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The redox-active nature of a pincer has been exploited to conduct C-C cross-coupling reactions under mild conditions. A nickel complex with a NNN pincer was dimeric in the solid state, and the structure displayed a Ni2 N2 diamond core. In the dimeric structure, both ligand backbones house an electron, in the iminosemiquinonate form, to keep the metal's oxidation state at +2. In the presence of an aryl Grignard reagent, only 3 mol % loading the nickel complex generates a Kumada cross-coupled product in good yield from a wide variety of aryl-X (X= I, Br, Cl) substrates. That the ligand-based radical remains responsible for promoting such a coupling reaction following a radical pathway is suggested by TEMPO quenching. Furthermore, a radical-clock experiment along with tracing product distribution unambiguously supported the radical's involvement through the catalytic cycle. A series of thorough mechanistic probation, including computational DFT analysis, disclosed the cooperative action of both redox-active pincer ligand and the metal centre to drive the reaction.

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A series of iridium complexes with bis(diisopropylphenyl)iminoacenaphtene (dpp-bian) ligands, [Ir(cod)(dpp-bian)Cl] (1), [Ir(cod)(NO)(dpp-bian)](BF4)2 (2) and [Ir(cod)(dpp-bian)](BF4) (3), were prepared and characterized by spectroscopic techniques, elemental analysis, X-ray diffraction analysis and cyclic voltammetry (CV). The structures of 1-3 feature a square planar backbone consisting of two C = C π-bonds of 1,5-cyclooctadiene (cod) and two nitrogen atoms of dpp-bian supplemented with a chloride ion (for 1) or a NO group (for 2) to complete a square-pyramidal geometry. In the nitrosyl complex 2, the Ir-N-O group has a bent geometry (the angle is 125°). The CV data for 1 and 3 show two reversible waves between 0 and -1.6 V (vs. Ag/AgCl). Reversible oxidation was also found at E1/2 = 0.60 V for 1. Magnetochemical measurements for 2 in a range from 1.77 to 300 K revealed an increase in the magnetic moment with increasing temperature up to 1.2 µB (at 300 K). Nitrosyl complex 2 is unstable in solution and loses its NO group to yield [Ir(cod)(dpp-bian)](BF4) (3). A paramagnetic complex, [Ir(cod)(dpp-bian)](BF4)2 (4), was also detected in the solution of 2 as a result of its decomposition. The EPR spectrum of 4 in CH2Cl2 is described by the spin Hamiltonian H = gßHS with S = 1/2 and gxx = gyy = 2.393 and gzz = 1.88, which are characteristic of the low-spin 5d7-Ir(II) state. DFT calculations were carried out in order to rationalize the experimental results.

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Antimony corrole cations have been prepared by one-electron oxidation of antimony(III) congeners with silver(I) and copper(II) salts. Isolation and crystallization was successful for the first time, and the X-ray crystallographic investigation unraveled structural similarities with antimony(III)corroles. EPR experiments showed strong hyperfine interactions of the unpaired electron with the 121 Sb (I=5/2) and 123 Sb nuclei (I=7/2). A DFT analysis supports the description of the oxidized form as a SbIII corrole radical with less than 2 % SbIV character. In the presence of water or a fluoride source like PF6 - , the compounds undergo a redox disproportionation to yield known antimony(III)corroles and either difluorido-antimony(V)corroles, or bis-µ-oxido-di[antimony(V)corroles] via novel cationic hydroxo-antimony(V) derivatives.

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Heteroleptic molybdenum complexes bearing 1,5-diaza-3,7-diphosphacyclooctane (P2 N2 ) and non-innocent dithiolene ligands were synthesized and electrochemically characterized. The reduction potentials of the complexes were found to be fine-tuned by a synergistic effect identified by DFT calculations as ligand-ligand cooperativity via non-covalent interactions. This finding is supported by electrochemical studies combined with UV/Vis spectroscopy and temperature-dependent NMR spectroscopy. The observed behavior is reminiscent of enzymatic redox modulation using second ligand sphere effects.

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The #MeToo movement has provoked a worldwide discussion about sexual violence. Some critics of the movement argue that it violates the presumption of innocence. In the current study, we investigated the determinants of the perception of the presumption of innocence in the context of media depictions of violence. We took into account previous studies that suggest that people view more favorably defendants in rape trials than they do men accused of other crimes and that people view more favorably defendants with a high socioeconomic status than they do those with a low socioeconomic status. The current study investigated whether the perception of the presumption of innocence is related to the type of crime (sexual vs. nonsexual assault) or to the socioeconomic status of the defendant (a famous writer vs. a maintenance worker). We conducted a vignette-based study with a sample of Polish people (N = 158). The type of crime did not influence the perception of the presumption of innocence; however, women who participated in the study endorsed the presumption of innocence to a greater extent when the defendant had a high socioeconomic status. The theoretical and practical implications of these results are discussed.

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The article dealt with the ruthenium complexes of redox active azo appended modified lawsone L1 - (HL1 : (E)-2-hydroxy-3-(p-tolyldiazenyl)naphthalene-1,4-dione))/L2 - (HL2 :5-hydroxy-6-p-tolylazobenzo[a]phenazine) derived [RuIII (acac)2 (L1 - )]/[RuIII (acac)2 (L2 - )] 1/5, [RuII (bpy)2 (L1 - )]ClO4 /[RuII (bpy)2 (L2 - )]ClO4 [2]ClO4 /[6]ClO4 , ctc-[RuII (pap)2 (L1 - )]ClO4 /ctc-[RuII (pap)2 (L2 - )]ClO4 [3]ClO4 /[7]ClO4 and [RuII (CO)(H)(PPh3 )2 (L1 - )]/[RuII (CO)(Cl)(PPh3 )2 (L2 - )] 4/8 (acac=acetylacetonate, bpy=2,2'-bipyridine, pap=2-phenylazopyridine). The ligands L1 - and L2 - differed with respect to the para-quinone versus phenazine moieties linked to the azo function. Structural analysis of the complexes established unreduced state of the azo (N=N) group of coordinated L1 - /L2 - or pap as well as unprecedented para-quinone form of L1 - . The involvement of selective redox center(s) towards the accessible redox steps of the complexes encompassing multiple redox active entities i. e. Ru, phenolate (L1 - /L2 - ), para-quinone (L1 - ), phenazine (L2 - ), azo (L1 - /L2 - , pap), diimine (bpy) was analyzed by combined experimental and DFT calculations. It revealed that under the prevailing competitive scenario oxidation was mostly dominated by the phenolate group of L1 - /L2 - (phenolate→phenoxide), while successive reductions were taken place either at the para-quinone/phenazine units of L1 - /L2 - or azo/diimine functions of pap/bpy. Though the azo function of pap in 3+ /7+ underwent facile reduction, the same azo function associated with L1 - /L2 - conspicuously remained unreduced in all occasions. The frontier molecular orbital analysis revealed that the propensity of pap for the azo reduction with special reference to that in L1 - /L2 - could be correlated with its relatively lower energy π* orbital (LUMO). Complexes displayed intense LMCT (1/5) and bpy (2+ /6+ ), pap (3+ /7+ ), L (4/8) targeted MLCT transitions in the visible region.

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Amendments to the Jordanian Code of Criminal Procedure (JCCP) concerning the rationale for detention have narrowed its scope of application and provided for alternatives. However, although these amendments are important, their drafting has not achieved the stated objectives. To address this issue, the laws of Jordan and France are reviewed. The study's novelty lies in the justification for detention in the JCCP, which takes advantage of the long experience of French law and justice. It is recommended that the Public Prosecutor and the competent court justify an extension to a period of detention or a denial of release based on Article 114(1) of the JCCP. It is also suggested that a detention warrant is only issued or extended when grounded on the details of the specific case; that is, detention must only be effected when an alternative cannot achieve one or more of the goals of detention.

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The unexplored 'actor' behavior of redox-active bis(aldimine) congener, p-phenylene-bis(picoline)aldimine (L1), towards dioxygen activation and subsequent functionalization of its backbone was demonstrated on coordination with {Ru(acac)2 } (acac= acetylacetonate). Reaction under aerobic condition led to the one-pot generation of dinuclear complexes with unperturbed L1, imino-carboxamido (L2- ), and bis(carboxamido) (L32- )-bridged isovalent {RuII (µ-L1)RuII }, 1/ {RuIII (µ-L32- )RuIII }, 3 and mixed-valent {RuII (µ-L2- )RuIII }, 2. Authentication of the complexes along with the redox non-innocence behavior of their bridge have been validated through structure, spectroelectrochemistry and DFT calculations. Kinetic and isotope labelling experiments together with DFT analyzed transition states justified the consideration of redox shuttling at metal/L1 interface for 3 O2 activation despite of the closed shell configuration of 1 (S=0) to give carboxamido derived 2/3.

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This article reflects on the manipulative practices of autocratic populist leaders in North and South America and looks at their speeches, which appeal to followers who desire love and protection, or who seek an outlet for aggressive impulses. Jung's considerations regarding the annihilation of the other, evil and the unconsciousness of the masses - manipulated for purposes of subjugation - are important for understanding the risks that threaten society. The behaviour of unscrupulous leaders seized by power complexes, reinforced by psychopathic traits in clinic and culture, creates an increasing number of victims. A lack of imagination for evil is behind the absence of malice as a defence and the idealization which opens doors to the violence of totalitarian leaders and of dominant figures in social and family relationships. The polarities evil-innocence and dominator-dominated are severely dissociated in contemporary society, endorsing Jung's vision as a warning against destructiveness.

Cet article examine les pratiques manipulatrices des leaders populistes autocrates d'Amérique du Nord et du Sud. Il étudie leurs discours, qui attirent les fidèles, c'est-à-dire ceux qui désirent amour et protection ou qui recherchent un exutoire à leurs impulsions agressives. Les considérations de Jung concernant l'annihilation de l'autre, le mal, et l'inconscience des masses - manipulées pour les asservir - sont importantes pour comprendre les risques qui menacent la société. Le comportement de leaders sans scrupules et en proie à des complexes de pouvoir, auxquels s'ajoutent des caractéristiques psychopathiques dans le sens clinique et culturel, crée un nombre de victimes qui va grandissant. Un manque d'imagination en ce qui concerne le mal est à l'origine d'une absence défensive de malveillance et d'une idéalisation qui ouvrent la voie à la violence de leaders totalitaristes et de personnages dominants dans les relations sociales et familiales. Les polarités mal-innocence et dominant-dominé sont sévèrement dissociées dans la société contemporaine, ce qui cautionne la vision de Jung en tant qu'avertissement contre la destructivité.

Este artículo reflexiona acerca de las prácticas manipuladoras por parte de líderes populistas autocráticos en América del Norte y del Sur, y atiende a sus discursos, los cuales atraen a seguidores que desean amor y protección o buscan una salida a sus impulsos agresivos. Las consideraciones de Jung sobre la aniquilación del otro, el mal y la inconsciencia de las masas - manipuladas para propósitos de dominación - son importantes para la comprensión de los riesgos que amenazan a la sociedad. La conducta de líderes inescrupulosos poseídos por complejos de poder, reforzado por rasgos psicopáticos en la clínica y en la cultura, crea un creciente número de víctimas. La ausencia de imaginación para el mal está detrás de la ausencia de malicia como defensa y de la idealización que abre las puertas a la violencia de líderes totalitarios y de figuras dominantes en las relaciones sociales y familiares. Las polaridades mal-inocencia y dominador-dominado se encuentran severamente disociadas en la sociedad contemporánea, ratificando la visión de Jung como un llamado de atención contra la destructividad.

Este artigo reflete sobre as práticas manipuladoras de líderes populistas autocráticos nas Américas do Norte e do Sul e analisa seus discursos, que atraem seguidores que desejam amor e proteção, ou que buscam uma saída para impulsos agressivos. As considerações de Jung sobre a aniquilação do outro, o mal e a inconsciência das massas - manipuladas para fins de subjugação - são importantes para entender os riscos que ameaçam a sociedade. O comportamento de líderes sem escrúpulos apreendidos por complexos de poder, reforçados por traços psicopáticos na clínica e na cultura, cria um número crescente de vítimas. A falta de imaginação para o mal está por trás da ausência de malícia como defesa e da idealização que abre portas para a violência dos líderes totalitários e das figuras dominantes nas relações sociais e familiares. As polaridades maldade/inocência e dominados/dominadores são severamente dissociadas na sociedade contemporânea, endossando a visão de Jung como um aviso contra a destrutividade.

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El presente artículo expone los argumentos que edificó la Corte Constitucional a la hora de revisar la acción pública de inconstitucionalidad que se presentó en contra del parágrafo 1 del artículo 8 de la Ley 1843 de 2017. La importancia de identificar la estructura argumentativa de la Corte Constitucional, permite entender de qué manera los presupuestos rectores del derecho fundamental al debido proceso son vinculantes, al momento de impedir que la extensión de la solidaridad en el pago de una sanción pecuniaria derivada del uso de las cámaras de fotodetección, ponga en riesgo la aplicación del principio de responsabilidad individual, la imputación, la tipicidad y la debida defensa.

This article sets out the arguments built by the Constitutional Court when reviewing the public action of unconstitutionality filed against paragraph 1 of Article 8 of Law 1843 of 2017. The importance of identifying the argumentative structure of the Constitutional Court, allows understanding how the guiding assumptions of the fundamental right to due process are binding, when preventing the extension of solidarity in the payment of a pecuniary sanction derived from the use of photodetection cameras, jeopardizing the application of the principle of individual responsibility, imputation, typicality and due defense.

Este artigo apresenta os argumentos construídos pelo Tribunal Constitucional ao rever a ação pública de inconstitucionalidade apresentada contra o parágrafo 1 do artigo 8 da Lei 1843 de 2017. A importância de identificar a estrutura argumentativa do Tribunal Constitucional, nos permite compreender como são vinculativas as premissas norteadoras do direito fundamental ao devido processo, ao impedir a extensão da solidariedade no pagamento de uma penalidade financeira derivada do uso de câmeras fotodetetoras, colocando em risco a aplicação do princípio da responsabilidade individual, imputação, criminalidade e devida defesa.

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We report the synthesis and spectroscopic characterization of a series of iron-carbene complexes in redox states {Fe=C(H)Ar}10-11 . Pulse EPR studies of the 1,2 H and 13 C isotopologues of {Fe=C(H)Ar}11 reveal the high covalency of the Fe-carbene bonding, leading to a more even spin distribution than commonly observed for reduced Fischer carbenes.

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We present two iridium complexes 1H + and 2H + that contain cationic ligands to extend the knowledge of charge-assisted hydrogen bonding (CAHB), which counts among the strongest non-covalent bonding interactions. Upon protonation, both complexes were converted into new hydrogen-bonding arrays with various selectivity for respective H-bonding partners. This study compares the association strengths of four hydrogen-bonding co-systems, emphasizing the roles of CAHB in supramolecular systems. We determined that the cationic charge in these systems contributed up to 2.7 kJ mol-1 in the H-bonding complexation processes.

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We report an efficient and broadly applicable palladium-catalyzed iodination of inexpensive and abundant aryl and vinyl carboxylic acids via in situ activation to the acid chloride and formation of a phosphonium salt. The use of 1-iodobutane as iodide source in combination with a base and a deoxychlorinating reagent gives access to a wide range of aryl and vinyl iodides under Pd/Xantphos catalysis, including complex drug-like scaffolds. Stoichiometric experiments and kinetic analysis suggest a unique mechanism involving C-P reductive elimination to form the Xantphos phosphonium chloride, which subsequently initiates an unusual halogen exchange by outer sphere nucleophilic substitution.

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A facile method for the quantitative preparation of silver dibenzo-fused corrole Ag-1 is described. In contrast to the saddle conformation resolved by single-crystal X-ray analysis for Ag-1, it adopts an unprecedented domed geometry, with up and down orientations, when adsorbed on an Ag(111) surface. Sharp Kondo resonances near Fermi level, both at the corrole ligand and the silver center were observed by cryogenic STM, with relatively high Kondo temperature (172 K), providing evidence for a non-innocent AgII -corrole.2- species. Further investigation validates that benzene ring fusion and molecule-substrate interactions play pivotal roles in enhancing Ag(4d(x2 -y2 ))-corrole (π) orbital interactions, thereby stabilizing the open-shell singlet AgII -corrole.2- on Ag(111) surface. Moreover, this strategy used for constructing metal-free benzene-ring fused corrole ligand gives rise to inspiration of designing novel metal-corrole compound for multichannel molecular spintronics devices.

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This is a brief response to the critique of my previous article, No Longer the Gold Standard: Probabilistic Genotyping is Changing the Nature of DNA Evidence in Criminal Trials, 24 Berkeley J. Crim. L. 110 (2019). The critique of my article was published earlier this year in this journal. I address both criticisms and misunderstandings of my arguments in an effort to frame the concerns of the criminal defense community about the impact of probabilistic genotyping on the deliberative process.

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Epindolidione (H2 L), a heteroatom-modified analogue of tetracene and a structural isomer of indigo, forms dinuclear complexes with [RuX2 ]2+ , X=bpy (2,2'-bipyridine, [1]2+ ) or pap (2-phenylazopyridine, [2]2+ ), in its doubly deprotonated bridging form µ-L2- . The dications in compounds meso-[1](ClO4 )2 and meso-[2](ClO4 )2 , [X2 Ru(µ-L)RuX2 ](ClO4 )2 , contain five-membered chelate rings N-C-C-O-RuII with π bridged metals at an intramolecular distance of 7.19 Å. Stepwise reversible oxidation and reduction is mainly ligand centered (oxidation: L2- ; reduction: X), as deduced from EPR of one-electron oxidized and reduced intermediates and from UV/Vis/NIR spectroelectrochemistry, supported by TD-DFT calculation results. The results for [1](ClO4 )2 and [2](ClO4 )2 are qualitatively similar to the ones observed with the deprotonated indigo-bridged isomers with their six-membered chelate ring structures, confirming the suitability of both π systems for molecular electronics applications, low-energy absorptions, and multiple electron transfers.

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The present article demonstrates that ruthenium-hydride [RuII (H)(Cl)(CO)(PPh3 )3 ] mediated diverse functionalization modes of benzodifuroxan (BDF) encompassing two furoxan rings. Hydride transfer from the metal precursor facilitated multiple cascade reactions involving unsymmetrical cleavage of the furoxan rings of BDF, leading to the one-pot formation of a series of ruthenium (II) coordinated functionalized ligands exhibiting bidentate κ2 -N,O, κ2 -N,N' and bis-bidentate µ-bis(κ2 -N,O) modes. Further, a moderately stable intermediate species was also encountered in the reaction sequence in which the transformed deoxygenated ligand coordinated to the metal ion via the rarely manifested furazan ring (κ2 -N,N'' mode). The products were authenticated by their single-crystal X-ray structures and other spectroscopic/analytical techniques. Redox non-innocence of the functionalized ligands in the complexes was illustrated by spectroelectrochemistry (cyclic voltammmetry, UV-Vis. and EPR) in conjunction with DFT/TD-DFT calculations. Mechanistic outline for the facile ring opening processes of BDF including interconversions of complexes (e. g. reductive ring opening) were also addressed.

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The dianion derived from (2Z,6Z)-3,7-diphenyl-N2,N6-di(pyridin-2-yl)pyrrolo[2,3-f]indole-2,6(1H,5H)-diimine (H2 BL), a modified BODIPY ligand precursor, is shown to be capable of bridging two metal complex fragments RuL2 , L=2,4-pentanedionato (acac- ), 2,2'-bipyridine (bpy) or 2-phenylazopyridine (pap) in [Ru(acac)2 Ru(µ-BL)Ru(acac)2 ] (1/2), [Ru(bpy)2 Ru(µ-BL)Ru(bpy)2 ](ClO4 )2 ([3](ClO4 )2 ) and [Ru(pap)2 Ru(µ-BL)Ru(pap)2 ](ClO4 )2 ([4](ClO4 )2 ). The compounds, including a diastereoisomeric pair 1 (meso) and 2 (rac) were spectroscopically and structurally characterized. Reversible electron transfers as revealed by cyclic and differential pulse voltammetry allowed for an EPR and UV-vis-NIR spectroelectrochemical investigation of several neighboring charge states. Together with susceptibility measurements and TD-DFT calculations the assignment of oxidation states reveals that 1, 2 are diruthenium(III) species which can be oxidized or reduced by one electron whereas 32+ and 42+ contain ruthenium(II) and get reduced or oxidized mainly at the dianionic bridge (32+ ) or are reduced at the ancillary ligands pap (42+ ).

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Stiffelman [1] gives a broad critique of the application of likelihood ratios (LRs) in forensic science, in particular their use in probabilistic genotyping (PG) software. These are discussed in this review. LRs do not infringe on the ultimate issue. The Bayesian paradigm clearly separates the role of the scientist from that of the decision makers and distances the scientist from comment on the ultimate and subsidiary issues. LRs do not affect the reasonable doubt standard. Fact finders must still make decisions based on all the evidence and they must do this considering all evidence, not just that given probabilistically. LRs do not infringe on the presumption of innocence. The presumption of innocence does not equate with a prior probability of zero but simply that the person of interest (POI) is no more likely than anyone else to be the donor. Propositions need to be exhaustive within the context of the case. That is, propositions deemed relevant by either defense or prosecution which are not fanciful must not be omitted from consideration.

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False confessions are a contributing factor in almost 30% of DNA exonerations in the United States. Similar problems have been documented all over the world. We present a novel framework to highlight the processes through which innocent people, once misidentified as suspects, experience cumulative disadvantages that culminate in pernicious consequences. The cumulative-disadvantage framework details how the innocent suspect's naivete and the interrogator's presumption of guilt trigger a process that can lead to false confession, the aftereffects of which spread to corrupt evidence gathering, bias forensic analysis, and virtually ensure wrongful convictions at trial or through pressured false guilty pleas. The framework integrates nascent research underscoring the enduring effects of the accumulated disadvantages postconviction and even after exoneration. We synthesize findings from psychological science, corroborating naturalistic evidence, and relevant legal precedents to explain how an innocent suspect's disadvantages can accumulate through the actions of law enforcement, forensic examiners, prosecutors, defense attorneys, judges, juries, and appeals courts. We conclude with prescribed research directions that can lead to empirically driven reforms to address the gestalt of the multistage process.

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