The silenes H 2 SidCH 2 (2), MeHSidCH 2 (7), and Me 2 SidCH 2 (8) have been prepared by low-pressure flow pyrolysis from the corresponding siletanes H 2 SiCH 2 CH 2 CH 2 (1), MeHSiCH 2 -CH 2 CH 2 (5), and Me 2 SiCH 2 CH 2 CH 2 (6). 2, 7, and 8 were identified by residual gas analysis of the pyrolysis stream and by low-temperature NMR spectroscopy of their complexes 2‚ O(CD 3 ) 2 ( 16), 7‚O(CD 3 ) 2 ( 17), and 8‚O(CD 3 ) 2 ( 18). The complexes 16-18 are stable to temperatures between -140 and -100 °C. Above these temperatures rapid polymerization occurs. The complexation with dimethyl ether obviously stabilizes the silenes and allows their spectroscopic investigation. The 29 Si chemical shifts of the complexes are -25.2 (16), -1.8 (17) and 16.8 ppm ( 18). The experimental results are supported by ab initio and density functional calculations of geometries and magnetic properties of the silenes 2, 7, and 8 and the dimethyl ether complexes 16-18. The calculations predict a relatively short Si-O separation of about 1.7 Å in the corresponding silene-ether adducts. Natural bond analysis of the donor-acceptor complex 16 reveals that the interaction between the ether molecule and the silene is predominantly ionic, despite the relatively short Si-O distance.
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