Arylthiolate coordination and reactivity at pseudotetrahedral nickel(II) centers: modulation by noncovalent interactions

Five new pseudotetrahedral nickel(II) arylthiolate complexes are prepared by metathesis reactions of known chloride complexes with sodium arylthiolate salts in THF. The reactivity of the nickel-thiolate linkage toward electrophilic alkylation with MeI is affected, indicating increased rates according to two distinct competing mechanisms, direct biomolecular alkylation of intact complex and rate-limiting unimolecular dissociation of free thiolate.