870100-99-5Relevant academic research and scientific papers
Synthesis and reactivity of trifluoromethyl isocyanide rhodium(I) complexes
Vicente, Jose,Gil-Rubio, Juan,Guerrero-Leal, Juan,Bautista, Della
, p. 5634 - 5643 (2008/10/09)
The complex trans- [Rh(CF3)(CNXy)2(PPh3)] (1) reacts with SO2, tetracyanoethylene (TCNE), or maleic anhydride (MA) to give the complexes [Rh(CF3)(CNXy)2(PPh 3)L] (L = SO2 (2), TCNE (3), MA (4)) and with CO or CF3CO2H to give, respectively, mixtures containing mainly [Rh(CF3)(CNXy)2(CO)(PPh3)] or trans-[Rh(CNXy)2(PPh3)2]CF3CO 2, which is prepared in better yield by reaction of trans-[RhCl(PPh3)2(CO)] with XyNC and NaCF 3-CO2. [Rh(CF3)(CNXy)3] (6) is prepared by reaction of [Rh(CF3)(CNXy)3(PPh3)] (7) with 35% H2O2 or, better, by reaction of [Rh(μ-OH)(COD)]2 with XyNC and Me3SiCF3. The reaction of 6 with tetracyanoethylene (TCNE) or maleic anhydride (MA) gives the complexes [Rh(CF3)-(CNXy)3L] (L = TCNE (8), MA (9)). The oxidative addition reaction of Mel or n-C4F9I with complex 6 gives the octahedral Rh(III) complexes [Rh(CF3)(R)I(CNXy) 3] (R = Me (10), n-C4F9 (11)). In an attempt to obtain single crystals of complex 11, a few crystals of [{Rh(CF 3)(n-C4F9)(CNXy)2} 2(μ-I)2] (12) were obtained. The crystal structures of complexes 2-4 and 12 have been determined by X-ray diffraction studies.
Synthesis of the first family of rhodium(I) perfluoroalkyl complexes from rhodium(I) fluoro complexes
Vicente, Jose,Gil-Rubio, Juan,Guerrero-Leal, Juan,Bautista, Delia
, p. 4871 - 4881 (2008/10/09)
The rhodium(I) fluoro complexes [RhF(COD)(PR3)] (R = Ph (1a), C6H4OMe-4 (1b), i-Pr (1d), Cy (1e); COD = 1,5-cyclooctadiene) react with Me3SiRF to afford the rhodium(I) perfiuoroalkyl complexes [Rh(RF)(COD)(PR3)] (RF = CF3, R = Ph (2a), C6H4OMe-4 (2b), i-Pr (2d), Cy (2e); RF = n-C3F7, R = Ph (2c)), of which 2a,c were isolated as pure solids. [Rh-(CF3)(NBD) PPh3)] (3) was prepared by reaction of 2a with norbornadiene. The reactions of 2a-c with 2,6-dimethylphenyl isocyanide (XyNC) or t-BuNC, in a 1:2 molar ratio, gave the compounds tarns-[Rh(RF)CNR′) 2(PR3)] (RF = CF3, R′ = Xy, R = Ph (4a), C6H4OMe-4 (4b); RF = CF3) R′ = t-Bu, R = Ph (4a′); RF = n-C3F 7, R′ = Xy, R = Ph (4c)). The reactions of 2a-c with an equimolar amount of XyNC gave mixtures containing complexes 4a-c as the major products. The peroxo complexes [Rh(CF3)(η2-O 2)(CNXy)2(PR3)], (R = Ph (7a), C 6H4OMe-4 (7b)) were isolated by reacting O2 with 4a,b, respectively. The complexes [Rh(RF)(CNR′) 3- (PR3)] (RF = CF3, R′ = Xy, R = Ph (8a), C6H4OMe-4 (8b); RF = n-C 3F7, R′ = Xy, R = Ph (8c)) were obtained by reaction of 2a-c with 3 equiv of XyNC. Formation of [Rh(CF3)PPh 3)-(CO)3] (9) in the reaction of complex 2a with CO was spectroscopically observed. The crystal structures of complexes 4a, 7a, and 8a have been determined by single-crystal X-ray diffraction studies. The dynamic behavior in solution of the prepared complexes was studied by variable-temperature NMR.
