Reactions of thioallenes with triiron dodecacarbonyl: A route to thioallyl-bridged diiron hexacarbonyl complexes

Article abstract of DOI:10.1021/om00059a042

Thioallenes, RSC(X)=C=CH₂ (R = CH₃, C₂H₅, Ph; X = OCH₃, H) react with Fe₃(CO)₁₂ to give products of type A. An additional product, B, is obtained when the thioallene used is PhSCH=C=CH₂. A complex (Matrix Presented) of this type and the isomer in which the RS groups are in trans position also are obtained in low yield in the case of CH₃SCH=C=CH₂, in addition to the type B major product The formation of (μ-RS)₂Fe₂(CO)₆ as by-products indicates that some C-S bond cleavage occurs as well. The structures of one example each of structural types A and B have been determined: (η¹:η³-CH₃SCHCCH₂)Fe ₂(CO)₆ (2a) for R = CH₃, X = H; (η³-PhSCHCCH₂)₂Fe₂(CO) ₆ (15b) for R = Ph. Compound 2a crystallizes in the monoclinic space group P2₁/c with a = 7.7134 (4) A?, b = 13.6321 (5) A?, c = 12.9757 (9) A?, β = 102.318 (6)°, V = 1333.0 (3) A?³, and Z = 4, and has refined to R = 0.041 and R_w = 0.047 based on 2192 unique observations. Compound 15b crystallizes in the triclinic space group P1 with a = 10.938 (1) A?, b = 12.064 (2) A?, c = 9.806 (1) A?, α = 92.02 (1)°, β = 93.03 (1)°; γ = 68.15 (1)°, V = 1199.2 (4) A?³, Z = 2, and has refined to R = 0.038 and R_w = 0.054 based on 3360 unique observations.