Reduction of CCl4 by CrCl2 in THF afforded a trinuclear chromium(III) carbyne [CrCl(thf)2)]3(μ3-CCl)(μ-Cl)3. The chlorocarbyne complex reacted with aldehydes to afford chloroallylic alcohols and terminal alkynes. The density functional theory...

Carbon tetrabromide can be reduced with CrBr2 in THF to form a dinuclear carbido complex, [CrBr2(thf)2)][CrBr2(thf)3](μ-C), along with formation of [CrBr3(thf)3]. An X-ray diffraction study of the pyridine adduct displayed...

A ligand‐controlled regiodivergence in Ni‐catalyzed rearrangement of vinylcyclopropanes to 1,4‐ or 1,5‐disubstituted cyclopentenes is reported. The 1,4‐ or 1,5‐disubstituted cyclopentene is selectively obtained depending on the choice of ligands. Detailed kinetic studies and density functional theory calculations on the catalytic cycle revealed that the product selectivity is determined at the reductive elimination step from the six‐membered η1‐allyl intermediate.

A ligand-controlled regiodivergence in Nicatalyzed rearrangement of vinylcyclopropanes to 1,4or 1,5-disubstituted cyclopentenes is reported. The 1,4or 1,5-disubstituted cyclopentene is selectively obtained depending on the choice of ligands. Detailed kinetic studies and density functional theory calculations on the catalytic cycle revealed that the product selectivity is determined at the reductive elimination step from the six-membered η 1 -allyl intermediate.