Stretched Central Double Bonds in Dialumene and Disilene by Amino Substituents: A Case of Lone Pair Repulsion.

There have been remarkable advances in the syntheses and applications of groups 13 and 14 homonuclear ethene analogues. However, successes are largely limited to aryl- and/or silyl-substituted species. Analogues bearing two or more heteroatoms are still scarce. In this work, the block-localized wavefunction (BLW) method at the density functional theory (DFT) level was employed to study dialumene and disilene bearing two amino substituents whose optimal geometries exhibit significantly stretched central M=M (M=Al or Si) double bonds compared with aryl- and/or silyl-substituted species. Computational analyses showed that the repulsion between the lone electron pairs of amino substituents and M=M π bond plays a critical role in the elongation of the M=M bonds. Evidently, replacing the substituent groups -NH with -BH can enhance the planarity and shorten the central double bonds due to the absence of lone pair electrons in BH .