375388-39-9

Photolysis of Cp′(CO)2FeSiMe2O (2-C5H4N) (1a: Cp′ = η5- C5H5 (Cp), 1b: Cp′ = η5-C5Me5 (Cp*)) afforded Cp′(CO)Fe[κ2 (Si,N)-SiMe2O(2-C5H4N)] (2a: Cp′ = Cp, 2b: Cp′ = Cp*) in good yield each. These cyclic compounds also formed in moderate yields through photoreaction of Cp′ (CO)2FeSiMe3 with HSiMe2O(2-C5H4N) (3). Single-crystal X-ray diffraction study confirmed the structure of 2b containing a five-membered chelate ring comprised of Fe, Si, O, C, and N. Complexes 2a and 2b were thermally stable and did not react with slight excess of PR3 (R = Me, Ph) in benzene-d6 solution below 80 °C. Above 80 °C, 2a reacted slowly with PR3 to give Cp(CO)(PR3)FeSiMe2O (2-C5H4N) (6: R = Me, 7: R = Ph) accompanied by the cleavage of the Fe-N bond. These results indicate that both Fe-Si bond and Fe-N bond in 2 are notably sturdy.

A novel hydridobis(silyl)iron(IV) complex Cp*(CO)Fe(H)-(SiMe2O(2-C5H4N)}2 (1) (Cp=η5-C5Me5) was synthesized in high yield. Two elimination processes from 1 were effectively controlled by the reaction conditions: HSiMe2O(Z-C5H4N) is eliminated on heating or UV-irradiation, whereas HO(2-C5H4N) is eliminated in the presence of Et3Al. The latter reaction was applied to a silylene introduction toward a silyl complex producing a silyl(silylene) complex.