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Dimethoxydimethylsilane from Silicon Atoms and Dimethyl Ether: A Combined Matrix‐Spectroscopic and Density Functional Theory Study
Author(s) -
Maier Günther,
Glatthaar Jörg
Publication year - 2003
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200300203
Subject(s) - dimethyl ether , chemistry , silylene , ether , adduct , irradiation , density functional theory , photochemistry , silicon , argon , singlet state , computational chemistry , organic chemistry , excited state , atomic physics , catalysis , physics , nuclear physics
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)