Transition Metal Complexes with Sulfur Ligands, 138 Synthesis, Structures, and Reactions of Sulfur-Rich Nickel and Platinum Complexes with [MS3] and [MNS2] Cores

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.