Synthesis and Characterization of Ferrocenylchalcogenopropargyl Complexes [Fe(η⁵-C₅H₄E^ICH₂C⋮CH)₂] (E^I = Se, S) and Their Reactions To Form Unusual Ferrocenyl-Containing Metal Clusters with Eclipsed Cp Rings and New Five-Membered FeE^ICHCCH₂ Ring Ligand System

Abstract

The new bis(chalcogenopropargyl)ferrocene complexes [Fe(η5-C5H4EICH2C⋮CH)2] (EI = Se, 1; EI = S, 2) have been prepared by treatment of the dilithiated [Fe(η5-C5H4Li)2] with Se or S powder, followed by reaction with propargyl bromide. Reaction of 1 and 2 with [Fe2M(μ3-E)2(CO)9] (E = S, Se and M = Fe, Ru) forms new clusters which feature an unusual five-membered FeEICHCCH2 ring with a π bond between the olefinic unit and the Fe atom, and the Cp rings adopt an eclipsed arrangement. The structures of 1 and [Fe(η5-C5H4EICH2C⋮CH)(η5-C5H4{Fe2M(CO)8(μ-E)(μ3-E)(EICHCCH2)})] (M = Fe, E = Se, EI = Se, 3; M = Fe, E = S, EI = Se, 4; M = Ru, E = S, EI = Se, 7) have been determined crystallographically.

Photochemical reactions of Fe(CO)5 with FcCCH in the presence of S-powder and CS2: Synthesis and characterization of [{μ-SC(H)C(Fc)S}(CO)6Fe2], [μ-SC(O)C(H)C(Fc)S}(CO)6Fe2]; cis-[μ-η1:η2:η1:η1-{C(Fc)C(H)CS2C(H)C(Fc)}(CO)6Fe2] and trans -[μ-η1:η2:η1:η1-{C(Fc)C(H)CS2C(Fc)C(H)}(CO)6Fe2]

“…The Fe(1)-S(1) bond distance of 2.282(2) Å in 5 and 2.279(17) Å in 6 is comparable with the average Fe-S bond distances of 2.2893 Å in [{l-SeC(H)@C(Ph)S}(CO) 6 Fe 2 ], 2.263(2) Å in [{lSC(H)@C(Ph)Te}(CO) 6 Fe 2 ] and 2.261 Å in [{l-SC(C" CCH 3 )@C(H)Te}(CO) 6 Fe 2 ] but longer than the average Fe-S bond distances of 2.228 Å observed in (CO) 6 Fe 2 S 2 . The average C-S bond distances of 1.77475 Å in 5 and 1.7705 Å in 6 is comparable with 1.763(3) Å in [(g 5 -C 5 Me 5 )MoFe 3 (l 3 -S){(l 3 -C(H)@C(Ph)S}(CO)6 (l 3 -CCPh)][8], but slightly shorter than the C-S bond distance in Os 4 (CO)12 [l 4 -g 3 -SC(Ph)@CH] (1.817(11) Å )[23]. The S-C-S bond angle of 109.5(4)°in 5 and 108.5(3)°in 6…”

“…With less bulky acetylenes, formation of substituted quinones was not observed. Contrast in behavior of ferrocenylacetylene and phenylacetylene has also been observed in their reactions with mixtures of [Fe 3 (CO) 9 were treated with [Fe 3 (CO) 9 (l 3 -S) 2 ] in the presence of different acetylenes HC"CR (R = Ph), n-Bu or Fc{(g 5 -C 5 H 5 )(g 5 -C 5 H 4 )Fe}, we isolated mixed-metal clusters [Fe 3 M[(g 5 -C 5 Me 5 )(CO) 6 [8].…”

Synthesis, structure and electrochemistry of CO incorporated diruthenium metallacyclic compounds [Ru2(CO)6{μ-η1:η1:η2:η2-1,4-Fc2C5H2O}] and [Ru2(CO)6{μ-η1:η1:η2:η2-1,5-Fc2C5H2O}]

“…Mass spectra (m/z): 818.4,790.5,762.5,734.5. Compound 2: IR (m(CO), cm À1 , n-hexane): 2085.9, 2064, 2024.5, 1892.9, 1724. 13 C NMR (d,CDCl 3 ): 69. Cp),120.3 (s,C@CH),139.8 (s,FcC@CH),192.5 (CO).…”

“…In recent times we have focused our attention on investigation of reactions of acetylenes with metal acetylides and have found that bulky acetylenes, such as ferrocenylacetylene introduce novel features in reactions with metal acetylides [13]. Under photolytic conditions, reaction between ferrocenylacetylene and Fe(CO) 5 yields 2,5-and 2,6-diferrocenylquinones [14], whereas from the reactions of ferrocenylacetylene with mononuclear metal carbonyls Fe(CO) 5 and M(CO) 6 (M = Mo, W) under thermolytic conditions, [Fe(CO) 2 {g 5 -2,5-Fc 2 C 5 H 2 CO}C(Fc)@CH], [Fe(CO) 2 {g 2 : g 2 -2,5-Fc 2 C 4 H 2 Fe(CO) 3 }l-CO] and [Fe(CO) 3 {g 2 :g 2 -2,5-Fc 2 C 4 H 2 CO}], 1,2,4-triferrocenylbenzene, 2,5-diferrocenylthiophene, and 2,5-diferrocenylselenophene, respectively, have been isolated.…”

Coupling reaction between the uncoordinated acetylenic bond of [Ru3(CO)10{μ3-FcC2CCFc}] and FcCCCCFc to form [Ru2(CO)6{C4Fc2(CCFc)2}2], [Ru2(CO)6[μ-η1:η1:η2:η2-{FcCCCC(Fc)–C(O)–C(Fc)CCCFc}] and [Ru2(CO)6[μ-η1:η1: η2:η2-{FcCCCC(Fc)–C(O)–C(–CCFc)C(Fc)}]

“…Reactions of ferrocenylacetylene with metal acetylides form ferrocenyl-incorporated mixed-metal clusters and such reactions contrast with others where acetylenes with less bulky substituents are used [13]. Ferrocenylacetylene and Fe(CO) 5 react under photolytic conditions to yield 2,5-and 2,6-diferrocenylquinones [14], and thermolytic reactions of ferrocenylacetylene with Fe(CO) 5 forms [Fe(CO) 2 {g 5 -2,5-Fc 2 C 5 H 2 CO}C(Fc)@CH], [Fe(CO) 2 {g 2 : g 2 -2,5-Fc 2 C 4 H 2 Fe(CO) 3 }l-CO], [Fe(CO) 3 {g 2 :g 2 -2,5-Fc 2 C 4 -H 2 CO}] and 1,2,or with MCO 6 (M = Mo, W) in presence of sulfur or selenium powder 2,5-diferrocenylthiophene, and 2,5-diferrocenylselenophene, respectively are formed.…”