Monomeric 16-Electron π-Diborene Complexes of Zn(II) and Cd(II)

Despite the prevalence of stable π-complexes of most d¹⁰ metals, such as Cu(I) and Ni(0), with ethylene and other olefins, complexation of d¹⁰ Zn(II) to simple olefins is too weak to form isolable complexes due to the metal ion's limited capacity for π-backdonation. By employing more strongly donating π-ligands, namely neutral diborenes with a high-lying π(B-B) orbital, monomeric 16-electron M(II)-diborene (M = Zn, Cd) π-complexes were synthesized in good yields. Metal-B₂ π-interactions in both the solid and solution state were confirmed by single-crystal X-ray analyses and their solution NMR and UV-vis absorption spectroscopy, respectively. The M(II) centers adopt a trigonal planar geometry and interact almost symmetrically with both boron atoms. The MB₂ planes significantly twist out of the MX₂ planes about the M-centroid(B-B) vector, with angles ranging from 47.0° to 85.5°, depending on the steric interactions between the diborene ligand and the MX₂ fragment.