Formation of 1:1 adducts between bis(1,2‐diaryl‐1,2‐ethylenedithiolato)metal(0) (metal = NI, PD, and PT) and quadricyclane and their photodissociation

Bis(1,2‐diaryl‐1,2‐ethylenedithiolato)metal(0) complexes (1; metal = Ni, Pd, and Pt) react with quadricyclane (Q) to give selectively 1:1 adducts which are identical with the adducts between 1 and norbornadiene (NBD). In the adducts, two sulfur atoms of the different dithiolato ligands are added to one of the double bonds of NBD. The reactions of 1 with Q are 103–104 times faster than those with NBD. The more electropositive dithiolatometal complexes react faster with Q and NBD. The adducts are dissociated to the free dithiolatometal complexes and NBD by UV‐irradiation (254–436 nm). Upon irradiation with 254 nm light, the photodissociation occurs before the decomposition of the dithiolatometal complexes.