Synthesis, Crystal Structure, Spectroscopy, and Theoretical Investigations of Tetrahedrally Distorted Copper(II) Chelates with [CuN2S2] Coordination Sphere

Photolytically-induced reactions of chromyl chloride with acetylene and but-2-yne (dimethylacetylene) in low-temperature argon matrices yield end-on ketene and dimethylketene complexes of O=CrCl2, respectively. The product formation probably results from an electrophilic attack of a Cr=O linkage on the C=C triple bonds, leading to radical-like transition states or intermediates, which subsequently rearrange through 1,2-H or 1,2-methyl shifts. Consequently, allene is attacked at its central carbon and the allyl radical thus generated undergoes subsequent ring-closure to give a cyclopropanone complex of O=CrCl2.