Ruthenium complexes fluorides

Some complex fluorides of ruthenium. Rec.Trav.Chim.Pays-Bas 75,576 (1956). 

Ruthenium complexes mediate the hydroamination of ethylene with pyridine.589 The reaction, however, is not catalytic, because of strong complexation of the amine to metal sites. Iridium complexes with chiral diphosphine ligands and a small amount of fluoride cocatalyst are effective in inducing asymmetric alkene hydroamination reaction of norbomene with aniline [the best enantiomeric excess (ee) values exceed 90%].590 Strained methylenecyclopropanes react with ring opening to yield isomeric allylic enamines 591... 

A ruthenium hydride fluoride, [RuHF(CO)L2] (L = P Bu2Me) has also figured in new chemistry of CF2 as a ligand [54], The complex was prepared by reaction of [RuHCl(CO)L2] and anhydrous CsF in acetone. Compounds of the same general formula have also been used in detailed studies on reactivity and stereochemistry of ligands attached to ruthenium centres. Thus, the relative electron-donating ability... 

Some of the modifications for the Nicholas reaction include the fixation of a propargylic substrate onto a solid phase,application of montmorillonite K-10 as acid to generate the propargylic cation, complexation of alkyne with a ruthenium complex, and application of tetrabutylammonium fluoride for decomplexation. ... 

The occurrence of piezoelectric behaviour in LB films has been known for some time [57,58], and a 30 X-type layer LB film of (37) was found to give opposite signs of the piezoelectric strain coefficients d i and d [59], the latter having a value of 1.5 pC which is approximately an order of magnitude lower than that of the well-documented polymer poly(vinylidene fluoride) (PVDF). Values for 31 of 0.023 and 0.170 pC N have also been obtained for alternate-layer structures of 22-tricosenoic acid with docosylamine, and a ruthenium complex with docosanoic acid respectively [60]. As the use of pyroelectric materials in detector applications requires that the materials possess only low levels of piezoelectricity (high levels introduce problems of microphony), this suggests that the former materials would be better suited for pyroelectric detector applications, while the latter system would be more appropriate for piezoelectric-based applications. 

Binary Compounds. The mthenium fluorides are RuF [51621 -05-7] RuF [71500-16-8] tetrameric (RuF ) [14521 -18-7] (15), and RuF [13693-087-8]. The chlorides of mthenium are RUCI2 [13465-51-5] an insoluble RuCl [10049-08-8] which exists in an a- and p-form, mthenium trichloride ttihydrate [13815-94-6], RuCl3-3H2 0, and RuCl [13465-52-6]. Commercial RuCl3-3H2 0 has a variable composition, consisting of a mixture of chloro, 0x0, hydroxo, and often nitrosyl complexes. The overall mthenium oxidation state is closer to +4 than +3. It is a water-soluble source of mthenium, and is used widely as a starting material. Ruthenium forms bromides, RuBr2 [59201-36-4] and RuBr [14014-88-1], and an iodide, Rul [13896-65-6]. 

Nothing seems to be known of the structures of some further hexa-fluorometallates, such as Ba(VFe)2 97) and the analogous compounds of ruthenium(V), A(RuF6)2 (As+ = Ca, Sr, Ba) 141). The same applies to some ternary fluorides of platinum(IV), A2(PtFe)3 (A3+ = La, Pr, Nd) 257) as well as to one other of cobalt(III), Ba3(CoFe)2 71, 225). The assumption of isolated MeFa-octahedra in these complexes remains still to be proved. 

The importance of fluorinated organic componnds both in medicinal chemistry and biochemistry has resulted in much recent attention towards efficient carbon fluorine bond formation [30]. The reactions developed include a very successful electrophilic asymmetric mono-fluormation of 1,3-dicarbonyl compounds [31]. A nucleophilic variant was also investigated. In this context, the groups of Togni and Mezzetti have established that ruthenium Lewis acids could efficiently catalyze fluorination reactions [32]. In the presence of [Ru(l,2-bis(diphenylphosphino)ethane)2Cl][PF6] (8) (10 mol%), fert-butyl iodide reacted at room temperature with TIF (1.1 equiv.) to yield fert-butyl fluoride (84% yield). This reaction was extended successfully to a range of organic halides (Entries 1-3, Scheme 10.19). The use of the chiral complex [Ru((lS,2S)-N,N bis[2-diphenylphos-phino)benzylidene]diaminocydohexane))Cl][PF6] (9) showed modest chiral induction at the outset of the reaction (Entry 4, Scheme 10.17). The near-racemic mixture obtained at completion points to an SNl-type process in this nucleophilic halide... 

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