Abstract:
Transition metal tetrylidyne complexes of the form LnM≡E−R (Ln = ligand sphere, M = group 9 transition metal, E = group 14 element, R = organyl group) as well as ditetrylynes RE≡ER are well established classes of compounds. However, the scope of tetrylidyne complexes can be significantly expanded by leveraging the thermodynamic properties of both, E≡E and M≡E, triple bonds.
Recent advancements enable metal-centered E≡E triple bond cleavage reactions of ditetrylynes and metathetical M≡E bond exchanges, offering elegant pathways to synthesize the first group 9 transition metal tetrylidene-tetrylidyne [LnM{ER}{E(X)R}] (X = halogen) and bis-tetrylidyne [LnM{ER}2]+ complexes.
Distinctive structural features of these novel compounds prompt inquiries regarding the correlations between bond lengths, bond strengths and bond orders. Consequently, a range of quantum chemical tools have been employed to probe and comparatively analyze thermodynamic properties and electronic structures of these compounds.