Synthesis and characterization of group 12 metal(I) complexes bearing extremely bulky boryl/silyl substituted amide ligands

Two extremely bulky boryl/silyl‐substituted amide ligands, –N{B(DipNCH)${}_2$}(SiR${}_3$) (R = Me ${}^{TBo}$L, R = Ph ${}^{PhBo}$L; Dip = 2,6‐diisopropylphenyl) were used in the preparation of the group 12 metal halide complexes, ${}^{PhBo}$LZnBr, {${}^{TBo}$LCd(μ‐I)}${}_2$, ${}^{TBo}$LHgI, and ${}^{PhBo}$LHgI. The reduction of these, and two previously reported compounds, ${}^{PhBo}$LZnBr(THF) and {${}^{PhBo}$LCd(μ‐I)}${}_2$, using a magnesium(I) compound, {(${}^{Mes}$Nacnac)Mg}${}_2$ (${}^{Mes}$Nacnac = [(MesNCMe)${}_2$CH]${}^{-}$, Mes = mesityl), were carried out, leading to mixed results. In several cases these reactions led to decomposition, and deposition of the group 12 metal. However, in two instances the homobimetallic metal(I) complexes, ${}^{TBo}$LM–M${}^{TBo}$L (M = Zn or Hg), were isolated and crystallographically characterized. The reduction of {${}^{PhBo}$LCd(μ‐I)}${}_2$ afforded the known cadmium(I) complex, ${}^{PhBo}$LCd–Cd${}^{PhBo}$L, but also gave a very low yield of the thermally unstable complex, ${}^{PhBo}$LCd–Mg(THF)(${}^{Mes}$Nacnac). The X‐ray crystal structure of this compound reveals it to contain the first example of a Cd–Mg bond in a molecular compound. (© 2019 WILEY‐VCH Verlag GmbH and Co. KGaA, Weinheim)