Ligands of low electronegativity in the VSEPR model: The structures of singlet carbenes

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Equilibrium structures and force constants for skeletal bending from linearity have been calculated, in the MNDO approximation, for twenty five singlet carbenes CX 2. When the substituent X bears neither vacant orbitals nor lone pairs, the force constant becomes steadily more negative as the electronegativity of X increases; when X bears vacant orbitals, the C→ X π bond order and the force constant both increase with the electronegativity of X. When X bears lone pairs, the force constant parallels the HOMO—LUMO gap at linearity. Previous discussions of the structures of singlet carbenes are shown to be inadequate: the reported results support the interpretation in terms of the second-order Jahn-Teller effect of the observed stereochemical inactivity of lone pairs in the presence of ligands of low electronegativity.