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

Abstract

AbstractThe 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)