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Complex 1 [(C^C)Au(dppv)]PF 6 (dppv = cis -1,2-diphenylphosphinoethylene) is reported to react efficiently and selectively with aliphatic and aromatic thiols in the presence of a base. This methodology enables the smooth introduction of various functional groups on the [(C^C)Au(P^P)] + scaffold.

A series of four binuclear complexes of general formula [(C^C)Au(Cl)(L^L)(Cl)Au(C^C)], where C^C is 4,4'-diterbutylbiphenyl and L^L is either a bridging diphosphine or 4,4'-bipyridine, are synthetized with 52 to 72 % yield and structurally characterized by X-ray diffraction. The use of the chelating 1,2-diphenylphosphinoethane ligand in a 1 : 2 (P^P):Au stoichiometry leads to the near quantitative formation of a gold double-complex salt of general formula [(C^C)Au(P^P)][(C^C^)AuCl 2 ]. The compounds display long-lived yellow-green phosphorescence with λ em in the range of 525 to 585 nm in the solid state with photoluminescence quantum yields (PLQY) up to 10 %. These Au III complexes are tested for their antiproliferative activity against lung adenocarcinoma cells A549 and results show that compounds 2 and 5 are the most promising candidates. The digold salt 5 shows anticancer activity between 66 and 200 nM on the tested cancer cell lines, whereas derivative 2 displays concentration values required to reduce by 50 % the cell viability (IC 50 ) between 7 and 11 μM. Reactivity studies of compound 5 reveal that the [(C^C)Au(P^P)] + cation is stable in the presence of relevant biomolecules including glutathione suggesting a structural mechanism of action., (© 2023 Sorbonne Université. ChemPlusChem published by Wiley-VCH GmbH.)

In this work, we report on the synthesis of several organogold(III) complexes based on 4,4'-diterbutylbiphenyl (C^C) and 2,6-bis(4-terbutylphenyl)pyridine (C^N^C) ligands and bond with variously substituted pyridine ligands (pyrR). Altogether, 33 complexes have been prepared and studied with mass spectrometry using higher-energy collision dissociation (HCD) in an Orbitrap mass spectrometer. A complete methodology including the kinetic modeling of the dissociation process based on the Rice-Ramsperger-Kassel-Marcus (RRKM) statistical method is proposed to obtain critical energies E 0 of the pyrR loss for all complexes. The capacity of these E H pyridinic NMR shift variation upon coordination and Au-N 0 values to describe the pyridine ligand effect is further explored, at the same time as more classical descriptors such as 1 H pyridinic NMR shift variation upon coordination and Au-N pyrR bond length measured by X-ray diffraction. An extensive theoretical work, including density functional theory (DFT) and domain-based local pair natural orbital coupled-cluster theory (DLPNO-CCSD(T)) methods, is also carried out to provide bond-dissociation energies, which are compared to experimental results. Results show that dissociation energy outperforms other descriptors, in particular to describe ligand effects over a large electronic effect range as seen by confronting the results to the pyrR p K with H a values. Further insights into the Au-N pyrR bond are obtained through an energy decomposition analysis (EDA) study, which confirms the isolobal character of Au + with H + . Finally, the correlation between the lability of the pyridine ligands toward the catalytic efficiency of the complexes could be demonstrated in an intramolecular hydroarylation reaction of alkyne. The results were rationalized considering both pre-catalyst activation and catalyst reactivity. This study establishes the possibility of correlating dissociation energy, which is a gas-phase descriptor, with condensed-phase parameters such as catalysis efficiency. It therefore holds great potential for inorganic and organometallic chemistry by opening a convenient and easy way to evaluate the electronic influence of a ligand toward a metallic center.

Efficient synthesis of original 1,6-naphthyridin-7(6 H )-ones and their optical properties are described. Their powerful fluorescence properties including dual fluorescence, solvatochromism, acidochromism, large Stokes shifts and high quantum yields, suitable for biological applications or as luminescent devices in materials science, are evidenced.

Commercially available Fe(TTP)Cl catalyzes three-component dearomative formal cycloaddition reactions between pyridines, diazo compounds, and coumalates. Diversely substituted annelated seven-membered N-heterocycles could be generated in less than 10 min in one step at room temperature. The reaction is compatible to gram scale. The extension to benzimidazoles in place of pyridines has been successfully demonstrated. The mechanism of this reaction has been carefully examined by computational studies that corroborate the observed regioselectivities.

Photosensitization of organogold intermediates is an emerging field in catalysis. In this context, an access to 2,3-disubstituted indoles from o-alkynyl aniline and iodoalkyne derivatives via a gold-catalyzed sequence under visible-light irradiation and in the absence of an exogenous photocatalyst was uncovered. A wide scope of the process is observed. Of note, 2-iodo-ynamides can be used as electrophiles in this cross-coupling reaction. The resulting N-alkynyl indoles lend themselves to post-functionalization affording valuable scaffolds, notably benzo[a]carbazoles. Mechanistic studies converge on the fact that a potassium sulfonyl amide generates emissive aggregates in the reaction medium. Static quenching of these aggregates by a vinylgold(I) intermediate yields to an excited state of the latter, which can react with an electrophile via oxidative addition and reductive elimination to forge the key C-C bond. This reactant-induced photoactivation of an organogold intermediate opens rich perspectives in the field of cross-coupling reactions., (© 2022. The Author(s).)

A library of eleven cationic gold(III) complexes of the general formula [(C C)Au(N N)] + when C C is either biphenyl or 4,4'-ditertbutyldiphenyl and N N is a bipyridine, phenanthroline or dipyridylamine derivative have been synthesized and characterized. Contrasting effects on the viability of the triple negative breast cancer cells MDA-MB-231 was observed from a preliminary screening. The antiproliferative activity of the seven most active complexes were further assayed on a larger panel of human cancer cells as well as on non-cancerous cells for comparison. Two complexes stood out for being either highly active or highly selective. Eventually, reactivity studies with biologically meaningful amino acids, glutathione, higher order DNA structures and thioredoxin reductase (TrxR) revealed a markedly different behavior from that of the well-known coordinatively isomeric [(C N C)Au(NHC)] + structure. This makes the [(C C)Au(N N)] + complexes a new class of organogold compounds with an original mode of action., (© 2021 Wiley-VCH GmbH.)

Cyclodextrins (CDs) are cyclic oligosaccharides mainly composed of six, seven, and eight glucose units, so-called α-, β-, and γ-CDs, respectively. They own a very particular molecular structure exhibiting hydrophilic features thanks to primary and secondary rims and delimiting a hydrophobic internal cavity. The latter can encapsulate organic compounds, but the former can form supramolecular complexes by hydrogen-bonding or electrostatic interactions. CDs have been used in catalytic processes to increase mass transfer in aqueous-organic two-phase systems or to prepare catalysts. In the last case, interaction between CDs and metal salts was considered to be a key point in obtaining highly active catalysts. Up to now, no work was reported on the investigation of factors affecting the binding of metal to CD. In the study herein, we present the favorable combination of electrospray ionization coupled to mass spectrometry [ESI-MS(/MS)] and density functional theory molecular modeling [B3LYP/Def2-SV(P)] to delineate some determinants governing the coordination of first-row divalent transition metals (Mn 2+ , Co 2+ , Ni 2+ , Cu 2+ , and Fe 2+ ) and one post-transition metal (Zn 2+ ) with α-, β-, and γ-CDs. A large set of features concerning the metal itself (ionic radius, electron configuration, and spin state) as well as the complexes formed (the most stable conformer, relative abundance in MS, CE 50 value in MS/MS, binding energy, effective coordination number, average bond lengths, binding site localization, bond dissociation energies, and natural bond orbital distribution) were screened. Taking into account all of these properties, various selectivity rankings have been delineated, portraying differential association/dissociation behaviors. Nonetheless, unique 3D topologies for each CD-metal complex were emphasized. The combination of these approaches brings a stone for building a compendium of molecular features to serve as a suitable descriptor or predictor for a better first round rationalization of catalytic activities.

In organometallic chemistry, especially in the catalysis area, accessing the finest tuning of a catalytic reaction pathway requires a detailed knowledge of the steric and electronic influences of the ligands bound to the metal center. Usually, the M-L bond between a ligand and metal is depicted by the Dewar-Chatt-Duncanson model involving two opposite interactions, σ-donor and π-acceptor effects of the ligand. The experimental evaluation of these effects is essential and complementary to in-depth theoretical approaches that are able to provide a detailed description of the M-L bond. In this work, we present a study of LMo(CO) 5 complexes with L being various tertiary phosphine ligands by means of mass-selected high-resolution photoelectron spectroscopy (PES) performed with synchrotron radiation, DFT, and energy decomposition analyses (EDA) combined with the natural orbitals for chemical valence (NOCV) analysis. These methods enable a separated access of the σ-donor and π-acceptor effects of ligands by probing either the electronic configuration of the complex (PES) or the interaction of the ligand with the metal (EDA). Three series of PR 3 ligands with various electronic influences are investigated: the strong donating alkyl substituents (PMe 3 , PEt 3 , and P i Pr 3 ), the intermediate PPh x Me (3- x ) ( x = 0-3) set, and the PPh x Pyrl (3- x ) set ( x = 0-3 with Pyrl being the strong electron withdrawing pyrrolyl group C 4 H 4 N). For each complex, their adiabatic and vertical ionization energies (IEs) could be determined with a 0.03 eV precision. Experiment and theory show an excellent agreement, either for the IE determination or electronic effect analysis. The ability to interpret the spectra is shown to depend on the character of the ligand. "Innocent" ligands provide the spectra that are the most straightforward to analyze, whereas the "non-innocent" ligands (which are ionized prior to the metal center) render the analysis more difficult due to an increased number of molecular orbitals in the energy range considered. A very good linear correlation is finally found between the measured adiabatic ionization energies and the interaction energy term obtained by EDA for each of these two types of ligands, which opens interesting perspective for the prediction of ligand characters.

The two independent and N N ^ coordination sites of a newly synthesized bis[2-(hydroxyphenyl)-1,2,4-triazole] platform have been exploited to prepare four monometallic neutral ()Pt II complexes carrying DMSO, pyridine, triphenylphosphine, or N-heterocyclic carbene as the fourth ligand. Then, the second N N ^ coordination site was used to introduce an IR-active rhenium tricarbonyl entity, affording the four corresponding heterobimetallic neutral Pt II /Re I complexes, as well as a cationic Pt II /Re I derivative. X-ray crystallographic studies showed that distortion of the organic platform occurred to accommodate the coordination geometry of both metal centers. No ligand exchange or transchelation occurred upon incubation of the Pt II complexes in aqueous environment or in the presence of Fe III , respectively. The antiproliferative activity of the ligand and complexes was first screened on the triple-negative breast cancer cell line MDA-MB-231. Then, the IC 50 values of the most active candidates were determined on a wider panel of human cancer cells (MDA-MB-231, MCF-7, and A2780), as well as on a nontumorigenic cell line (MCF-10A). Low micromolar activities were reached for the complexes carrying a DMSO ligand, making them the first examples of highly active, but hydrolytically stable, Pt II complexes. Finally, the characteristic mid-IR signature of the {Re(CO) 3 } fragment in the Pt/Re heterobimetallic complexes was used to quantify their uptake in breast cancer cells., (© 2020 Wiley-VCH GmbH.)

The well-established oxidative addition-reductive elimination pathway is the most followed one in transition metal-catalysed cross-coupling reactions. While readily occurring with a series of transition metals, gold(I) complexes have shown some reluctance to undergo oxidative addition unless special sets of ligands on gold(I), reagents or reaction conditions are used. Here we show that under visible-light irradiation, an iridium photocatalyst triggers-via triplet sensitization-the oxidative addition of an alkynyl iodide onto a vinylgold(I) intermediate to deliver C(sp) 2 -C(sp) coupling products after reductive elimination. Mechanistic and modelling studies support that an energy-transfer event takes place, rather than a redox pathway. This particular mode of activation in gold homogenous catalysis was applied in several dual catalytic processes. Alkynylbenzofuran derivatives were obtained from o-alkynylphenols and iodoalkynes in the presence of catalytic gold(I) and iridium(III) complexes under blue light-emitting diode irradiation.

Proline proton affinity PA(Pro) was previously measured by extended kinetic methods with several amines as reference bases using a triple quadrupole mass spectrometer ( J Mass Spectrom 2005; 40: 1300). The measured value of 947.5 ± 5 kJ.mol -1 differs by more than 10 kJ.mol -1 from previous reported experimental or calculated values. This difference may be explained in part by the existence of relatively large entropy difference between the two dissociation channels (ΔΔS ‡ avg  = 31 ± 10 J.mol -1 .K -1 ) and by the inaccuracy of the amines proton affinity used as reference bases. In the present work, these experimental measurements were reinvestigated by RRKM modeling using MassKinetics software. From this modeling, a new PA value of 944.5 ± 5 kJ.mol -1 and a ΔΔS ‡ avg(600K) value of 33 ± 10 J.mol -1 .K -1 are determined. However, the difference between experiment and recent theoretical calculations remains large (10 kJ.mol -1 ). These RRKM simulations allow also accessing to the effective temperature parameter (T eff ) and to discuss the meaning of this term. As previously reported, T eff mainly depends on the internal energy and on the decomposition time as well. It also depends on the critical energies and on the transition state. Considering the entrance of the collision cell as a new ion source, T eff is finally shown to be close to a characteristic temperature (T char ).

Ligand electronic effects in gold(i) chemistry have been evaluated by means of the experimental determination of M-CO bond dissociation energies for 16 [L-Au-CO] + complexes, bearing L ligands widely used in gold catalysis. Energy-resolved analyses have been made using tandem mass spectrometry with collision-induced dissociation. Coupled with DFT calculations, this approach enables the quantification of ligand effects based on the LAu-CO bond strength. A further energy decomposition analysis gives access to detailed insights into this bond's characteristics. Whereas small differences are observed between phosphine- and phosphite-containing gold complexes, carbene ligands are shown to stabilize the gold-carbonyl bond much more efficiently.

Perfluorocarbons, a class of fully fluorinated compounds, are highly persistent and toxic pollutants that are receiving increasing attention due to their widespread environmental distribution. In this study, attention was focused on one compound in particular, namely, perfluorooctanoic acid (PFOA). The first investigation of the UV/VUV photochemistry of the PFOA anion in the gas phase by action spectroscopy of selected ions is reported. Two main relaxation channels were identified: photodissociation and photodetachment. Absolute cross sections for the individual observed processes were measured. DFT calculations and natural transition orbital analysis were carried out to help in the interpretation of the experimental results., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Electron-ion coincidence imaging is used to study chiral asymmetry in the angular distribution of electrons emitted from randomly-oriented enantiomers of two molecules, methyloxirane and trifluoromethyloxirane, upon ionization by circularly polarized VUV synchrotron radiation. Vibrationally-resolved photoelectron circular dichroism (PECD) measurements of the outermost orbital ionization reveal unanticipated large fluctuations in the magnitude of the forward-backward electron scattering asymmetry, including even a complete reversal of direction. Identification and assignment of the vibrational excitations is supported by Franck-Condon simulations of the photoelectron spectra. A previously proposed quasi-diatomic model for PECD is developed and extended to treat polyatomic systems. The parametric dependence of the electronic dipole matrix elements on nuclear geometry is evaluated in the adiabatic approximation. It provokes vibrational level dependent shifts in amplitude and phase, to which the chiral photoelectron angular distributions are especially sensitive. It is shown that single quantum excitation of those vibrational modes, which experience only a relatively small displacement of the ion equilibrium geometry along the normal coordinate and which are then only weakly excited in the Franck-Condon limit, can be accompanied by big shifts in scattering phase; hence the observed big fluctuations in PECD asymmetry for such modes., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nonpolar anabolic steroids are doping agents that typically do not provide strong signals by electrospray ionization-mass spectrometry (ESI-MS) owing especially to the low polarity of the functional groups present. We have investigated the addition of anions, in ammonium salt form, to anabolic steroid samples as ionization enhancers and have confirmed that lower instrumental limits of detection (as low as 10 ng/mL for fluoxymesterone-M) are obtained by fluoride anion attachment mass spectrometry, as compared to ESI(+)/(-) or atmospheric pressure photoionization (APPI)(+). Moreover, collision-induced decomposition (CID) spectra of precursor fluoride adducts of the bifunctional steroid "reduced pregnenolone" (containing two hydroxyl groups) and its d4-analogue provide evidence of regiospecific decompositions after attachment of fluoride anion to a specific hydroxyl group of the steroid. This type of charting of specific CID reaction pathways can offer value to selected reaction monitoring experiments (SRM) as it may result in a gain in selectivity in detection as well as in improvements in quantification.

Rationale: 2,4-Dinitrotoluene (2,4-DNT) is a nitroaromatic explosive which is commonly found in environmental samples close to training points, firing places, and manufacturers. Mass spectrometry analysis of this compound shows one main product ion that distinguishes it from the other isomers of DNT. We present here a detailed mechanistic study on the formation of this ion., Methods: 2,4-DNT was analyzed using negative electrospray ionization high-resolution mass spectrometry (ESI-HRMS) using a linear ion trap quadrupole LTQ-Orbitrap XL mass spectrometer. Collision-induced dissociation (CID) experiments were performed on the [M-H](-) ion obtained. Density functional theory (DFT) calculations were used to support experimental observations., Results: Fragmentation of deprotonated 2,4-DNT [M-H](-) (m/z 181) yields a main product ion at m/z 116. The mechanism of formation of this diagnostic product ion is not obvious and it has never been rationalized. Calculations were performed to probe different mechanistic variants, which are discussed in this work., Conclusions: Analysis of possible pathways to form the m/z 116 ion from the m/z 181 precursor shows that its formation is likely to proceed first via NO(•) loss, followed by eliminations of H2 O and then HO(•) ., (Copyright © 2014 John Wiley & Sons, Ltd.)

Explosive detection and identification play an important role in the environmental and forensic sciences. However, accurate identification of isomeric compounds remains a challenging task for current analytical methods. The combination of electrospray multistage mass spectrometry (ESI-MS(n) ) and high resolution mass spectrometry (HRMS) is a powerful tool for the structure characterization of isomeric compounds. We show herein that resonant ion activation performed in a linear quadrupole ion trap allows the differentiation of dinitrotoluene isomers as well as aminodinitrotoluene isomers. The explosive-related compounds: 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), 2-amino-4,6-dinitrotoluene (2A-4,6-DNT) and 4-amino-2,6-dinitrotoluene (4A-2,6-DNT) were analyzed by ESI-MS in the negative ion mode; they produced mainly deprotonated molecules [M - H](-) . Subsequent low resolution MS(n) experiments provided support for fragment ion assignments and determination of consecutive dissociation pathways. Resonant activation of deprotonated dinitrotoluene isomers gave different fragment ions according to the position of the nitro and amino groups on the toluene backbone. Fragment ion identification was bolstered by accurate mass measurements performed using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS). Notably, unexpected results were found from accurate mass measurements performed at high resolution for 2,6-DNT where a 30-Da loss was observed that corresponds to CH2 O departure instead of the expected isobaric NO(•) loss. Moreover, 2,4-DNT showed a diagnostic fragment ion at m/z 116, allowing the unambiguous distinction between 2,4- and 2,6-DNT isomers. Here, CH2 O loss is hindered by the presence of an amino group in both 2A-4,6-DNT and 4A-2,6-DNT isomers, but nevertheless, these isomers showed significant differences in their fragmentation sequences, thus allowing their differentiation. DFT calculations were also performed to support experimental observations., (Copyright © 2014 John Wiley & Sons, Ltd.)

Gas-phase studies of biomolecules are often difficult to initiate because of the thermolability of these systems. Such studies are nevertheless important to determine fundamental intrinsic properties of the molecules. Here we present the valence shell photoionization of gas-phase vitamins A and B1 close to their ionization threshold. The study was performed by means of an aerosol thermodesorption source coupled to an electron/ion coincidence spectrometer and synchrotron radiation (SOLEIL facility, France). Ion yield curves were recorded for both molecules over a few electronvolt energy range and the threshold photoelectron spectrum was also obtained for vitamin A. Some fundamental properties were extracted for both ions such as adiabatic and the three first vertical ionization energies of retinol (IEad = 6.8 ± 0.2 eV and IEvert = 7.4, 8.3, and 9.2 eV) and dissociation appearance energies for the main fragment ions of vitamin B1. Analysis of the data was supported by ab initio calculations which show a very good agreement with the experimental observations.

Photoelectron circular dichroism (PECD), a forward-backward asymmetry along the light propagation direction observed in the angular distribution of photoelectrons formed in the ionization of a chiral gas phase target with circularly polarized light, is becoming an established technique for chiral differentiation. In this work some of the fundamental and analytical properties of PECD are confirmed and explored further through a comparative study of the valence shell photoionization of enantiomerically pure trifluoromethyl-oxirane and methyl-oxirane, namely the sensitivity of PECD to the initial orbital and to chemical substitution. The recorded PECD experimental data and corresponding continuum multiple scattering calculations for the outermost orbitals obtained at various photon energies reveal the dramatic effect of substituting the CF3 and CH3 groups attached at the asymmetric chiral center. The previously unknown trifluoromethyl-oxirane ion spectroscopy and the fragmentation pattern measured by threshold electron/ion coincidence techniques over the first four eVs above the ionization threshold are also presented in this work and assigned through the use of ab initio calculations. The state-selected photochemistry and threshold electron spectroscopy of methyl-oxirane have additionally been recorded to complement previous spectroscopic studies.

The reactivity of the explosive tetryl (N-methyl-N,2,4,6-tetranitroaniline; Mw = 287 u) was studied using electrospray ionization in negative mode. The main species detected in the spectrum corresponds to the ion observed at m/z 318 (previously assumed to be the odd-electron ion [tetryl + HNO](-•), C7H6O9N6). In this study, we show using D-labeling combined with high-resolution mass spectrometry that this species corresponds to an even-electron anion (i.e. C8H8O9N5), resulting from the formation of a Meisenheimer complex between tetryl and the methanol used as the solvent. Fragmentation of this complex under CID conditions revealed an unexpected fragment: the formation of a 2,4,6-trinitrophenoxide anion at m/z 228. (18)O-labeling combined with quantum chemical calculations helped us better understand the reaction pathways and mechanisms involved in the formation of this product ion. This occurs via a transition state leading to a SN2-type reaction, consequently evolving toward an ion-dipole complex. The latter finally dissociates into deprotonated picric acid., (Copyright © 2013 John Wiley & Sons, Ltd.)

Azaphilones represent numerous groups of wild fungal secondary metabolites that exhibit exceptional tendency to bind to nitrogen atoms in various molecules, especially those containing the amine group. Nitrogenized analogues of mitorubrin azaphilones, natural secondary metabolites of Hypoxylon fragiforme fungus, have been detected in the fungal methanol extract in very low concentrations. Positive electrospray ionization interfaced with high-resolution mass spectrometry was applied for confirmation of the elemental composition of protonated species. Collision-induced dissociation (CID) experiments have been performed, and fragmentation mechanisms have been proposed. Additional information regarding both secondary metabolite analogue families has been reached by application of gas-phase proton/deuterium (H/D) exchanges performed in the collision cell of a triple quadrupole mass spectrometer. An incomplete H/D exchange with one proton less than expected was observed for both protonated mitorubrin azaphilones and their nitrogenized analogues. By means of the density functional theory, an appropriate explanation of this behavior was provided, and it revealed some information concerning gas-phase H/D exchange mechanism and protonation sites., (Copyright © 2012 John Wiley & Sons, Ltd.)