines and the ketimine Ph C=NPh could be successfully reduced by PhSiH at temperatures between 25-60 °C with catalyst loadings down to 2.5 mol %.

Calcium stilbene complexes: structures and dual reactivity.

Addition of a calcium hydride complex to diphenylacetylene gave a complex in which the stilbene dianion symmetrically bridges two Ca ions. DFT calculations discuss the effect of the metal stilbene coordination. The stilbene complex reacts as a base (with H) or an electron donor (with I) and catalyzes the reduction of diphenylacetylene.