Enantioselective Amination of 4-Substituted Pyrazolones Catalyzed by Oxindole-Containing Thioureas and by a Recyclable Linear-Polymer-Supported Analogue in a Continuous Flow Process.

A highly efficient organocatalytic amination of 4-substituted pyrazolones with azodicarboxylates mediated by a novel quinine-derived thiourea with a 3,3-diaryl-oxindole scaffold is reported. This synthetic method furnished 4-amino-5-pyrazolones in high yields and with excellent enantioselectivities (up to 97:3 er) at room temperature in short reaction times. Moreover, a linear-polymer-supported bifunctional thiourea, synthesized by reacting a bifunctional aromatic monomer (biphenyl) with isatin in superacidic media and further derivatization, was proven to be also an efficient heterogeneous organocatalyst for this α-amination reaction. The practical value of this process was demonstrated by the use of the immobilized catalyst in recycling experiments, maintaining the activity without additional reactivation, and in flow processes, allowing the synthesis of 4-amino-pyrazolone derivatives in a gram scale with high yield and enantioselectivity.

Palladium Catalysts Supported in Microporous Phosphine Polymer Networks.

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, and FeCl3 as a promoting catalyst. These polymer networks display moderate thermal stability and high microporosity, boasting BET surface areas above 760 m2/g. They are capable of coordinating with palladium acetate, using the phosphine derivative as an anchoring center, and have proven to be highly efficient catalysts in Suzuki-Miyaura coupling reactions involving bromo- and chloroarenes under environmentally friendly (using water and ethanol as solvents) and aerobic conditions. These supported catalysts have achieved excellent turnover numbers (TON) and turnover frequencies (TOF), while maintaining good recyclability without significant loss of activity or Pd leaching after five consecutive reaction cycles.

Aromatic Polyimide Membranes with tert-Butyl and Carboxylic Side Groups for Gas Separation Applications-Covalent Crosslinking Study.

A set of aromatic copolyimides was obtained by reaction of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), and mixtures of the diamines 1,4-bis(4-amino-2-trifluoromethylphenoxy)-2,5-di-tert-butylbenzene (CF3TBAPB) and 3,5-diamino benzoic acid (DABA). These polymers were characterized and compared with the homopolymer derived from 6FDA and CF3TBAPB. All copolyimides showed high molecular weight values and good mechanical properties. The presence of carboxylic groups in these copolymers allowed their chemical crosslinking by reaction with 1,4-butanediol. Glass transition temperatures (Tg) were higher than 260 °C, showing the non-crosslinked copolyimides had the highest Tg values. Degradation temperature of crosslinked copolyimides was lower than their corresponding non-crosslinked ones. Mechanical properties of all polymers were good, and thus, copolyimide (precursor, and crosslinked ones) films could be tested as gas separation membranes. It was observed that CO2 permeability values were around 100 barrer. Finally, the plasticization resistance of the crosslinked material having a large number of carboxylic groups was excellent.

Mixed Matrix Membranes Loaded with a Porous Organic Polymer Having Bipyridine Moieties.

Mixed matrix membranes (MMMs), derived from three aromatic polyimides (PIs), and an affordable porous organic polymer (POP) having basic bipyridine moieties were prepared. Matrimid and two fluorinated polyimides, which were derived from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 2,2'-bis(4-aminophenyl)hexafluoropropane (6F6F) or 2,4,6-trimethyl-m-phenylenediamine (6FTMPD), were employed as polymer matrixes. The used POP was a highly microporous material (surface area of 805 m2 g-1) with excellent thermal and chemical stability. The MMMs showed good compatibility between the PIs and POP, high thermal stabilities and glass transition temperatures superior to those of the neat PI membranes, and good mechanical properties. The addition of POP to the matrix led to an increase in the gas diffusivity and, thus, in permeability, which was associated with an increase in the fractional free volume of MMMs. The increase in permeability was higher for the less permeable matrix. For example, at 30 wt.% of POP, the permeability to CO2 and CH4 of the MMMs increased by 4- and 7-fold for Matrimid and 3- and 4-fold for 6FTMPD. The highest CH4 permeability led to a decrease in CO2/CH4 selectivity. The CO2/N2 separation performance was interesting, as the selectivity remained practically constant. Finally, the POP showed no molecular sieving effect towards the C2H4/C2H6 and C3H6/C3H8 gas pairs, but the permeability increased by about 4-fold and the selectivity was close to that of the matrix. In addition, because the POP can form metal ion bipyridine complexes, modified POP-based MMMs could be employed for olefin/paraffin separations.

Porous Organic Polymers Containing Active Metal Centers for Suzuki-Miyaura Heterocoupling Reactions.

A new generation of confined palladium(II) catalysts covalently attached inside of porous organic polymers (POPs) has been attained. The synthetic approach employed was straightforward, and there was no prerequisite for making any modification of the precursor polymer. First, POP-based catalytic supports were obtained by reacting one symmetric trifunctional aromatic monomer (1,3,5-triphenylbenzene) with two ketones having electron-withdrawing groups (4,5-diazafluoren-9-one, DAFO, and isatin) in superacidic media. The homopolymers and copolymers were made using stoichiometric ratios between the functional groups, and they were obtained with quantitative yields after the optimization of reaction conditions. Moreover, the number of chelating groups (bipyridine moieties) available to bind Pd(II) ions to the catalyst supports was modified using different DAFO/isatin ratios. The resulting amorphous polymers and copolymers showed high thermal stability, above 500 °C, and moderate-high specific surface areas (from 760 to 935 m2 g-1), with high microporosity contribution (from 64 to 77%). Next, POP-supported Pd(II) catalysts were obtained by simple immersion of the catalyst supports in a palladium(II) acetate solution, observing that the metal content was similar to that theoretically expected according to the amount of bipyridine groups present. The catalytic activity of these heterogeneous catalysts was explored for the synthesis of biphenyl and terphenyl compounds, via the Suzuki-Miyaura cross-coupling reaction using a green solvent (ethanol/water), low palladium loads, and aerobic conditions. The findings showed excellent catalytic activity with quantitative product yields. Additionally, the recyclability of the catalysts, by simply washing it with ethanol, was excellent, with a sp2-sp2 coupling yield higher than 95% after five cycles of use. Finally, the feasibility of these catalysts to be employed in tangible organic reactions was assessed. Thus, the synthesis of a bulky compound, 4,4'-dimethoxy-5'-tert-butyl-m-terphenylene, which is a precursor of a thermal rearrangement monomer, was scaled-up to 2 g, with high conversion and 96% yield of the pure product.

Fluorescent perylenylpyridine complexes: an experimental and theoretical study.

The perylene derivative 2-(3-perylenyl)-4-methylpyridine (HPerPy) was prepared and used to synthesize [Ag(HPerPy)(PPh3)(OClO3)], with the perylene ligand bonded to the metal centre only by the pyridine nitrogen. The treatment of HPerPy with [Pd(OAc)2] in methanol or acetic acid led to acetate bridged dimers (µ-OOCCH3)2[Pd(PerPy)]2, six-membered or five-membered cycled at the perylenyl fragment. Substitution reactions afforded mononuclear compounds [Pd(PerPy)(acac)] (six-member or five-member cycled) and [Pd(PerPy)(S2COMe)] (six-member or five-member cycled). The reaction of HPerPy with a platinum(ii) fragment led to a five-membered cyclometallated Pt(ii) complex [Pt(PerPy)(acac)]. The oxidative addition with MeI gave the corresponding cyclometallated Pt(iv) compound [Pt(PerPy)(acac)MeI]. X-ray single crystal studies of compounds [Ag(HPerPy)(PPh3)(OClO3)], (µ-OOCCH3)2[Pd(PerPy)]2-five-membered, [Pd(PerPy)(acac)]-six-membered, [Pd(PerPy)(S2COMe)]-five-membered, [Pt(PerPy)(acac)]-five-membered, and [Pt(PerPy)(acac)MeI]-five-membered confirmed the proposed structures. The UV-Vis spectra show one intense absorption with vibronic coupling in the visible region with maxima in the range of 448-519 nm. DFT calculations were carried out for the absorption spectra of the HPerPy molecule and representative complexes [M(PerPy)(acac)] (M: Pd, Pt; five and six-membered isomers) and [Pt(PerPy)(acac)MeI], showing that the lowest energy most intense transition in the complexes corresponds to the HOMO → LUMO transition in the perylene moiety, although affected by the metallacycle size and the metal nature. All the compounds are fluorescent in solution, due to the perylene fragment. The emission spectra display maxima in the range of 468-549 nm, with quantum yields from 1.1 to 82%. The attenuation of the intensity of fluorescence by the presence of heavy atoms and the formation of metallacycles has been experimentally determined and sequenced.

Novel phosphine sulphide gold(i) complexes: topoisomerase I inhibitors and antiproliferative agents.

This work describes the synthesis of the gold(i) complexes of phosphine sulphides. The formation of these new derivatives has been confirmed by X-ray crystallography. The coordination of gold(i) with the sulphur atom of the phosphine sulphides favors the inhibition of topoisomerase I as well as a high cytotoxicity of the gold(i)-complexed compounds against the cancer line A549 with IC50 values in the nanomolar range and IC50 values below 5 µM against the SKOV3 cell line. It should be noted that the cytotoxicities observed for the new gold(i) complexes are higher than those observed for phosphine sulphide ligands before binding to gold. Furthermore, the results also indicate that the presence of a nitrogenated heterocycle, such as tetrahydroquinoline or quinoline, is also necessary for the TopI inhibition to be maintained. In addition, no toxicity was observed when the non-cancerous lung fibroblast cell line (MRC5) was treated with the new phosphine sulphide gold(i) complexes prepared.

Higher fluorescence in platinum(iv) orthometallated complexes of perylene imine compared with their platinum(ii) or palladium(ii) analogues.

The reaction of 3-perylenylmethylen-4'-ethylaniline () with [Pt2Me4(µ-SMe2)2] (and subsequent addition of PPh3) or with [Pt2(η(3)-C4H7)2(µ-Cl)2] produced cyclometallated Pt(II) complexes [Pt(C^N)Me(PPh3)] () and, respectively, [Pt2(C^N)2(µ-Cl)2] () (HC^N = 3-C20H11CH[double bond, length as m-dash]NC6H4-p-C2H5), with Pt bound to the ortho site of the perylenyl fragment. From the mononuclear complexes [Pt(C^N)L2] (L2 = acac (); S2COMe (); S2CNEt2 () are easily formed. Oxidative addition of methyl iodide to the square-planar Pt(II) complexes , , and gave the corresponding cyclometallated Pt(IV) compounds [Pt(C^N)L2MeI] , and . The X-ray structures of , , and show that the perylenyl fragment remains essentially flat in and and slightly twisted in . Comparison of the optical properties of these Pt(II) complexes with those reported for similar Pd(II) derivatives reveals that the change of metal exerts a notable influence on the UV-vis spectra. In solution at room temperature, all the Pt complexes exhibit fluorescence associated with the perylene fragment with low emission quantum yields for the Pt(II) complexes (<1%) and remarkably higher emission values for the Pt(IV) complexes: up to 29%, with emission lifetimes of 1-5 ns. Time-dependent density functional theory (TD-DFT) calculations were performed on the perylene imine and on representative complexes [M(C^N)(acac)] (M = Pd, Pt) and [Pt(C^N)(acac)MeI] to analyse the absorption spectra. These calculations support a perylene-dominated intraligand π-π*emissive state based on the HOMO and LUMO orbitals of the perylene chromophore, and a ligand-to-ligand charge-transfer (more intense for the Pt(II) complex) that explains the observed influence of the metal on the absorption properties.

Highly fluorescent complexes with gold, palladium or platinum linked to perylene through a tetrafluorophenyl group.

Treatment of 3-(1-hexynyl)perylene with Co2(CO)8 resulted in the formation of the dinuclear cobalt complex [Co2(CO)6(µ-η(2)-C4H9C≡C-Per)] (Per = 3-perylenyl) (1). The perylene derivatives 3-(2,3,5,6-tetrafluorophenyl)perylene (PerC6F4H) and 3-(2,3,5,6-tetrafluorophenyl)-9(10)hexylperylene (C6-PerC6F4H) were prepared and used to synthesize [AuR(CN(t)Bu)] (R = PerC6F4 2a), [AuR(CN(C6H2)-3,4,5-(OC12H25)3)] (R = PerC6F4 (3a), R = C6-PerC6F4 (3b)), trans-[PdR(PR'3)2X] (R = PerC6F4, R' = Ph, X = I (4a)); (R = C6-PerC6F4, R' = Ph, X = I (4b)); (R = PerC6F4, R' = Et, X = I (5a)); (R = C6-PerC6F4, R' = Et, X = I (5b)); (R = PerC6F4, R' = Ph, X = NCS (6a)), and trans-[Pd(PerC6F4)(PEt3)2X] (X = Br (7a); X = I (8a)). The molecular structure of complexes 1, 2a and 6a has been determined by X-ray diffraction analysis. The perylenyl fragments of complexes 2a or 6a are essentially planar and make dihedral angles to the tetrafluorophenyl plane of 57.49° (2a) and 77.75° (6a). No π-π stacking of perylenyl rings is observed in any of the three molecules, but 2a shows association of two monomers (arranged almost antiparallel), with an Au···Au distance of 3.114 Å. DFT calculations were performed on the absorption spectra of representative PerC6F4Y (Y = H, F, Au(CNMe), PtBr(PMe3)2 and PdBr(PMe3)2). All complexes exhibit fluorescence associated with the perylene fragment with emission quantum yields, in solution at room temperature, in the range 0.20-0.90 and emission lifetimes ~4 ns, and no significant differences in the emission maxima, due to an efficient electronic decoupling of the metal fragment from the HOMO and LUMO of the perylene chromophore. The latter is confirmed by DFT calculations.

Cyclopalladated complexes of perylene imine: mononuclear complexes with five- or six-membered metallacycles.

Mononuclear palladium complexes [Pd(C^N)L(2)] (HC^N = 3-C(20)H(11)CH=NC(6)H(4)-p-C(2)H(5)) have been prepared with Pd bound to the peri site or to the ortho site of the perylenyl fragment. These metallations correspond, respectively to six-membered (L(2) = S(2)COMe (3); acac (4); Cl, PMe(3) (5); Cl, PPh(3) (6); S(2)CNEt(2) (7)) or five-membered (L(2) = S(2)COMe (8); acac (9)) isomeric palladacyclic compounds. The X-ray structures of 3, 5, 7 and 8 show that the perylenyl fragment remains essentially flat for 3, 7 and 8 and twisted for 5. Intermolecular π-π stacking of perylenyl rings is observed only for 7. All palladium complexes exhibit fluorescence associated to the perylene fragments, with emission quantum yields (in solution at room temperature) in the range 0.01-0.12 (compared to 0.13 for the free imine), and emission lifetimes ∼ 1 ns. The complexes with five-membered palladacycles show lower quantum yields than their six-membered analogs. The similarity in shape of the luminescence spectra of these metallated complexes with perylene, although red-shifted, strongly suggests a perylene-dominated intraligand π-π* emissive state, metal-perturbed by interaction of the perylene orbitals with the palladium fragment.

Highly fluorescent platinum(II) organometallic complexes of perylene and perylene monoimide, with Pt σ-bonded directly to the perylene core.

3-Bromoperylene (BrPer) or N-(2,5-di-tert-butylphenyl)-9-bromo-perylene-3,4-dicarboximide (BrPMI) react with [Pt(PEt(3))(4)] to yield trans-[PtR(PEt(3))(2)Br] (R = Per, 1a; R = PMI, 1b). Neutral and cationic perylenyl complexes containing a Pt(PEt(3))X group have been prepared from 1a,b by substitution of the Br ligand by a variety of other ligands (NCS, CN, NO(3), CN(t)Bu, PyMe). The X-ray structures of trans-[PtR(PEt(3))(2)X] (R = Per, X = NCS (2a); R = PMI, X = NO(3) (4b); R = Per, X = CN(t)Bu (5a)) show that the perylenyl fragment remains nearly planar and is arranged almost orthogonal to the coordination plane: The three molecules appear as individual entities in the solid state, with no π-π stacking of perylenyl rings. Each platinum complex exhibits fluorescence associated to the perylene or PMI fragments with emission quantum yields, in solution at room temperature, in the range 0.30-0.80 and emission lifetimes ∼4 ns, but with significantly different emission maxima, by influence of the X ligands on Pt. The similarity of the overall luminescence spectra of these metalated complexes with the perylene or PMI strongly suggests a perylene-dominated intraligand π-π*emissive state, metal-perturbed by interaction of the platinum fragment mostly via polarization of the Ar-Pt bond.

Genuine examples of tetrahedral tetradentate sulfide ligand bridging four Pd atoms: controlled formation of [(mu(4)-S){(mu(2)-X)Pd(2)(C(wedge)N)(2)}(2)] (X = OH or Cl; HC(wedge)N = p-C(2)H(5)OC(6)H(4)CH=NC(6)H(4)-p-C(2)H(5)) complexes.

A smooth reaction of [(mu3-S)(mu3-OH)Pd3(CwedgeN)3] (2) with [(mu2-X)2Pd2(CwedgeN)2] (2:1; HCwedgeN = p-C2H5OC6H4CH=NC6H4-p-C2H5, X = OH, Cl) provides [(mu4-S){(mu2-OH)Pd2(CwedgeN)2}2] (3) and [(mu4-S)(mu2-Cl)(mu2-OH)Pd4(CwedgeN)4] (4). Treatment of 3 with HCl (molar ratio 1:2) leads to the corresponding tetranuclear complex [(mu4-S)(mu2-Cl)2Pd4(CwedgeN)4] (5). The three complexes contain a (mu4-S)Pd4 core. A density functional theory study of the bonds in 3 supports that the bonding of the S atom can be described in terms of four two-center two-electron S-Pd bonds, in contrast to most other (mu4-S)M4 systems in the literature, where the presence of M-M bonds prevents a bond-localized description of the molecule. The X-ray structures of 2, 3, and 5 are reported.

Formation of trinuclear palladium orthometalated complexes with unprecedented asymmetrical (mu 3-S)(mu 3-X) bridges (X = OH, SR, O2CR) from mu 2-hydroxo dimeric complexes and CS2.

Complexes [Pd(3)(mu(3)-S)(mu(3)-X)(L)(3)] (L = orthometalated imine), obtained by an unusual reaction of mu(2)-OH dimeric complexes and CS(2), are an unprecedented type of asymmetrical bridges between metallatriangles, which force an all-cis arrangement of the three orthometalated ligands relative to the metallatriangle.

Palladium Complexes with the Tridentate Dianionic Ligand Pyridine-2,6-dicarboxylate, dipic. Crystal Structure of [Pd(dipic)(PBu(3))](2).

The reactions of [Pd(acac)(2)] or [Pd(OAc)(2)](3) with pyridine-2,6-dicarboxylic acid (H(2)dipic) in acetonitrile afford [Pd(dipic)(NCMe)] in high yield. This complex has been used as starting material in the preparation of a variety of neutral an anionic complexes. The dipicolinate anion behaves as a tridentate ligand in all cases, but two modes of coordination are found, depending on the ligand: as a pincer ligand O,N,O-bonded to the same palladium, giving mononuclear complexes, and as an O,N-chelate N,O'-bridging ligand in dinuclear complexes. An X-ray determination of the structure of a dimer, [Pd(dipic)(PBu(3))](2) (monoclinic, space group P2(1)/n, a = 18.144(4) Å, b = 13.191(2) Å, c = 19.571(3) Å, beta = 113.45(2) degrees, Z = 4, R = 0.050, R(w) = 0.054) shows that the ligand is coordinated to one palladium in a eta(2)-N,O chelate fashion and one oxygen atom of the other carboxylate group makes a bridge to the other palladium atom, in a novel bonding mode for the dipic ligand.