105472-01-3Relevant academic research and scientific papers
Novel anionic rearrangements in hexacarbonyldiiron complexes of chelating organosulfur ligands
Seyferth, Dietmar,Womack, Gary B.,Gallagher, Michael K.,Cowie, Martin,Hames, Barry W.,Fackler Jr., John P.,Mazany
, p. 283 - 294 (2008/10/08)
Bridging organosulfur chelate ligands of type -SCHRS- (R = H, Ph), -SCH2CH2S-, -S(CH2)3S-, and -SCH2-o-C6H4CH2S- in their Fe2(CO)6 complexes are deprotonated by lithium diisopropylamide. The resulting anion in the case of the -SCH2CH2S- ligand undergoes β-elimination to produce (μ-LiS)(μ-CH2=CHS)Fe2(CO)6, but the anions derived from the other ligands undergo an intramolecular rearrangement which involves nucleophilic attack by the carbanion at an iron atom with displacement of an electron pair onto one of the sulfur atoms. Addition of an organic halide then results in alkylation of a sulfur atom. In the case of (μ-SCH2S)Fe2(CO)6 this sequence results in formation of an Fe2(CO)6 complex of an alkyl dithioformate, (HC(S)SR)Fe2(CO)6. Complexes of the latter type also can be deprotonated. A similar anionic rearrangement then results in formation of novel RR′S-CS-[Fe(CO)3]2 complexes after alkylation of the intermediate sulfur-centered anion with R′X. The structures of three products of such reactions were determined by X-ray crystallography. (μ-CH3C(O)CH2SCHS)Fe2(CO)6 (10) crystallizes in the space group P1 (a = 10.296 (2) A?, b = 11.306 (2) A?, c = 6.617 (1) A?, α = 100.45 (1)°, β = 93.36 (1)°, γ = 103.38 (1)°, V = 732.9 A?3, and Z = 2). On the basis of 2073 observations and 194 parameters varied the structure has converged at R = 0.042 and Rw = 0.055. (μ-C2H5SCHC6H4CH 2S)Fe2(CO)6 (19) crystallizes in P21/n (a = 15.003 (2) A?, b = 7.530 (1) A?, c = 16.599 (2) A?, β = 92.11 (1)°, V = 1874.0 A?3, and Z = 4) and has refined to R = 0.053 and Rw = 0.055 with 2004 observations and 223 parameters varied. (μ-SCS-(CH3)2)Fe2(CO)6 (22) crystallizes in P1 (a = 9.586 (1) A?, b = 10.276 (1) A?, c = 7.601 (1) A?, α = 92.18 (1)°, β = 111.52 (1)°, γ = 86.94 (1)°, V = 695.3 A?3, and Z = 2) and has refined to R = 0.029 and Rw = 0.039 with 2395 observations and 196 parameters varied.
