Dimethoxydimethylsilane from Silicon Atoms and Dimethyl Ether: A Combined Matrix‐Spectroscopic and Density Functional Theory Study

The reaction between silicon atoms and dimethyl ether ( 6 ) has been studied in an argon matrix at 10 K and in solid dimethyl ether ( 6 ) at temperatures up to 80 K. In the initial step, a triplet n‐adduct T‐5 is formed between a silicon atom and 6 . The next step needs photochemical activation. Depending on the relative dimethyl ether/argon ratio, the photoproduct is either dimethylsilanone ( 1 ) or singlet methoxymethylsilylene ( S‐2 ), which, in the presence of an excess of 6 , exists as a dimethyl ether complex 8 of silylene S‐2. Longer irradiation transforms dimethyl ether addition compounds S‐8‐t/S‐8‐c into dimethoxydimethylsilane ( 7 ). If irradiation is applied directly during cocondensation of silicon atoms with 6 , the only detectable products are 8 and 7 . Upon further irradiation of the pure dimethyl ether matrix, the rest of 8 is also photoisomerized, and dimethoxydimethylsilane ( 7 ) is observed exclusively. The structural elucidation of all new species is based on comparison of the experimental observations with density functional theory calculations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)