Lewis Acid Chemistry of a Cationic [CCH] Subunit in a Bisdisphenoidal Eight-Atom Tetrairon–Tetracarbon Cluster
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Reaction of [(η5-C5H4Me)4Fe4(HCCH)(HCCBr)](PF6) ([2](PF6)) with AgPF6 in acetonitrile gave [(η5-C5H4Me)4Fe4(HCCH)(HCCNCMe)](PF6)2 ([3](PF6)2). The X-ray diffraction study revealed that the cationic [CCH] subunit is stabilized through coordination of the acetonitrile molecule to the cationic carbon atom. As a synthon for a donor-free [(η5-C5H4Me)4Fe4(HCCH)(HCC)]2+, [(η5-C5H4Me)4Fe4(HCCH)(HCCL)](PF6)2 ([6](PF6)2, L = pyrazine) was synthesized by the reaction of [2](PF6) with AgPF6 in the presence of pyrazine. Treatment of [6](PF6)2 with tertiary amines in acetonitrile led to deprotonation of acetonitrile to form [(η5-C5H4Me)4Fe4(HCCH)(HCCCH2CN)](PF6) ([11](PF6)). Treatment of [6](PF6)2 with maleimide in the presence of tertiary amine in acetonitrile allowed the functionalization of the coordinated acetonitrile through the nucleophilic attack of maleimide at the nitrile carbon atom.
