| Title
| - Photochemistry of the Three Possible Isomeric CyclicDisilyliron Complexes, FpSi2R5 (Si2R5 =1,2,2-Trimethyldisilacyclohexyl,(1-Methylsilacyclopentyl)dimethylsilyl, and1-(Trimethylsilyl)silacyclopentyl, Fp = (η5-C5H5)Fe(CO)2)
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| Abstract
| - The three cyclic disilyliron complexes FpSi2R5 (Si2R5 = 1,2,2-trimethyldisilacyclohexyl (3),(1-methylsilacyclopentyl)dimethylsilyl (6), 1-(trimethylsilyl)silacyclopentyl (9)) have beensynthesized and characterized. Photolysis of these complexes resulted in the formation ofFpSiMe3 and FpSiR3 (SiR3 = methylsilacyclopentyl) in the same ratio of 34:66 via silyleneeliminations. Irradiation of 3, 6, and 9 independently in the presence of HMPA ledsurprisingly to the formation of only the unique silylene intermediate [(η5-C5H5)Fe(CO)(SiMe2·HMPA)(SiR3)], 11, which has been characterized by 1H, 13C, 29Si, 13C−1H COSY,13C−1H COLOC, and 29Si−1H COLOC NMR spectroscopy.
- Photochemistry of three distinct, but isomeric, Fp-disilanes resulted in the formation of the same product distribution as expected from the intermediacy of equilibrating silyl(silylene) complexes. However, photolysis in the presence of HMPA results in the formation of the same HMPA-stabilized silyl(silylene) complex, not three different species.
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