2923-17-3Relevant articles and documents
Alkali metal trifluoroacetates for the nucleophilic trifluoromethylation of fullerenes
Bogdanov, Viktor P.,Dmitrieva, Veronika A.,Ioutsi, Vitaliy A.,Belov, Nikita M.,Goryunkov, Alexey A.
, (2019/07/17)
Fullerene C60 readily reacts with potassium and cesium trifluoroacetates yielding C60(CF3)–M+ salts, and subsequent acid hydrolysis gives ortho-C60(CF3)H. The reaction rate and the probability of the alternative reaction pathways strongly depend on the particular metal cation. Thus, the reactivity increases in the order Li 2- rather than CF3-functionalization of the fullerene, in good accordance with the hard/soft acids and bases theory. The nucleophilic trifluoromethylation is found to be applicable to other pristine fullerenes like C70 as well as to fullerene derivatives like p7mp-C70(CF3)10. It enables selective preparation of low trifluoromethylated fullerenes via regioselective consecutive trifluoromethylation under accurately controlled solution-phase conditions.
Carbamoyl (Carboxamido) Complexes as Precursors for Metallaoxetene, Isonitrile, and Aminomethylidyne Complexes of Iron
Anderson, Stephen,Hill, Anthony F.,Ng, Ying Thong
, p. 15 - 21 (2008/10/08)
The reaction of [Fe{C(=O)NiPr2}(CO)4]Li with (CF3CO)2O in diethyl ether followed by triphenylphosphine provides carbamoyl complexes [Fe{η2-OCNiPr2}(CF3)(CO) 2(PPh3)] (1) or [Fe(η2-OCNiPr2)(CO)2(PPh 3)2](O2CCF3) (2a·O2CCF3) depending on the reaction conditions. The same procedure performed in dichloromethane provides the aminomethylidyne complex [Fe(≡CNiPr2)(CO)3(PPh 3)](O2CCF3) (5·O2CCF3) as well as traces of [Fe(η2-OCNiPr2)(CO)2-(PPh 3)2](O2CCF3) (2a·O2CCF3). The reactions of 1 with moist AgBF4 or HBF4 provide [Fe-{η2-OCNiPr2}(CO)3(PPh 3)]BF4 (2b·BF4), via a putative difluorocarbene intermediate, [Fe{η2-OCNiPr2}(=CF2)(CO) 2(PPh3)]BF4. In a similar manner, [Fe(η2-OCNiPr2)(CF3)(CO)(dPPe)] (3) (obtained from 1 and dppe) reacts with HBF4(aq) to provide [Fe{η2-OCNiPr2}(CO) 2(dppe)]-BF4 (4·BF4). A difluorocarbene complex is also implicated in the formation of the ferraoxetene [Fe{κ2-C(NiPr2)OCF 2}(CO){HB(pz)3}] (6) (pz = pyrazol-1-yl), which results from treatment of 1 with K[HB(pz)3] under high dilution. Under more concentrated conditions [Fe{HB(pz)3}2] is obtained. The ferraoxetene undergoes an unusual acid hydrolysis with HBF4(aq)/CO to provide the isonitrile salt [Fe(CNiPr)(CO)2{HB(pz)3}]PF6 (7·PF6). The salt [Fe(≡CNiPr2)-(CO)3(PPh3)]I (5·I) is the product of the reaction of 1 with iodine, via an as yet obscure mechanism, which may however also involve ferraoxetene intermediates.
Synthesis of Pentafluorophenyl(ylide)silver(I) Complexes: X-Ray Structures of two Modifications of
Uson, Rafael,Laguna, Antonio,Uson, Alfredo,Jones, Peter G.,Meyer-Baese, Karen
, p. 341 - 346 (2007/10/02)
Monomeric silver ylide complexes (ER3=PPh3, PPh2Me, PPhMe2, or AsPh3) can be prepared by the reaction of Ag(CF3CO2) with Li(C6F5) and .The free ylides CH2PPh3, CH2PPh2Me, or CH(CO2Me)PPh3 react with Ag(C6F5) or AgClO4 to afford or ClO4 respectively.Several novel ylide-transfer reactions from silver ylides to other silver or gold centres are reported.The structures of two forms of have been established.The molecules differ mainly in the orientation of one phenyl ring.The C6F5 groups are highly distorted at the ipso carbon .
