Synthesis of rhodium(I) and rhodium(III) perfluoroalkyl complexes from [Rh(micro-OH)(COD)]2.
Complexes [Rh(RF)(PMexPh3-x)3] (RF = CF3, x = 1 ( 2); RF = n-C3F7, x = 1 ( 3), x = 2 ( 4)) are quantitatively generated in situ when [Rh(-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(CF3)(COD)(PMe2Ph)2] ( 7) and [Rh(CF3)(COD)(PMe2Ph)] ( 8), the relative amounts of which depend on the Rh:PMe2Ph molar ratio. [Rh(CF3)(2-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(RF)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, RF = n-C3F7, x = 2 ( 14)). Oxidative addition of MeI (i) to 2 gives (PMe2Ph2)[OC-6-43]-[Rh(CF3)(Me)I2(PMePh2)2] ( 15), which reacts with Tl(acac) (acac = acetylacetonato) to give [OC-6-14]-[Rh(CF3)(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)(PMe2Ph)2] ( 19), respectively. Oxidative addition of iodotrifluoroethene to 12 affords [OC-6-32]-[Rh(CFCF2)(CF3)I(CNXy)(PMePh2)2] ( 20). The crystal structures of 10, 15 and 19 were determined.
Grupo de Química Organometálica, Departamento de Química Inorgánica, Facultad de Química, Universidad de Murcia, E-30071, Murcia, Spain. jvs1@um.es
José
J
Vicente
Juan
J
Gil-Rubio
Juan
J
Guerrero-Leal
Delia
D
Bautista