Activation of Isocyanides and Hydrosilanes by a Cationic [CCH] Subunit in a Tetrairon-Tetracarbon Cluster

作者：Taniwaki Wataru; Ohta Shun; Okazaki Masaaki^*

来源：Bulletin of the Chemical Society of Japan, 2016, 89(1): 11-19.

DOI：10.1246/bcsj.20150289

The reactivity of [(eta(5)-C5H4Me)(4)Fe-4(HCCH)(HCC-NC4H4N)](PF6)(2) (1) toward isocyanides and hydrosilanes was examined. The reaction of 1 with tert-butyl isocyanide led to C(sp(3))-N(sp) bond cleavage to give [(eta(5)-C5H4Me)(4)Fe-4(HCCH)-(HCC-CN)](PF6) (2), 1-tert-butylpyrazinium salt, and isobutene. In the reactions with cyclohexyl and benzyl isocyanides, isocyanide adducts [(eta(5)-C5H4Me)(4)Fe-4(HCCH)(HCC-CNR)](PF6)(2) (R = Cy (5), CH2Ph (6)) were obtained and further transformed to 2 (70 degrees C, 10 h for 5; RT, 120h for 6). The reactions of 1 with aryl isocyanides such as 2,6-dimethylphenyl and 2,4,6-tri-tert-butylphenyl isocyanides yielded thermally stable [(eta(5)-C5H4Me)(4)Fe-4(HCCH)(HCC-CNAr)](PF6)(2) (Ar = 2,6-Me2C6H3 (8), 2,4,6-(Bu3C6H2)-Bu-t (9)). The Si-H bonds of R3SiH (R = Et, Ph), Ph2SiH2, and PhSiH3 were activated to give [(eta(5)-C5H4Me)(4)Fe-4(HCCH)(2)](PF6) together with the corresponding fluorosilanes. Coordination of the substrates with a cationic [CCH] subunit promoted the cleavage of the carbon-nitrogen and silicon hydrogen bonds to give the products.

• 出版日期2016-1-15