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Reductive deoxygenation of acylferrocenes to the corresponding alkylferrocenes proceeded in excellent yields on utilizing a combination of sodium cyanotrihydroborate and boron trifluoride-diethyl ether.This method allows the synthesis of alkylferrocenes with functionalized tethers and is adaptable to large-scale preparations.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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A bis(phosphine)borane ambiphilic ligand, [Fe(h5-C5H4PPh2)(h5-C5H4PtBu{C6H4 (BPh2)-ortho})] (FcPPB), in which the borane occupies a terminal position, was prepared. Reaction of FcPPB with tris(norbornene)platinum(0) provided [Pt(FcPPB)] (1) in which the arylborane is h3BCC-coordinated. Subsequent reaction with CO and CNXyl (Xyl=2,6-dimethylphenyl) afforded [PtL(FcPPB)] {L=CO (2) and CNXyl (3)} featuring h2BC-And h1B-Arylborane coordination modes, respectively. Reaction of 1 or 2 with H2 yielded [PtH(m-H)(FcPPB)] in which the borane is bound to a hydride ligand on platinum. Addition of PhC2H to [Pt(FcPPB)] afforded [Pt(C2Ph)(m-H)(FcPPB)] (5), which rapidly converted to [Pt(FcPPB’)] (6; FcPPB’=[Fe(h5-C5H4PPh2)(h5- C5H4PtBu{C6H4 (BPh-CPh=CHPh-Z)-ortho}]) in which the newly formed vinylborane is h3BCC-coordinated. Unlike arylborane complex 1, vinylborane complex 6 does not react with CO, CNXyl, H2 or HC2Ph at room temperature.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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In recent years, redox flow batteries (RFBs) and derivatives have attracted wide attention from academia to the industrial world because of their ability to accelerate large-grid energy storage. Although vanadium-based RFBs are commercially available, they possess a low energy and power density, which might limit their use on an industrial scale. Therefore, there is scope to improve the performance of RFBs, and this is still an open field for research and development. Herein, a combination between a conventional Li-ion battery and a redox flow battery results in a significant improvement in terms of energy and power density alongside better safety and lower cost. Currently, Li-ion redox flow batteries are becoming a well-established subdomain in the field of flow batteries. Accordingly, the design of novel redox mediators with controllable physical chemical characteristics is crucial for the application of this technology to industrial applications. This Review summarizes the recent works devoted to the development of novel redox mediators in Li-ion redox flow batteries.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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The first 2-phospha[3]ferrocenophanes containing stereogenic carbon atoms in the three-atom bridge have been synthesised from phenylphosphane by stereospecific ring-closing phosphanation reactions. Either alpha-substituted 1,1?-bis-(hydroxymethyl)ferrocenes or the corresponding 2-oxa-[3]ferrocenophanes have been used as diastereomerically pure starting materials. The resolution of 1,2,3-triphenyl-[2]phosphaferrocenophane has been achieved by chromatographic separation of the diastereomeric adducts of a chiral cyclopalladate complex. The X-ray crystal structures of two 2-phospha[3]ferrocenophane-borane complexes are also reported. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Reaction of l,l’,3,3′-tetra(tert-amyl)benzobis(imidazolylidene) (1) with 2 equiv of FcN3 or FcNCS afforded bisadducts [(FcN3) 2(1)] (2) or [(FcNCS)2(1)] (3), respectively (Fc = ferrocene). To the best of our knowledge, these represent the first examples of complexes comprising metals indirectly connected to the carbene atoms of N-heterocyclic carbenes (NHCs) via their ligand sets. Cyclic and differential pulse voltammetry indicated that bis(NHC) 1 facilitated significant electronic coupling between ferrocene centers in 2 (DeltaE = 140 mV), but not in 3. We believe the different degrees of electronic interaction are due to geometric factors: the triazene linker in 2 is nearly coplanar with the bis(NHC) scaffold, whereas the isothiocyanate linker is orthogonal, as determined by X-ray crystallography. Employing this “indirect connection” strategy should enable tuning of metalmetal interactions by simple alteration the organic linker between NHC and MLn fragments rather than complete redesign thereof. Given that NHC-reactive azide or isothiocyanate groups can be incorporated into both organic and inorganic compounds, this approach is envisioned to facilitate access to otherwise inaccessible catalysts and materials.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Treatment of decaallylferrocene (1) with the Grubbs-II catalyst in refluxing dichloromethane has promoted the 5-fold ring-closing metathesis in 1 to afford single-bridged bis(1,4,5,8-tetrahydrofluorenyl)iron(II) species 3 in excellent yield. The preferential formation of 3 over quintuply bridged “superferrocenophane” 2 was explained as the intraannular RCM process being preferred over the interannular one in the reactions of polyallylferrocenes.

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1,1′-Diaminoferrocene (3) was conveniently synthesized by employing a Gabriel synthesis in two steps starting from 1,1′-dibromoferrocene (1). Compound 1 was reacted with 2.5 equivalents of phthalimide in the presence of Cu 2O using 4-picoline as a solvent to give 1,1′-diphthalimidoferrocene (2) in a moderate yield. Hydrazinolysis of 2 in EtOH afforded 3 in good yields of ca. 70%. The subsequent reaction of 3 with two equivalents of ethyloxalyl chloride in THF gave the diethyl ester of N,N’-ferrocenylene bis(oxamic acid) (1,1′-fcbaH2Et2, 4). The solution obtained by treating 4 with two equivalents of n-Bu4NOH in H2O was added to a solution of Pd(AcO)2 in THF to give the palladium complex [n-Bu 4N]2[Pd(1,1′-fcba)] (5) in ca. 80% yield. The compounds 24 were characterized by 1H, 13CNMR and IR spectroscopy as well as elemental analysis and the heterobinuclear complex 5 by 1H NMR and IR spectroscopy, elemental analysis and by a single-crystal X-ray diffraction study.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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To determine the trans effect on the rates of reductive eliminations from arylpalladium(II) amido complexes, the reactions of arylpalladium amido complexes bearing symmetrical and unsymmetrical DPPF (DPPF = bis(diphenylphosphino)ferrocene) derivatives were studied. THF solutions of LPd(Ar)(NMeAr?) (L = DPPF, DPPF-OMe, DPPF-CF3, DPPF-OMe,Ph, DPPF-Ph,CF3, and DPPF-OMe,CF3; Ar = C6H 4-4-CF3; Ar? = C6H4-4-CH 3, Ph, and C6H4-4-OMe) underwent C-N bond forming reductive elimination at -15 C to form the corresponding N-methyldiarylamine in high yield. Complexes ligated by symmetrical DPPF derivatives with electron-withdrawing substituents on the DPPF aryl groups underwent reductive elimination faster than complexes ligated by symmetrical DPPF derivatives with electron-donating substituents on the ligand aryl groups. Studies of arylpalladium amido complexes containing unsymmetrical DPPF ligands revealed several trends. First, the complex with the weaker donor trans to nitrogen and the stronger donor trans to the palladium-bound aryl group underwent reductive elimination faster than the regioisomeric complex with the stronger donor trans to nitrogen and the weaker donor trans to the palladium-bound aryl group. Second, the effect of varying the substituents on the phosphorus donor trans to the nitrogen was larger than the effect of varying the substituents on the phosphorus donor trans to the palladium-bound aryl group. Third, the difference in rate between the isomeric arylpalladium amido complexes was similar in magnitude to the differences in rates resulting from conventional variation of substituents on the symmetric phosphine ligands. This result suggests that the geometry of the complex is equal in importance to the donating ability of the dative ligands. The ratio of the differences in rates of reaction of the isomeric complexes was similar to the relative populations of the two geometric isomers. This result and consideration of transition state geometries suggest that the reaction rates are controlled more by substituent effects on ground state stability than on transition state energies. In addition, variation of the aryl group at the amido nitrogen showed systematically that complexes with more electron-donating groups at nitrogen undergo faster reductive elimination than those with less electron-donating groups at nitrogen.

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Photocatalytic oxidation of iron(ii) complexes by dioxygen occurred using the organic photocatalysts, 9-mesityl-10-methylacridinium ions (Acr+-Mes) and 2-phenyl-4-(1-naphthyl) quinolinium ions (QuPh+-NA), in the presence of triflic acid in acetonitrile under visible light irradiation. The electron-transfer state of Acr+-Mes produced upon photoexcitation oxidized the iron(ii) complexes, whereas it reduced dioxygen with protons to produce iron(iii) complexes and H2O2.

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A convenient new method was developed for the preparation of 1?-substituted-1-bromoferrocenes which are important precursors for the preparation of 1?,1?-disubstituted-biferrocenes. This method can also be applied to prepare asymmetrical disubstituted ferrocenes, which are potentially useful materials possessing non-linear optical and liquid crystalline properties.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion