RESUMEN
The κ2-(P,N)-phosphine ligand precursor NH(CH2CH2PCy2)2 can be used for the synthesis of the rhodium(I) complex [Rh(CO){ĸ3-(P,N,P)-Cy2PC2H4NHC2H4PCy2}][Cl] (1). The deprotonated complex [Rh(CO){ĸ3-(P,N,P)-Cy2PC2H4NC2H4PCy2}] (2) shows a cooperative reactivity of the PNP ligand in the activation reaction of SO2F2 to yield the rhodium fluorido complex trans-[Rh(F)(CO){ĸ2-(P,P)-Cy2PC2H4N(SO2F)C2H4PCy2}]2 (3) by S-F bond cleavage. It is remarkable that no reaction was observed when 3 was treated with hydrogen sources e. g. dihydrogen, organosilicon compounds such as triethylsilane or TMS-CF3 and different fluorine sources such as SF4 or Selectfluor®. However, the treatment of complex 3 with XeF2 in the presence of CsF resulted in the formation of the unique fluorido rhodium(III) complex cis,trans-[Rh(F)3(CO){ĸ2-(P,P)-Cy2PC2H4N(SO2F)C2H4PCy2}]2 (4). In the presence of pyridine(HF)X or BF3 the fluorido complex 3 converted into the dicationic complexes [Rh(CO){ĸ2-(P,P)-Cy2PC2H4N(SO2F)C2H4PCy2}]2[XF]2, X=HF (5) or BF3 (6), respectively.
RESUMEN
The AuI complex [Au{N(F)SO2 Ph}(SPhos)] (SPhos=dicyclohexyl(2',6'-dimethoxy[1,1'-biphenyl]-2-yl)phosphane) (2) bearing a fluoroamido ligand has been synthesized by reaction of the fluorido complex [Au(F)(SPhos)] (1) with NFSI (NFSI=N-fluorobenzenesulfonimide). A reaction with CO resulted in an unprecedented insertion into the N-F bond at 2. With the carbene precursor N2 CH(CO2 Et) N-F bond cleavage gave the Au-F bond insertion product [Au{CHF(CO2 C2 H5 )}(SPhos)] (7). The presence of CNtBu led to Au-N cleavage at 2 and concomitant amide formation to give the cationic complex [Au(CNtBu)(SPhos)][N(F)SO2 Ph)] (5), which reacted further to give FtBu as well as the cyanido complex [Au(CN)(SPhos)] (6). These results led to the development of a process for the amination of electrophilic organic substrates by transfer of the fluoroamido group NF(SO2 Ph)- .
RESUMEN
Gold(I) fluorido complexes with phosphine ligands have been synthesized from their respective iodido precursors. The bonding situation in comparison between complexes bearing phosphines and N-heterocyclic carbenes (NHCs) was explored quantum-chemically, obtaining similar results for both. Calculations of the 19F NMR chemical shifts match the experimental values well, including the approximately 40 ppm low-field shifts for the phosphine complexes compared to the NHC complexes, in spite of similar negative charges on fluorine. The reactivity of the highly water-sensitive gold(I) fluorido complexes was studied, resulting in substitution at the metal using trimethylsilyl reagents. The compounds studied were characterized using NMR as well as X-ray diffraction methods.
RESUMEN
Reactions of the trityl cations with germanes afford the germylium ions [R3Ge][B(C6F5)4] (1a: R = Et, 1b: R = Ph, 1c: R = nBu). These compounds react with germane or fluorogermane to give polynuclear species, which are sources of the mononuclear ions, The latter convert with phosphines to yield the [R3Ge-PR3]+ (4a: R = Et, 4b: R = Ph) cations. Catalytic dehydrofluorination reactions were observed for the C-F bond activation of fluoroalkanes when using germanes as hydrogen source.
RESUMEN
This communication describes an efficient palladium pincer complex-catalyzed allylic C-H borylation of alkenes. The transformation exhibits high regio- and stereoselectivity with a variety of linear alkenes. A synthetically useful feature of this allylic C-H borylation method is that all allyl-Bpin products can be isolated in usually high yields. Preliminary mechanistic studies indicate that this C-H borylation reaction proceeds via Pd(IV) pincer complex intermediates.