Remarkable Reactions of (η4-1-azadiene)Fe(CO)3 Complexes with Aryllithium Reagents. Syntheses and Structures of Novel Chelated Furanyl-Coordinated Alkoxy(amino)carbeneiron, η4-Azadiene-Coordinated 17e Acyliron, and Iron Inner Salt Complexes

Abstract

The reactions of a (η4-1-azadiene)Fe(CO)3 complex, [(η4-C4H3OCHCHCHNC6H11)Fe(CO)3] (1), with aryllithium reagents, ArLi (Ar = C6H5, p-CH3C6H4, o-CH3OC6H4, p-CH3OC6H4, p-CF3C6H4), in ether at low temperature followed by alkylation with Et3OBF4 in aqueous solution at 0 °C or in CH2Cl2 at −60 °C gave novel chelated furanyl-coordinated alkoxy(amino)carbeneiron complexes [{η4-C4H3OCHCHCH(Ar)N(C6H5)C(OC2H5)}Fe(CO)2] (4, Ar = C6H5; 5, Ar = p-CH3C6H4; 6, Ar = o-CH3OC6H4; 7, Ar = p-CH3OC6H4; 8, Ar = p-CF3C6H4). The analogous reactions of compounds [(η4-C4H3OCHCHCHNC6H11)Fe(CO)3] (2) and [(η4-C6H5CHCHCHNC6H11)Fe(CO)3] (3) with ArLi (Ar = C6H5, o-, m-, p-CH3C6H4) afforded novel η4-azadiene-coordinated 17e acyliron complexes [{η4-C4H3OCHCHCHNC6H11}Fe(CO)2(COAr)] (9, Ar = C6H5; 10, Ar = o-CH3C6H4; 11, Ar = m-CH3C6H4; 12, Ar = p-CH3C6H4) and [(η4-C6H5CHCHCHNC6H11)Fe(CO)2(COAr)] (15, Ar = C6H5; 16, Ar = m-CH3C6H4; 17, Ar = p-CH3C6H4), respectively. Unexpectedly, 2 reacts similarly with p-CH3OC6H4Li and p-CF3C6H4Li to yi...