London Dispersion Effects in a Distannene/Tristannane Equilibrium: Energies of their Interconversion and the Suppression of the Monomeric Stannylene Intermediate

Abstract

AbstractReaction of {LiC6H2−2,4,6‐Cyp3⋅Et2O}2 (Cyp=cyclopentyl) (1) of the new dispersion energy donor (DED) ligand, 2,4,6‐triscyclopentylphenyl with SnCl2 afforded a mixture of the distannene {Sn(C6H2−2,4,6‐Cyp3)2}2 (2), and the cyclotristannane {Sn(C6H2−2,4,6‐Cyp3)2}3 (3). 2 is favored in solution at higher temperature (345 K or above) whereas 3 is preferred near 298 K. Van't Hoff analysis revealed the 3 to 2 conversion has a ΔH=33.36 kcal mol−1 and ΔS=0.102 kcal mol−1 K−1, which gives a ΔG300 K=+2.86 kcal mol−1, showing that the conversion of 3 to 2 is an endergonic process. Computational studies show that DED stabilization in 3 is −28.5 kcal mol−1 per {Sn(C6H2−2,4,6‐Cyp3)2 unit, which exceeds the DED energy in 2 of −16.3 kcal mol−1 per unit. The data clearly show that dispersion interactions are the main arbiter of the 3 to 2 equilibrium. Both 2 and 3 possess large dispersion stabilization energies which suppress monomer dissociation (supported by EDA results).