Ferrocenyl thiolate

The analogy between phenyl thiolate (Ph-S ) and ferrocenyl thiolate (Fc-S ) anions leads to the expectation that many compounds containing ferrocenyl thiolate units as either substituents or ligands should exist. This is indeed the case and, although with fewer examples, is also true for ferrocenyl selenolate and tellurolate. Similarly, l,T-ferrocenylene dithiolate compounds (which correspond to o-phenylene dithio-lates) are known, together with the analogous l,r-ferrocenylene diselenolates and ditellurolates. 

Main group element derivatives containing three or four ferrocenyl thiolate ligands are accessible from the corresponding element chlorides and Fc-SLi. Thus, the reaction of PCI3 with a suspension of 3 equivalents Fc-SLi in toluene — THF (3 1) leads to tris(ferrocenyl thiolato) phosphine, P(SFc)3 the oxide and sulfide, P(0)(SFc)3 and P(S)(SFc)3, are formed as side-products in addition to Fc-SS-Fc. The corresponding tris (ferrocenyl thiolato) element compounds As(SFc)3 and Sb(SFc)3 are also known the antimony derivative decomposes under the influence of either air or light [235]. 

Scheme5-39. Ferrocenyl thiolate and l,l -ferrocenylene dithiolate derivatives of half-sandwich transition metal complexes.

Ferrocenyl and ferrocenyl thiolate derivatives of the metals are heterobimetallic compounds, one component of which is iron. In principle, complex fragments of different metals may be combined with a ferrocene unit, as in the trimetallic l,T-ferrocenylene dithiolate, Cp(NO)2Cr-[S(fc)S]-W(CO)3Cp. Another versatile method to synthesize heterobimetallic complexes makes use of chelating ligands such as l,l -bis(diphenylphosphinyl) ferrocene, fc(PPh2)2 (see Chapter 1), and 1,1 -bis(methylchalcogenyl) ferrocene, fc(EMe)2 (E = S, Se), (Sect. 5.4). 

Karlstrom ASE, Huerta FF, Meuzelaar GJ, Backvall JE (2001) Ferrocenyl thiolates as ligands in the enantioselective copper-catalyzed substitution of allylic acetates with Grignard reagents. Synlett 923-926... 

Fig. 8 Titration of ATP2- with 9-Fc-thiolate dendron-AuNPs (Scheme 5). Decrease of the intensity of the initial CV wave ( ) increase of the intensity of the new CV wave ( ) vs. the number of equiv. of [m-Bu4N]2[ATP] added per ferrocenyl branch. Nanoparticles 3.8 x 10 M in CH2C12...

The monosulfide, Fc-S-Fc, was first prepared in 1961 by Rausch [48] by reaction of the thiolate Fc-SNa with iodoferrocene, Fc-I, in the presence of copper bronze at 150 °C. The disulfide, Fc-SS-Fc, had been obtained independently by Knox and Pauson [81] and by Nesmeyanov et al. [82] at an even earlier date (1958) by aerial oxidation of mercaptoferrocene, Fc-SH hydrolytic cleavage of ferrocenyl thiocya-... 

Figure 13. (a) Formation of mixed SAM on Au electrode, (b) immobilization of Fc-D, (c) immobilization of thiolated capture probe with bifunctional linker (succinimidyl 4-(/V-maleimidomethyl)cyclohexane-l-carboxylate (SMCC)), (d) hybridization with target, (e) hybridization with biotinylated detection probe, (f) association with avidin-alkaline phosphatase, (g) description of the process of the electrocatalytic reaction of />-aminophenol (p-AP) via electronic mediation of ferrocenyl dendrimer (Adapted from Ref. [160])... 

Scheme 6.3 Thiolation of BSA by SATA and labeling with N-(ferrocenyl)iodoacetamide 5.

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