Pauvreté et paupérisation en milieu urbain. Une enquête préliminaire

Les mesures relatives à la mise en place du programme « de stabilisation et d'ajustement structurel » n'ont fait qu'accentuer la détérioration de la situation économique et sociale des classes laborieuses en Égypte, tandis qu'on assiste à une redistribution du revenu et des biens en faveur des détenteurs de capitaux et au détriment des salariés. La baisse de la part du facteur humain dans le revenu national est due au gel des salaires, à la hausse des prix, à la suppression de nombreuses subv..

Ammonia Synthesis from a Pincer Ruthenium Nitride via Metal-Ligand Cooperative Proton-Coupled Electron Transfer

The conversion of metal nitride complexes to ammonia may be essential to dinitrogen fixation. We report a new reduction pathway that utilizes ligating acids and metal-ligand cooperation to effect this conversion without external reductants. Weak acids such as 4-methoxybenzoic acid and 2-pyridone react with nitride complex [(H-PNP)RuN]+ (H-PNP = HN(CH2CH2PtBu2)2) to generate octahedral ammine complexes that are κ2-chelated by the conjugate base. Experimental and computational mechanistic studies reveal the important role of Lewis basic sites proximal to the acidic proton in facilitating protonation of the nitride. The subsequent reduction to ammonia is enabled by intramolecular 2H+/2e- proton-coupled electron transfer from the saturated pincer ligand backbone

Synthesis and bonding analysis of pentagonal bipyramidal rhenium carboxamide oxo complexes

Seven-coordinate rhenium oxo complexes supported by a tetradentate bipyridine carboxamide/carboxamidate ligand are reported. The neutral dicarboxamide H2Phbpy-da ligand initially coordinates in an L4 (ONNO) fashion to an octahedral rhenium oxo precursor, yielding a seven-coordinate rhenium oxo complex. Subsequent deprotonation generates a new oxo complex featuring the dianionic (L2X2) carboxamidate (NNNN) form of the ligand. Computational studies provide insight into the relative stability of possible linkage isomers upon deprotonation. Structural studies and molecular orbital theory are employed to rationalize the relative isomer stability and provide insight into the rhenium-oxo bond order

Dimerization of Aldehydes into Esters by an Octahedral d6-Rhodium cis-Dihydride Catalyst: Inner-versus Outer-Sphere Mechanisms

The tripodal ligated octahedral complex d6-[Rh(PhB(CH2PPh2)3)(H)2(NCMe)] (1-RhH) was discovered by Tejel and co-workers to catalyze the Tishchenko reaction in which two aldehydes are dimerized into an ester. Two fundamentally different mechanisms can be envisaged for this system: (i) an inner-sphere mechanism starting with substitution of the acetonitrile ligand of 1-RhH by an aldehyde and (ii) an outer-sphere mechanism starting with direct insertion of an aldehyde into a Rh-H bond of the intact 1-RhH to make an octahedral Rh-alkoxide intermediate. We use DFT methods to investigate the two mechanisms. The inner-sphere mechanism is computed to be energetically favorable. The outer-sphere one, in contrast, is prohibitively high in energy. This is opposite to catalysis of the same reaction using Gusev's pincer-ligated octahedral catalyst trans-[(PHNN)Os(H)2(CO)] (2-OsH) where the outer-sphere mechanism was previously reported to have very low energy. The different behaviors of 1-RhH and 2-OsH can be attributed to a role from the different metals in the two catalysts as well as a role from their different ligands. Specifically, the higher oxidation state of the metal in 1-RhH, Rh(III) versus Os(II), greatly diminishes its thermodynamic hydricity leading to separated ions compared to 2-OsH, whereas the amino functionality of the ligand in 2-OsH greatly favors the kinetic hydricity in the reaction with an aldehyde by hydrogen bonding with the carbonyl group being reduced. Comparisons are also made with Milstein's trans-[PNN-Ru(H)2(CO)] alcohol dehydrogenative coupling catalyst (3-RuH) which also lacks the amino functionality. Copyright © 2020 American Chemical Society

High Activity and Selectivity for Catalytic Alkane-Alkene Transfer (De)hydrogenation by (tBuPPP)Ir and the Importance of Choice of a Sacrificial Hydrogen Acceptor

The triphosphorus-coordinating pincer iridium fragment (tBuPPP)Ir was recently reported to be highly active for the catalytic dehydrogenation of n-alkanes. Dehydrogenation is calculated to be highly regioselective for the terminal position of n-alkanes. The extremely high intermolecular selectivity observed in n-alkane/cycloalkane competition experiments supports the prediction of extremely high regioselectivity for dehydrogenation of n-alkanes. The use of sterically unhindered hydrogen acceptors is key to observing the high activity of the (tBuPPP)Ir fragment. 4,4-Dimethylpent-1-ene (TBP) is found to be particularly convenient for this purpose. With the commonly used hydrogen acceptor 3,3-dimethylbut-1-ene (TBE), (tBuPPP)Ir affords n-alkane dehydrogenation at a rate no different than that obtained with the well-known fragment (iPrPCP)Ir. However, with the use of TBP as acceptor, (tBuPPP)Ir shows much greater activity for n-alkane transfer dehydrogenation than previously reported catalysts, affording appreciable rates even at 50 °C, an unprecedentedly low temperature for catalytic alkane transfer dehydrogenation. Also critical to the identification of (tBuPPP)Ir as a highly effective catalyst is the use of n-alkane substrate rather than the commonly used model dehydrogenation substrate, cyclooctane, with which dehydrogenation rates are much lower than those with n-alkanes. © 2022 American Chemical Society. All rights reserved

Dinitrogen Reduction to Ammonium at Rhenium Utilizing Light and Proton-Coupled Electron Transfer

The direct scission of the triple bond of dinitrogen (N2) by a metal complex is an alluring entry point into the transformation of N2 to ammonia (NH3) in molecular catalysis. Reported herein is a pincer-ligated rhenium system that reduces N2 to NH3 via a well-defined reaction sequence involving reductive formation of a bridging N2 complex, photolytic N2 splitting, and proton-coupled electron transfer (PCET) reduction of the metal-nitride bond. The new complex (PONOP)ReCl3 (PONOP = 2,6-bis(diisopropylphosphinito)pyridine) is reduced under N2 to afford the trans,trans-isomer of the bimetallic complex [(PONOP)ReCl2]2(μ-N2) as an isolable kinetic product that isomerizes sequentially upon heating into the trans,cis and cis,cis isomers. All isomers are inert to thermal N2 scission, and the trans,trans-isomer is also inert to photolytic N2 cleavage. In striking contrast, illumination of the trans,cis and cis,cis-isomers with blue light (405 nm) affords the octahedral nitride complex cis-(PONOP)Re(N)Cl2 in 47% spectroscopic yield and 11% quantum yield. The photon energy drives an N2 splitting reaction that is thermodynamically unfavorable under standard conditions, producing a nitrido complex that reacts with SmI2/H2O to produce a rhenium tetrahydride complex (38% yield) and furnish ammonia in 74% yield

Reactivity of Iridium Complexes of a Triphosphorus-Pincer Ligand Based on a Secondary Phosphine. Catalytic Alkane Dehydrogenation and the Origin of Extremely High Activity

The selective functionalization of alkanes and alkyl groups is a major goal of chemical catalysis. Toward this end, a bulky triphosphine with a central secondary phosphino group, bis(2-di-t-butyl-phosphinophenyl)phosphine (tBuPHPP), has been synthesized. When complexed to iridium, it adopts a meridional (“pincer”) configuration. The secondary phosphino H atom can undergo migration to iridium to give an anionic phosphido-based-pincer (tBuPPP) complex. Stoichiometric reactions of the (tBuPPP)Ir complexes reflect a distribution of steric bulk around the iridium center in which the coordination site trans to the phosphido group is quite crowded; one coordination site cis to the phosphido is even more crowded; and the remaining site is particularly open. The (tBuPPP)Ir precursors are the most active catalysts reported to date for dehydrogenation of n-alkanes, by about 2 orders of magnitude. The electronic properties of the iridium center are similar to that of well-known analogous (RPCP)Ir catalysts. Accordingly, DFT calculations predict that (tBuPPP)Ir and (tBuPCP)Ir are, intrinsically, comparably active for alkane dehydrogenation. While dehydrogenation by (RPCP)Ir proceeds through an intermediate trans-(PCP)IrH2(alkene), (tBuPPP)Ir follows a pathway proceeding via cis-(PPP)IrH2(alkene), thereby circumventing unfavorable placement of the alkene at the bulky site trans to phosphorus. (tBuPPP)Ir and (tBuPCP)Ir, however, have analogous resting states: square planar (pincer)Ir(alkene). Alkene coordination at the crowded trans site is therefore unavoidable in the resting states. Thus, the resting state of the (tBuPPP)Ir catalyst is destabilized by the architecture of the ligand, and this is largely responsible for its unusually high catalytic activity. © 2022 American Chemical Society

Calculation of ionization energy, electron affinity, and hydride affinity trends in pincer-ligated d8-Ir(tBu4PXCXP) complexes: Implications for the thermodynamics of oxidative H2 addition

DFT methods are used to calculate the ionization energy (IE) and electron affinity (EA) trends in a series of pincer ligated d8-Ir(tBu4PXCXP) complexes (1-X), where C is a 2,6-disubstituted phenyl ring with X = O, NH, CH2, BH, S, PH, SiH2, and GeH2. Both C2v and C2 geometries are considered. Two distinct σ-type (2A1 or 2A) and π-type (2B1 or 2B) electronic states are calculated for each of the free radical cation and anion. The results exhibit complex trends, but can be satisfactorily accounted for by invoking a combination of electronegativity and specific π-orbital effects. The calculations are also used to study the effects of varying X on the thermodynamics of oxidative H2 addition to 1-X. Two closed shell singlet states differentiated in the C2 point group by the d6-electon configuration are investigated for the five-coordinate Ir(III) dihydride product. One electronic state has a d6-(a)2(b)2(b)2 configuration and a square pyramidal geometry, the other a d6-(a)2(b)2(a)2 configuration with a distorted-Y trigonal bipyramidal geometry. No simple correlations are found between the computed reaction energies of H2 addition and either the IEs or EAs. To better understand the origin of the computed trends, the thermodynamics of H2 addition are analyzed using a cycle of hydride and proton addition steps. The analysis highlights the importance of the electron and hydride affinities, which are not commonly used in rationalizing trends of oxidative addition reactions. Thus, different complexes such as 1-O and 1-CH2 can have very similar reaction energies for H2 addition arising from opposing hydride and proton affinity effects. Additional calculations on methane C-H bond addition to 1-X afford reaction and activation energy trends that correlate with the reaction energies of H2 addition leading to the Y-product. © 2014 American Chemical Society

Synthesis and bonding analysis of pentagonal bipyramidal rhenium carboxamide oxo complexes

Seven-coordinate rhenium oxo complexes supported by a tetradentate bipyridine carboxamide/carboxamidate ligand are reported. The neutral dicarboxamide H2Phbpy-da ligand initially coordinates in an L4 (ONNO) fashion to an octahedral rhenium oxo precursor, yielding a seven-coordinate rhenium oxo complex. Subsequent deprotonation generates a new oxo complex featuring the dianionic (L2X2) carboxamidate (NNNN) form of the ligand. Computational studies provide insight into the relative stability of possible linkage isomers upon deprotonation. Structural studies and molecular orbital theory are employed to rationalize the relative isomer stability and provide insight into the rhenium-oxo bond order. © 2023 The Royal Society of Chemistry

Ammonia Synthesis from a Pincer Ruthenium Nitride via Metal-Ligand Cooperative Proton-Coupled Electron Transfer

The conversion of metal nitride complexes to ammonia may be essential to dinitrogen fixation. We report a new reduction pathway that utilizes ligating acids and metal-ligand cooperation to effect this conversion without external reductants. Weak acids such as 4-methoxybenzoic acid and 2-pyridone react with nitride complex [(H-PNP)RuN]+ (H-PNP = HN(CH2CH2PtBu2)2) to generate octahedral ammine complexes that are κ2-chelated by the conjugate base. Experimental and computational mechanistic studies reveal the important role of Lewis basic sites proximal to the acidic proton in facilitating protonation of the nitride. The subsequent reduction to ammonia is enabled by intramolecular 2H+/2e- proton-coupled electron transfer from the saturated pincer ligand backbone. © 2017 American Chemical Society