Insertion reactions of dimethylsilylene: relative reactivity towards oxygenz.sbnd;hydrogen,siliconhydrogen,and siliconz.sbnd;alkoxy bonds

Photochemically-generated dimethylsilylene is found in competition experiments to insert preferentially into oxygenhydrogen bonds of alcohols compared to either siliconhydrogen bonds of silanes or siliconoxygen bonds of alkoxysilanes. This selectivity for OH bonds compared to SiH bonds is quite high in tetrahydrofuran and in dilute hydrocarbon solutions. However, it decreases in more concentrated hydrocarbon solutions. These effects are discussed in terms of aggregation of alcohols, hydrogen bonding, and solvent-mediated dimethylsilylene reactivity.