Matrix Isolation and Photochemical Interconversion of Siiacyciopentadienes

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Abstract
1-Silacyclopenta-2,4-diene 1 has been generated by vacuum pyrolysis of 5-silaspiro[4.4]nona-2,7-diene 5 and by photolysis of matrix-isolated 1,1-diazido-1-silacyclopent-3-ene 6 , and characterized by matrix-isolation IR and UV spectroscopy; reversible interconversion of 1 with 1-silacyclopenta-1,3-diene 2 , 1-silacyclopenta-1,4-diene 3 and 1-silacyclopent-3-ene-1,1-diyl 4 has been observed upon irradiation at various wavelengths; the red-shifted UV absorption of 2 and 3 , together with their low Si C stretching frequencies, provide evidence for Si C—C C π conjugation. References 1 T.J. Barton G.T. Burns J Organomet. Chem. 179 1979 C17 2 A. Laporterie, J. Dubac, P. Mazerolles and H. Iloughmane, J. Organomet. Chem ., 1981, 206 , C25; A. Laporterie, P. Mazerolles, J. Dubac and H. Iloughmane, J. Organomet. Chem ., 1981, 216 , 321; G. T. Burns and T. J. Barton, J. Organomet. Chem ., 1981, 209 , C25; J. Dubac, A. Laporterie and H. Iloughmane, J. Organomet. Chem ., 1985, 293 , 295; J. Dubac, A. Laporterie, G. Manuel and H. Iloughmane, Phosphorus Sulfur , 1986, 27 , 191. 3 J.-P. Béteille G. Manuel A. Laporterie H. Iloughmane J. Dubac Organometallics 5 1986 1742 4 B. H. Boo and P. P. Gaspar, Organometallics , 1986, 5 , 698; D. Lei, Ph.D. Thesis, Washington University, St. Louis, Missouri, December 1988. 5 J.-P. Béteille M.P. Clarke I.M.T. Davidson J. Dubac Organometallics 8 1989 1292 6 E.A. Chernyshev S.A. Bashkirova A.B. Petrunin P.M. Matveichev V.M. Nosova Zh. Metalloorg. Khim. 4 1991 378 7 T.J. Drahnak J. Michl R. West J. Am. Chem. Soc. 101 1979 2136 1981, 103 , 1845 8 M.J. Michalczyk M.J. Fink D.J. De Young C.W. Carlson K.M. Welsh R. West J. Michl Silicon. Germanium, Tin Lead Compd. 9 1986 75 9 K.M. Welsh J. Michl R. West J. Am. Chem. Soc. 110 1988 6689 10 G. Raabe H. Vancik R. West J. Michl, J. Am. Chem. Soc. 108 1986 671