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4 results on '"Guerrero-Leal, J."'

1. Synthesis and Reactivity of Trifluoromethyl Isocyanide Rhodium(I) Complexes

Author

Vicente, J., Gil-Rubio, J., Guerrero-Leal, J., and Bautista, D.

Abstract

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(PPh3)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]CF3CO2, which is prepared in better yield by reaction of trans-[RhCl(PPh3)2(CO)] with XyNC and NaCF3CO2. [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 MeI 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(CF3)(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.

Published
2005

2. Synthesis of the First Family of Rhodium(I) Perfluoroalkyl Complexes from Rhodium(I) Fluoro Complexes<SUP>1</SUP>

Author

Vicente, J., Gil-Rubio, J., Guerrero-Leal, J., and Bautista, D.

Abstract

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) perfluoroalkyl 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 trans-[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-C3F7, 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-O2)(CNXy)2(PR3)], (R = Ph (7a), C6H4OMe-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-C3F7, R‘ = Xy, R = Ph (8c)) were obtained by reaction of 2a−c with 3 equiv of XyNC. Formation of [Rh(CF3)(PPh3)(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.

Published
2004

3. New media for classical coordination chemistry: phase transfer of Werner and related polycations into highly nonpolar fluorous solvents.

Author

Ghosh SK, Ojeda AS, Guerrero-Leal J, Bhuvanesh N, and Gladysz JA

Subjects
Cations chemistry, Models, Molecular, Molecular Structure, Organometallic Compounds chemical synthesis, Solvents chemistry, Stereoisomerism, Boron Compounds chemistry, Cobalt chemistry, Organometallic Compounds chemistry, Polymers chemistry
Abstract

Optimized procedures for the previously reported conversions of 1,3-diiodobenzene and perfluorohexyliodide (Rf6I; copper, DMSO, 140 °C) to 1,3-C6H4(Rf6)2 (3; 86-70%) and 3 to Br(3,5-C6H3(Rf6)2 (2; NBS, H2SO4/CF3CO2H; 88-75%) are described. The latter is converted (t-BuLi, BCl3) to the "fluorous BArf" salt NaB(3,5-C6H3(Rf6)2)4 (1 or NaBArf6; 77-70%), as given earlier. When orange aqueous solutions of [Co(en)3]Cl3 (en = ethylenediamine) are treated with perfluoro(methylcyclohexane) (PFMC) solutions of 1 (1:3 mol ratio), the aqueous phase decolorizes and [Co(en)3](BArf6)3 can be isolated from the fluorous phase (96%). Similar reactions with the trans-1,2-cyclohexanediamine analogue [Co(R,R-chxn)3]Cl3 and [Ru(bipy)3]Cl2 give [Co-(R,R-chxn)3](BArf6)3 (92%) and [Ru(bipy)3](BArf6)2 (95%). All of these salts are isolated as hydrates and exhibit toluene/PFMC partition coefficients of ≤1:≥99, establishing that the anion BArf6(-) can efficiently transport polar polycations into highly nonpolar fluorous phases. When equal volumes of CH2Cl2 and PFMC are charged with the "nonfluorous" BArf (B(3,5-C6H3-(CF3)2)4) salt [Co(en)3](BArf)3 and 3.0 equiv of the fluorous salt NaBArf6, the cobalt trication partitions predominantly into the fluorous phase (64:36). The arene 2 crystallizes in a polar space group (tetragonal, I4, Z = 8) with fluorous and nonfluorous domains and all eight bromine atoms located essentially on one face of the unit cell.

Published
2013
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4. Synthesis of rhodium(I) and rhodium(III) perfluoroalkyl complexes from [Rh(micro-OH)(COD)]2.

Author

Vicente J, Gil-Rubio J, Guerrero-Leal J, and Bautista D

Abstract

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.

Published
2009
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