Camino Bartolomé

• University of Valladolid

Using non-classical polyfluorophenyl ligands in Pt(II) complexes and other transition metals such as silver is a promising approach in the search for more effective and safer antitumoral drugs. In this work, a series of chelating N-donor ligands with 1,10-phenanthroline and 4,5-diazafluorene backbones and ketone groups were synthesized (1,10-phenan...

A new set of microporous organic polymers (POPs) containing diphosphine derivatives synthesized by knitting via Friedel–Crafts has been attained. These amorphous three-dimensional materials have been prepared by utilizing diphosphines, 1,3,5-triphenylbenzene, and biphenyl as nucleophile aromatic groups, dimethoxymethane as the electrophilic linker,...

By employing a variation of the polyamidation method using in situ silylated diamines and acid chlorides, it was possible to obtain a rod-type polyamide: poly(p-phenylene terephthalamide) (PPTA, a polymer used in the high-value-added material Kevlar), with a molecular weight much higher than that obtained with the classical and industrial polyamida...

19F NMR monitoring shows that heating trans-[AuIIIRf2I2]- solutions (Rf = C6F3Cl2-3,5) leads to formation of cis-[AuRf2I2]-, [AuRf3I]- and [AuRfI3]-via kinetic competition between isomerization and Rf/I scrambling. The system evolution is driven by the easy Rf-I reductive elimination from [AuRfI3]- (forming also [AuI2]-), which is faster than any o...

By employing a variation of the polyamidation method using in situ silylated diamines and acid chlorides, it has been possible to obtain a rod-type polyamide: poly(p-phenylene terephthalamide) (PPTA, a polymer used in the high value-added material Kevlar), with a molecular weight much higher than that obtained with the classical, and industrial, po...

Aromatic copolyimides (PIx) and aromatic-aliphatic copolyimides (PIxEOy) were synthesized by reacting 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) with mixtures obtained from 2-2′-bis(4-aminophenyl)hexafluoropropane (6FpDA), 5-diaminobenzoic acid (DABA) and Jeffamine ED-2003 (PEO). The selective thermal removal of PEO from PIxEOy yie...

Analysis of the bonding contributions in molecules [MIIICp*(L)XY] (M = Rh, Ir; Cp* = C5Me5; L = CO, CN–, CNR) has uncovered a rich variety of types of interaction that seem to have escaped detection so far, in spite of the continuous popularity of cyclopentadienyl transition-metal complexes since the 1970s. At variance with the M—C≡O bond in square...

Aryl rearrangements triggered by Cl⁻ extraction from trans-[AuIII(Rf)2Cl2]⁻ (Rf = C6F3Cl2-3,5), led quickly to a mixture of [Au(Rf)3(solv)], cis-[Au(Rf)2Cl(solv)] and [Au(Rf)Cl2(solv)] (solv = OEt2, OH2). ¹⁹F NMR and X-ray diffraction studies led us to identify the species present in solution and the role of the solvent in their formation, while DF...

By combining kinetic experiments, theoretical calculations, and microkinetic modeling, we show that Pf/Rf (C6F5/C6Cl2F3) exchange between [AuPf(AsPh3)] and trans‐[RhRf(CO)(AsPh3)2] does not occur by typical concerted Pf/Rf transmetalation via electron‐deficient double bridges. Instead, it involves asymmetric oxidative insertion of the RhI complex i...

By combining kinetic experiments, theoretical calculations and microkinetic modelling, we show that the Pf/Rf (C6F5/C6Cl2F3) exchange between [AuPf(AsPh3)] and trans‐[RhRf(CO)(AsPh3)2] does not occur through the typical concerted Pf/Rf transmetalation via electron deficient double bridges. Instead, it involves asymmetric oxidative insertion of the...

A new generation of porous polymer networks, PPNs, has been obtained in quantitative yield by reacting in superacidic media two rigid trifunctional aromatic monomers (1,3,5-triphenylbenzene and triptycene) with two ketones having electron-withdrawing groups (trifluoroacetophenone and isatin). The resulting amorphous networks are microporous materia...

The pentacoordinated [RhCp*Rf2] (Rf = C6F3Cl2-3,5) and the octahedral (μ-Cl)2[RhCp*Rf]2, obtained by stoichiometric rearrangement with (μ-Cl)2[RhCp*Cl]2, are general precursors of [RhCp*RfXL] (X = Rf, Cl; L = ligand) complexes, which were studied by NMR (L dissociation and fluxional processes) and X-ray diffraction (structural effects affecting the...

Experiments mixing the stable 16e 5-coordinate complexes [RhCp*Ar 2 ] (Cp* = C 5 Me 5 ; Ar = C 6 F 5 , C 6 F 3 Cl 2 -3,5) uncover fast aryl transmetalations. Unexpectedly, as supported computationally, these exchanges are not spontaneous, but catalyzed...

This study deals with two striking phenomena: the complete protection against decomposition of hypothetically monocoordinated AuI intermediates [AuL]Y (L = strongly coordinating ligand; Y⁻ = poorly coordinating anion) by addition of small substoichiometric amounts (5 mol % relative to Au) of not strongly coordinating ligands (e.g., AsPh3) and the f...

The first now-named Stille reaction was published 38 years ago, and the last comprehensive revision of this catalysis was in 2004. Since then, the knowledge of the different steps of the three possible (and sometimes competing) reaction pathways (cyclic, open, and ionic) has been almost completed by synergistic experimental and theoretical studies:...

Neutral gold complexes with hydrogen-bond-supported heterocyclic carbene (HBHC) and nitrogen acyclic carbene (NAC) ligands have been synthesized by the reactions of isocyanogold derivatives [AuCl(CNR)] with amines. Cationic [Au(carbene)(AsPh3)][SbF6] complexes have also been prepared. The catalytic activity of both types of complex (for the former,...

The X-ray structure of the title compound [Pd(Fmes)(2) (tmeda)] (Fmes=2,4,6-tris(trifluoromethyl)phenyl; tmeda=N,N,N',N'-tetramethylethylenediamine) shows the existence of uncommon CH⋅⋅⋅FC hydrogen-bond interactions between methyl groups of the TMEDA ligand and ortho-CF(3) groups of the Fmes ligand. The (19) F NMR spectra in CD(2) Cl(2) at very l...

Mononuclear and dinuclear chiral gold(I) carbene complexes with carbene ligands of the type HBHC (hydrogen bonded heterocyclic carbenes) and NAC (nitrogen acyclic carbenes) have been prepared by reaction of isocyanide gold(I) complexes and chiral amines or diamines. The reaction of [AuCl(CNPy-2)] (1) (Py = pyridyl) with the corresponding chiral pri...

The catalytic activity of the recently reported nitrogen acyclic carbene (NAC) complexes of gold(I) has been investigated and compared with the reported activity of other gold(I) and gold(III) complexes. The complexes studied, [AuCl{C(NEt2)(NHTol-p)}], [AuCl{C(NEt2)(NHXylyl)}], and [Au(NTf2){C(NEt2)(NHXylyl)}], are very active in processes such as...

The silver(I) complexes [Ag{C5H4N(NC)}]n(BF4)n (1), [Ag{C5H4N(NC)}2]n(BF4)n (2), [Ag{C6H4(NC)2}]n(BF4)n (3), and [Ag{C6H4(NC)2}2]n(BF4)n (4) have been synthesized using different Ag:L ratios of 2-isocyanopyridine (or 2-pyridylisocyanide, CNPy-2) or 1,2-phenylenediisocyanide ligands. The polymeric complex 2 has been characterized by X-ray diffractio...

Complexes [AuCl{C(NHR)(NHR′)}] and [AuCl{C(NHR)(NEt2)}] (R = tBu, p-Tol, Xylyl, p-C6H4COOH, p-C6H4COOEt, R′ = Me, nBu, iPr, nheptyl, p-Tol) have been prepared by reaction of the corresponding isocyanogold complexes [AuCl(CNR)] with either primary amines or diethylamine. All the prepared carbenes are reactive and highly selective catalysts for skele...

Complexes [AuCl{C(NHR)(NHPy-2)}] (Py-2 ) 2-pyridyl; R ) Me, tBu, nBu, iPr, nheptyl) have been prepared in amodular way from [AuCl(CNPy-2)]. The carbene moiety has a hydrogen-bond supported heterocyclic structure similar to the nitrogen heterocyclic carbenes in the solid state, and in CH2Cl2 or acetone solution, which is open in the presence of MeOH...

Isocyanide [AuX(CNPy-2)] (X = Cl, C6F5, fluoromesityl, 1/2 octafluorobiphenyl) and carbene [AuX{C(NR1R2)(NHPy-2)}] (R1R2NH = primary or secondary amines or 1/2 primary diamine) gold(I) complexes have been synthesized and characterized. For X = Cl, the carbene complexes show aurophilic interactions. The fragment NHPy-2, formed in the carbenes, can g...

Monomeric gold(I) carbenes of the type [AuR[C(NR1R2)(NHPy-4)]] (Py-4 = 4-pyridyl) have been prepared with R = C6F5, Fmes (2,4,6-tris(trifluoromethyl)phenyl) by reaction of the corresponding isocyanide compounds [AuR(CNPy-4)] with primary or secondary amines. The single crystal X-ray diffraction structures of [Au(C6F5)[C(NEt2)(NHPy-4)]].OH2, [Au(Fme...

The reinvestigation of the title compounds, which are the only examples reported to show experimentally (by NMR) O-H...F-C bonds in solution proves that the NMR data were misinterpreted and the restrictions to rotation of one CF(3) group are due to crowding, not to intramolecular O-H...F-C bond.

Halide abstraction from [Pd(μ-Cl)(Fmes)(NCMe)]2 (Fmes = 2,4,6-tris(trifluoromethyl)phenyl or nonafluoromesityl) with TlBF4 in CH2Cl2/MeCN gives [Pd(Fmes)(NCMe)3]BF4, which reacts with monodentate ligands to give the monosubstituted products trans-[Pd(Fmes)L(NCMe)2]BF4 (L = PPh3, P(o-Tol)3, 3,5-lut, 2,4-lut, 2,6-lut; lut = dimethylpyridine), the dis...

A subtle interplay of covalent bond, hydrogen bond, aurophilic interactions, and steric hindrance controls the nuclearity and the luminescent properties of [Au{2-PyN C(E)Me}]n (E = O, NH) complexes. For E = O a molecular structure with n = 4 is formed, describing a 20-membered tetrametallacycle. For E = NH the structure formed shows a trigonal pris...

Bisarylated complexes trans-[Pd(Fmes)2(SR2)2] [Fmes = 2,4,6-tris(trifluoromethyl)phenyl (fluoromesityl); SR2 = SMe2, tht; tht = tetrahydrothiophene] are precursors for various bisarylated fluoromesityl palladium(II) complexes by ligand-substitution reactions. Boiling under reflux in acetonitrile gives the mixed complexes trans-[Pd(Fmes)2(NCMe)(SR2)...

Monoarylated complexes [PdCl(Fmes)(L-L)] [Fmes = 2,4,6-tris(trifluoromethyl)phenyl or fluoromesityl] and trans-[PdCl(Fmes)L2] have been obtained by arylation of [PdCl2(L-L)] (L-L = tmeda) or trans-[PdCl2L2] (L = SMe2), by splitting the bridging chloro ligands in [Pd(μ-Cl)(Fmes)(NCMe)]2 {L-L = 4,4′-Me2bipy, biquinolyl (2,2′-biquinoline), OPPhPy2-N,N...

The treatment of [Pd(dmba)(Fmes)(OH2)] with I2 leads to the formation of [Pd(Fmes)I{NMe2(CH2-o-C6H4-I)-N,I}]. The X-ray structure shows that a new halocarbon ligand, (2-iodobenzyl)dimethylamine has been formed and is acting as N–I chelate. The two different types of iodine, one iodide ligand and one organic iodide coordinated to Pd, are mutually tr...

The reactions of chlorobridged cyclometalated complexes [Pd(C−N)(μ-Cl)]2 (C−N = orthometalated N,N-dimethylbenzylamine, dmba; 2-(para-tolyl)pyridine, p-tolpy; azobenzene, azb; N,N-dimethyl-1-naphthylamine, dmna; and 2-benzylpyridine, bzpy) with Li(Fmes) (Fmes = 2,4,6-tris(trifluoromethyl)phenyl or nonafluoromesityl) give, after hydrolysis, neutral...

Halide ions act as the template for the self-assembly of tetrapalladium macrocyclic pyramidal structures. These undergo easy inversion in which the halide ion apparently jumps across the macrocycle (see scheme).