Reactions Of Bromoacetylene With Primary Amine On A Butterfly-Type Tetrairon Core To Give Isonitrile And Methyne Through Oxidation And Deprotonation

Reaction of [(eta(5)-C(5)H(4)Me)(4)Fe(4)(HCCH)(HCC-Br)]-(PF(6)) with (t)BuNH(2) forms [(eta(5)-C(5)H(4)Me)(4)Fe(4)(HCCH)(HCC-NH(t)Bu)](PE(6)), of which one electron oxidation leads to carbon carbon bond cleavage to give [(eta(5)-C(5)H(4)Me)(4)Fe(4)(HCCH)(mu(3)-CH)-(mu(3)-CNH(t)Bu)](PF(6))(2), and further treatment with 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU) affords [(eta(5)-C(5)H4(M)e)(4)Fe(4)(HCCH)(mu(3)-CH)(mu(3)-eta(1)-CN(t)Bu)](PE(6)). Thus, the HCCBr group is converted to (t)BuNC and CH groups on the redox-responsive tetrairon core.