On the Reactivity of a NHC Nickel Bis-Boryl Complex: Reductive Elimination and Formation of Mono-Boryl Complexes.

ABSTRACT

The synthesis of the first terminal mono-boryl complexes of nickel, which are not stabilized by a pincer ligand, is reported. The reaction of the nickel bis-boryl complex cis-[Ni(i Pr2 ImMe )2 (Bcat)2 ] 1 (cat=1,2-O2 C6 H4 ) with the small donor ligand PMe3 led to a complete ligand exchange at nickel with reductive elimination of B2 cat2 and formation of the bis-NHC adduct [B2 cat2 ⋅ (i Pr2 ImMe )2 ] 3 and [Ni(PMe3 )4 ] 2 as the metal-containing species. Electrophilic attack of MeI on complex 1 or ligand dismutation of 1 with trans-[Ni(i Pr2 ImMe )2 Br2 ] led to loss of only one boryl ligand of 1 and afforded the nickel mono-boryl complexes trans-[Ni(i Pr2 ImMe )2 (Bcat)Br] 4 a and trans-[Ni(i Pr2 ImMe )2 (Bcat)I] 4 b.