Treatment of Fe2(CO)6μ-EC(Ph)=C(E′)-[C(OEt)=M(CO) 5] (1: E, E′ = Se; M = Cr. 2: E, E′ = Se; M=W. 3: E = S; E′ = Te; M = W) with excess Bu3SnH in hexane at 0 °C produces enol ether derivatives: (CO)6Fe2μ-EC(Ph)(H)-C(E′)=C(H)(OEt) ((Z)-4a: E, E′ = Se. (E)-4b: E, E′ = Se. (Z)-5a: E = S; E′ = Te. (E)-5b: E = S; E′ = Te). For E, E′ = Se, using 1 equiv of Bu3SnH, the α-alkoxyallylstannane complex, (CO)6Fe2μ-Se(Ph)C=C(Se)-C(OEt)(H)SnBu3 (6), was isolated. The molecular structure of (E)-4b was confirmed by X-ray analysis.