1165953-15-0Relevant articles and documents
Synthesis of rhodium(i) and rhodium(iii) perfluoroalkyl complexes from [Rh(μ-OH)(COD)]2
Vicente, Jose,Gil-Rubio, Juan,Guerrero-Leal, Juan,Bautista, Delia
, p. 3854 - 3866 (2009)
Complexes [Rh(RF)(PMexPh3-x)3] (RF = CF3, x = 1 (2); RF = n-C 3F7, x = 1 (3), x = 2 (4)) are quantitatively generated in situ when [Rh(μ-OH)(COD)]2 (1) is reacted with the corresponding Me3SiRF and PMexPh3-x. In contrast, the reaction of 1 with Me3SiCF3 and PMe2Ph gives mixtures containing [Rh(CF3)(PMe2Ph)3] (5), [Rh(CF3)(PMe2Ph)4] (6), [Rh(CF 3)(COD)(PMe2Ph)2] (7) and [Rh(CF 3)(COD)(PMe2Ph)] (8), the relative amounts of which depend on the Rh:PMe2Ph molar ratio. [Rh(CF3)(η2- O2)(PMePh2)3] (9) was isolated after bubbling air through a solution of 2 in THF. Reactions of in situ generated 2-5 with L = CO, XyNC (Xy = 2,6-dimethylphenyl) gives pentacoordinate complexes [Rh(R F)L(PMexPh3-x)3] (L = CO, x = 1, RF = CF3 (10), n-C3F7 (11); L = XyNC, RF = CF3, x = 1 (12), 2 (13); L = XyNC, R F = n-C3F7, x = 2 (14)). Oxidative addition of MeI (i) to 2 gives (PMe2Ph2)[OC-6-43]-[Rh(CF 3)(Me)I2(PMePh2)2] (15), which reacts with Tl(acac) (acac = acetylacetonato) to give [OC-6-14]-[Rh(CF 3)(Me)(acac)(PMePh2)2] (16), (ii) to 5 gives [Rh(CF3)(Me)I(PMe2Ph)3] as a ca. 5: 1 mixture of the isomers OC-6-34 (17) and OC-6-43 (17′), and (iii) to 12 or 14 leads to [OC-6-52]-[Rh(CF3)(Me)I(CNXy)(PMePh2)2] (18) or [OC-6-52]-[Rh(n-C3F7)(Me)I(CNXy)(PMe 2Ph)2] (19), respectively. Oxidative addition of iodotrifluoroethene to 12 affords [OC-6-32]-[Rh(CFCF2)(CF 3)I(CNXy)(PMePh2)2] (20). The crystal structures of 10, 15 and 19 were determined.
