Ferrocene, with

Fluorodiazirines are obtained from suitable perfluoro compounds by reduction. Difluorodiazirine (218) was prepared from perfluoromethylenediamine (290) by reduction with ferrocene (66JHC245), or from perfluoroformamidine (291) by iodide reduction (67JOC1944). 

Cyclopentadienyl derivatives of divalent lanthanides are also known [Ln ( j -C5H5)2] (Ln = Sm, Eu, Yb) might be expected to be isostructural with ferrocene but are bent ie rather than the two rings being parallel they are tilted relative to each other. 

The synthesis of cyclopentadienyliron(Ti -indolyl) proceeds through formation of 110 (88PAC1193). Transformation into the -complex occurs at elevated temperatures. Carbazole forms only the A-carbazolyl complex 111 under these circumstances. However, carbazole with ferrocene and aluminum chloride/aluminum powder gives the Ti -coordinated dication 112 [80JOM(186)265]. 

Asymmetric catalysis using chiral ligands, including cyclic phosphine or pyra-zole fragments covalent-bonded with ferrocene system 98PAC1477. 

Hie necessity of an anionic tbiolale ligand was established by perforniing reactions with ferrocene tliioetliets 37 as ligands. Here, essentially racemic products... 

IrCl4(PMe2Ph)2 undergoes a redox reaction with ferrocene forming... 

The burning rates of standard aluminized hydrocarbon binder composite proplnts may be increased significantly not only with ferrocene derivatives but also with compatible carborane-type burning rate additives. However, most ferrocene derivatives are volatile solids or liquids which have a tendency to evaporate from the proplnt during storage, thereby degrading ballistic performance. Rudy (Ref 71) minimized this problem by the use of polynuclear ferrocene... 

Scheme 10.13 1,3-Dipolar cycloadditions of azomethine ylides with ferrocene-derived S/P ligands and AgOAc.

The reaction of the crowded stibole 53 and bismole 54 with lithium followed by addition of lithium cyclopentadienide (Scheme 9) gives mixtures of the corresponding monostibaferrocene 69 and monobismaferro-cene 70, respectively, with ferrocene.25 The more volatile ferrocene is easily removed by sublimation. Rather small amounts of the crowded diheteroferrocenes 55 or 56 are formed in this reaction. 

Evidence for slow inversion at nitrogen in the compound (106) and its tetrachloro analogue has been obtained 142>. The adduct of tetra-fluorobenzyne with cyclopentadiene has been obtained but of rather more interest is the isolation of the isomeric adducts (108) and (109) from the reaction of tetrafluorobenzyne with nickelocene 143>. No adducts were obtained from attempted reactions with ferrocene 144 80). 

Jaworska-Augustyniak, A., Transition Met. Chem., 1979, 4, 207-208 Contact of tetranitromethane with ferrocene under various conditions leads to violent explosions, though not if the latter is dissolved in methanol or cyclohexane. Other ferrocene derivatives react violently, but not the dimethyl compound. 

V.B. Kandimalla, V.S. Tripathi, and H.X. Ju, A conductive ormosil encapsulated with ferrocene conjugate and multiwall carbon nanotubes for biosensing application. Biomaterials 27,1167-1174 (2006). 

The combination of [Rh(Cl(NBD)]2 and ligands 89, 90, 91, or 92 with diphenylsilane asymmetrically reduces aryl alkyl ketones, including acetophenones, in excellent yields and in 81 to 90% ee (Eq. 346).574 The best results are with ferrocene 91 and acetophenone in toluene.575 Other phosphine-substituted ferrocenes do not give comparable results. Rhodium(I) complexes of TADDOL-derived... 

One of the most interesting organometallic compounds of a transition metal is ferrocene (see Chapter 21). Butyllithium reacts with ferrocene to produce the mono and dilithiated compounds that have the following structures ... 

A great deal of chemistry has been carried out on complexes of the ferrocene type. Although most of the discussion here will deal with ferrocene itself, many of the reactions can be carried out with other metallocenes however, the conditions might be different. 

Starting with ferrocene, predict how you could prepare the following. 

Elimination of hydrogen halides from dihalogenoorganylboranes by reaction with ferrocene-1,1 -dithiol resulted in l,3-dithia-2-boryl[3]ferrocenophanes.170 These borylferrocenophanes were air sensitive, but were characterized by NMR, MS, and elemental analysis.170 A series of l,3-dibora-2-X-[3]fer-rocenophanes (X=S, Se, Te) were prepared and characterized and the crystal structure of [Se N Pr2)BC5Fl4 2Fe] has been reported.171... 

Diathiadiphosphetane disulfides are probably the most studied and the most thermally and hydrolytically stable of all the phosphorus-chalcogen heterocycles. They contain a central four membered P2S2 ring and can be prepared from heating phosphorus pentasulfide with aromatic compounds. The most well-known of these is Lawesson s reagent (43), which is made from anisole and phosphorus pentasulfide,92 and is used extensively in organic synthesis procedures (see Section 5.4.1). Other dithiadiphosphetane disulfides of note are 44 and 45, formed from the reaction of phosphorus pentasulfide with ferrocene or 1 -bromonaphthalene respectively.93... 

A two-term rate law is inferred, having one term (k0) for reaction of the free Co111 cation with ferrocene and the other term (kx) for reaction of... 

With ferrocenes, an alternative approach has been to attach the phosphorus moieties only to side chains. The WalPhos family (36) forms an eight-mem-bered chelate with the metal. Members of this family provide good selectivity and reactivity for the reductions of dehydroamino and itaconic acid derivatives as well as a,/ -unsaturated carboxylic acids [145, 156],... 

Enantioselective Hydrogenation of Alkenes with Ferrocene-Based Ligands... 

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