CF3SO3, cationic complexes with

CFjClj/CCFjCl, CU ) redox couple, 33 111 CF3SNCO, reactions of, 18 159 CF3SO3, cationic complexes with, 34 182 Chain structure supramolecular complexes, 46 251, 263... 

Perchlorate salts of organic or organometallic cations or complexes with organic ligands must be handled with extreme caution substitution of C104 by CF3SO3 or other non-coordinating anions is always advisable. 

Surprisingly, cationic complexes of Cu(I) and Ag(I), namely, [(NHC)2M] (CF3SO3), have been prepared by substitution of anionic ligand of M(CF3S03)2 with two equivalents of free carbene. ... 

Another thoroughly studied example of a lr2 system able to promote C-H bond activations is also nonsymmetric. The cationic A-frame complex [Ir2(CH3) (CO)2(dppm)2l [CF3SO3] accomplishes a double geminal C-H activation of butadiene to form the hydride-vinylvinylidene-bridged complex [lr2(CH3)( i-C=C(H)C (H)=CH2)(C0)2(dppm)2(H)( r-H)][CF3S03l (Scheme 23) [109, 110]. The proposed mechanism involves the activation of one of the geminal bonds to form an alkynyl complex with a bridging hydride, followed by a p-H inversion [109], to end with the second C-H activation. 

On the other hand, the reactions of the cationic Ru " complex [Cp RuCl(ju-SPr%Ru(OH2)Cp ](OTf) 4 (OTf = CF3SO3) with RNHNH2 (R = Ph or H) result in the formation of the terminal hydrazine complexes [Cp RuCl(/i-SPr%Ru(NH2NHR)Cp ][OTf] 5, which have been characterised spectroscopically as well as by a preliminary X-ray analysis for the phenylhydrazine complex 5a (R = Ph Figure ICb))." No disproportionation product has been detected in these reaction mixtures, in contrast to the reactions shown in Equations 1 and 2. 

More remarkably, structurally well-characterized Phen-containing transition metal complexes have been prepared and further applied in challenging organic transformations. Thus, cationic palladium complexes of t)fpe Pd(phen)2X2 (where X = CF3SO3, PFs, BF4) are very stable and found fairly active in combination with either benzoic acids or phosphorus acids as cocatalysts in the conversion of nitroarenes to the corresponding carbamate derivatives. Extensive studies have evidenced the key role of the nature of counteranion X of such Phen-based catalysts in the reaction outcome and even metaUacycles of type A have been isolated and identified as active intermediates in the reductive carbonyla-tion of nitrobenzene (eq l). ... 

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