Reaction Chemistry of Silver(I) Trifluoromethanesulfonate Complexes of Nitrogen-Confused C‑Scorpionates

Two new C-scorpionate ligands with a bis­(3,5-dimethylpyrazol-1-yl)­methyl group bound to the 3 position of either an N-tosyl (TsL*) or an N–H pyrazole (HL*) ring have been prepared. The silver­(I) complexes of these new ligands and the two previously reported analogous ligands with unsubstituted bis­(pyrazol-1-yl)­methyl groups (TsL and HL) in both 1:1 and 2:1 ligand/metal ratios were investigated to explore the effects of ligand sterics on their physical and chemical properties. The structurally characterized derivatives of the type [Ag­(L)2]­(OTf) are four-coordinate, where the confused pyrazolyl is not bound to the metal. On the other hand, three 1:1 complexes [Ag­(L)]­(OTf) had all pyrazolyls bound, while the μ–κ1,κ1-TsL derivative had an unbound confused pyrazolyl. The molecularity of the latter four ranged from polymeric to dimeric to monomeric in the solid with increasing steric bulk of the ligand. The utility of these complexes in stoichiometric ligand-transfer reactions and in styrene aziridination was demonstrated. Thus, tricarbonylmanganese­(I) complexes were prepared as kinetically inert models for comparative solution diffusion NMR studies. Also, [Fe­(HL)2]­(OTf)2 was prepared for similar reasons and to compare the effects of anion on spin-crossover properties.