Ferrocene substitution

The lithium benzamidinates Li[PhC(NR)2] (R = Cy, Pr ) and Li[2,4,6-(Cp3)3C6H2C(NCy)2] have been prepared analogously. Reaction of FcLi (Fc = ferrocenyl) with 1,3-dicyclohexylcarbodiimide ( = DCC, Scheme 6), followed by addition of water, afforded the ferrocene-substituted amidine Fc(NCy)NHCy in 50% yield. The amidine is readily deprotonated by LLN(SiMe3)2 or NaN(SiMe3)2 to yield the alkali metal amidinates, Li[FcC(NCy)2l and Na[FcC(NCy)2l in high yields. ... 

Ferrocene compounds containing heteroelements are versatile building blocks for polynuclear complexes. They possess electrochemically active iron centers as well as unique cylindrical shapes. An example of ferrocene-substituted thiolato ligands is l,l -ferrocenedithiolate (S2fc). Its complex with Pd(II) lacks a Pd—Fe bond. 

Replacements of ferrocene-substituted p-diketone ligands, p-dik, in cyclooctadiene-rhodium(I) complexes [Rh(p-dik)(cod)] by 1,10-phenan-throline are characterized by large negative activation entropies, indicating the operation of the expected associative mechanism, although the... 

Polycarboxylic acid dendrimers obtained in this way were reacted with ferrocene-substituted tertiary amines N[(CH2)4-Fc]3 (Fc=ferrocenyl), leading to ammonium salts containing a total of 243 terminal ferrocene units [6]. 

Ferrocenes substituted with silicon-silicon groupings are prepared by (1) the reaction of lithiated ferrocenes with an appropriate chloropolysilane and/ or (2) lithiation of a cyclopentadienyldisilane followed by treatment with ferrous chloride. The following give examples (116,117) ... 

SCHEME 10. Redox and complexation equilibria for ferrocene-substituted ionophore, Fcl. f, denotes free (uncomplexed) ionophore c, denotes complexed species Kj = kjlkr... 

Spencer J, Mendham AP, Kotha AK, Richardson SCW, Hillard EA, Jaouen G, Male L, Hursthouse MB (2009) Structural and biological investigation of ferrocene-substituted 3-methylidene-l, 3-dihydro-2H-indol-2-ones. Dalton Trans 6 918-921... 

A powerful route to dithiolene complexes employs alkenedithiolate dianions generated by the hydrolysis of cyclic unsaturated dithiocarbonates, which are formally called l,3-dithiole-2-ones. Representative of the many examples (60), the base hydrolysis route has been used to prepare the ferrocene-substituted dithiolene Ni[S2C2H(C5H4)FeCp]2 (61), the sulfur-rich dithiolene [Ni(S2C2S2-C2H4)2F (62), the cyano(dithiolenes) fra s- Ni[S2C2H(CN)]2 (n = 1, 2) (63), 2,3-thiophenedithiolates [Au(S2C,H2S)21 (64), and the tris(styryldithiolate)... 

L3039>, and diarylbenzo[c]selenophenes <2005TL7201>. The reversible redox reactions of ferrocene-substituted benzo[f]selenophenes 15 were also studied and established a new type of multistep reversible redox system <2006TL2887, 2007JOM(692)60>. 

Scheme 3 Synthesis of ferrocene-substituted poly(ene) by alternating copolymerization...

Ferrocene substituted amldinate complexes are also known. For example, reaction of fer-rocenyl lithium with DCC affords the lithium amldinate 44, which on hydrolysis gives the... 

Electron transfer across ferrocene-substituted oligo(phenylene-ethynylene)thiols (System 14) on gold has been studied using the ILIT technique [122] (see above) and electrochemistry [50]. Values of / = 0.57 + 0.02 and 0.36 A were obtained, respectively. Using the electrochemistry method, is 350 s for the 43 A, 36-bond, six-unit conjugated spacer, compared with 1.25 s for the 23 A, 18-bond alkanethiol... 

Ferrocene is an attractive and convenient organometallic species to incorporate into conjugated polymers—it is stable, easy to functionalize, has reversible electrochemistry, and its derivatives (both monomeric and polymeric) can be easily characterized [e.g., by nuclear magnetic resonance (NMR) spectroscopy]. Ferrocene has been incorporated into the backbone and side chains of polythiophene 45 In 1999, both Higgins and Wolf independently reported the synthesis of polythiophenes with ferrocene in the backbone.46,47 Electropolymerization of ferrocene substituted... 

Gale. P.A. Hursthouse. M.B. Light, M.E. Sessler, J.L. Wamner, C.N. Zimmerman. R.S. Ferrocene-substituted calix[4]pyrole A new electrochemical sensor for anions involving CH... anion hydrogen bonds. Tetrahedron Lett. 

Studies of synthetic porphyrin-based anion receptors should form the basis for more effective sensors. Metallocene-substituted porphyrins examined by Beer and coworkers have proven successful in the solution-phase binding of ions such as chloride, bromide and nitrate." The cobaltocenium-substituted and ferrocene-substituted porphyrins (Figure 134) bind ions in solution, as shown by H NMR and electrochemical studies. The latter measurements reveal that the porphyrin and ferrocene redox... 

Chen, J., A.K Burrell, G.E. Collis, D.L. Officer, G.F. Swiegers, C.O. Too, and G.G. Wallace. 2002. Preparation, characterization and biosensor application of conducting polymers based on ferrocene substituted thiophene and terthiophene. Electrochim Acta 47 (17) 2715. 

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