An expedient approach to ferrocenyl thioamides via Fischer carbenes

Preparation, Properties, and Reactivity of (Aminoferrocenyl)(ferrocenyl)carbene(pentacarbonyl)chromium(0) as Bulky Isolobal Trimetallo‐amide

“…The isolobal relationship of M (CO) 5 ( M = Cr, Mo, W) complex fragments and the chalcogens O and S5e has been utilized in the synthesis of ferrocenyl thioesters and thio‐ and selenoamides (Fc)( R )C= X [ X = S; R = OEt, NH R ′; R ′ = H, Me, Et, Pr; X = Se: R = NH R ′; R ′ = (CH 2 ) n OH, n = 1–3, CH 2 (C(H)OH)Me, CH 2 (C(H)OH)Me], as formal oxidation products of corresponding Fischer carbene complexes (Fc)( R )C= M (CO) 5 [ X = S: R = OEt, NH R ′'; R ′ = H, Me, Et, Pr, M = Cr, Mo, W; X = Se: R = NH R ′; R ′ = (CH 2 ) n OH, n = 1–3, CH 2 (C(H)OH)Me, CH 2 (C(H)OH)Me, M = Cr] 20a,20b. From this perspective, we envisaged the title compound (Fc)(NHFc)C=Cr(CO) 5 ( 3 ) as a metallo amide analogous to the respective diferrocenyl chalcogene amides (Fc)(NHFc)C= X (Scheme b, 4 : X = O; 5 : X = S) in addition to the description of 3 as a novel oligometallic heteroatom stabilized Fischer carbene complex 17e,23…”

Organized Molecular Assemblies based on Ferrocenyl Derivatives

“…The synthesis of aminoferrocenyl carbene was conducted through an aminolysis reaction with hexadecylamine, figure 3. The synthesis of ferrocenylthioamide (1b), figure 5, was obtained following a process previously described [8]. The new thioamide, with long alkyl side chain, was characterized by conventional spectroscopic techniques.…”

“…For these ferrocene derivatives different elements as S, Se and Cr have been included, wherein a charge transfer donor group of ferrocene to these elements is possible by means of the conjugated bonds. For these LB films the photochemical behavior, semiconductor and their potential optical-electronic properties will be studied To obtain alkyl thioamides [8] and seleniumcarbonyl [9] compounds, ferrocenyl carbene complexes were used as precursors, figure 2, which were treated with NaBH4 to promote demetalation of ferrocenyl aminocarbene complexes with elemental sulfur or selenium to produce ferrocenylthioamide (1b) or ferrocenylselenoamide (1c) compounds. Finally, these nanostructures obtained from ferrocenyl derivatives were developed as Langmuir films (L) at the air-water interface.…”

Nanostructured LB Films Developed from Ferrocenylthioamide and Ferrocenylselenoamide Compounds

“…Then, different procedures were developed to remove the metal moiety and to transform Fisher carbene complexes into organic products. The synthesis of ferrocenylthioamide, figure 3, was obtained following a process previously described [6]. The new thioamide was characterized by conventional spectroscopic techniques.…”

“…In a similar way, alkyl thioamides, new thiocarbonyl [6] and seleniumcarbonyl [7] moieties bonded to the ferrocene have been used as precursors of LB films. From ferrocenyl carbene complexes, previously synthesized [8], compounds were treated with NaBH 4 -promoted demetalation of ferrocenyl aminocarbene complexes with elemental sulfur or selenium as an alternative to obtain ferrocenylthioamide or ferrocenylselenoamide compounds.…”