New bonding modes of carbon and heavier group 14 atoms Si–Pb

Abstract

Recent theoretical studies are reviewed which show that the naked group 14 atoms E = C–Pb in the singlet ¹D state behave as bidentate Lewis acids that strongly bind two σ donor ligands L in the donor–acceptor complexes L→E←L. Tetrylones EL₂ are divalent E(0) compounds which possess two lone pairs at E. The unique electronic structure of tetrylones (carbones, silylones, germylones, stannylones, plumbylones) clearly distinguishes them from tetrylenes ER₂ (carbenes, silylenes, germylenes, stannylenes, plumbylenes) which have electron-sharing bonds R–E–R and only one lone pair at atom E. The different electronic structures of tetrylones and tetrylenes are revealed by charge- and energy decomposition analyses and they become obvious experimentally by a distinctively different chemical reactivity. The unusual structures and chemical behaviour of tetrylones EL₂ can be understood in terms of the donor–acceptor interactions L→E←L. Tetrylones are potential donor ligands in main group compounds and transition metal complexes which are experimentally not yet known. The review also introduces theoretical studies of transition metal complexes [TM]–E which carry naked tetrele atoms E = C–Sn as ligands. The bonding analyses suggest that the group-14 atoms bind in the ³P reference state to the transition metal in a combination of σ and π_∥ electron-sharing bonds TM–E and π_⊥ backdonation TM→E. The unique bonding situation of the tetrele complexes [TM]–E makes them suitable ligands in adducts with Lewis acids. Theoretical studies of [TM]–E→W(CO)₅ predict that such species may becomes synthesized.