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The direct functionalization of Si−H bonds by the nitrene insertion methodology is described. A copper(I) complex bearing a trispyrazolylborate ligand catalyzes the transfer of a nitrene group from PhINTs to the Si−H bond of silanes, disilanes, and siloxanes, leading to the exclusive formation of Si−NH moieties in the first example of this transformation. The process tolerates other functionalities in the substrate such as several C−H bonds and alkyne and alkene moieties directly bonded to the silicon center. Density functional theory (DFT) calculations provide a mechanistic interpretation consisting of a Si−H homolytic cleavage and subsequent rebound to the Si-centered radical., We thank the Ministerio de Ciencia e Innovación for Grants PID2020-113797RB-C21, PID2020-112825RB-I00, and CEX2019-000925-S as well as FEDER for “Una manera de hacer Europa” funding. We also thank Junta de Andalucía (P20-00348) and Universidad de Huelva (P.O.Feder UHU202016). A.M.R. and R.P.-S. thank Ministerio de Universidades for the FPU fellowships (FPU17/02738 and FPU18/ 01138, respectively), and J.P.-R. thanks Fondo de Garantía Juvenil for a research contract. CERCA Programme/Generalitat de Catalunya is also acknowledged. We thank Prof. T. R. Belderrain for helpful discussions on 29Si NMR spectroscopy. Funding for open access charge: Universidad de Huelva / CBUA

The objective of this study was to compare performance on a comprehensive impulsivity battery of SUD outpatients who dropout versus those who do not dropout and of abstainers versus relapsers at 3 and 12 months of treatment follow-up. Impulsivity was measured at the start of treatment and adherence and relapse at 3 and 12 months. The participants are 115 outpatients with SUD. Motor impulsivity (Affective Go/No Go), attentional impulsivity (Stroop), delay discounting (Monetary Choice Questionnaire; MCQ), and decision making (Iowa Gambling Task; IGT) were assessed. Impulsivity was not associated with dropout. There were no relationships between treatment outcomes and the MCQ and IGT. Stroop and affective Go-No Go were associated with relapse at 3 and 12 months. Affective motor disinhibition and cognitive disinhibition predict relapse in outpatients. No cognitive aspect of impulsiveness is related to dropout., Funding for open access publishing: Universidad de Huelva/CBUA This study was supported by the “Longitudinal study about the effect of treatment on executive function recovery in patients with cocaine and alcohol dependence: implications on treatment outcomes” funded by the Delegación del Gobierno para el Plan Nacional sobre Drogas (Spain) (grant number Q7150008F-2016/034). Funding for open access charge: Universidad de Huelva / CBUA.

Control of the regioselectivity in the functionalization of C–H bonds of linear alkanes C2H2n+2 via carbene transfer from diazo compounds is restricted to the use of rhodium-based catalysts, which govern the reaction outcome employing donor–acceptor diazo reagents. At variance with that catalyst-controlled strategy, we present an alternative approach in which employing the appropriate silver complexes containing trispyrazolylborate ligands as catalysts with large differences in their steric and electronic properties, the regioselection is mainly governed by the diazo reagent, which leads to the functionalization of primary or secondary sites of linear alkanes (lacking any activating or directing groups). Donor–acceptor aryl diazoacetates exclusively provide the functionalization of the secondary sites of hexane or pentane, whereas acceptor ethyl diazoacetate leads to an unprecedented level of primary functionalization., We thank to Ministerio de Ciencia e Innovación for Grant PID2020-113797RB-C21. We also thank Junta de Andalucía (P18-1536) and Universidad de Huelva (P.O.Feder UHU- 202024). M.A. thanks Junta de Andalucia for a postdoctoral fellowship.

Complexes [(NHC)MCl] (M = coinage metal) have been evaluated as catalyst for the olefin aziridination reaction using PhI=NTs as nitrene source, with moderate to high activity being found depending of the metal and the olefin. At variance with frequently employed copper catalysts with bi-, tri- or tetradentate, N-donor ligands, these monodentante, C-donor ligand infer a remarkable effect in the reaction mechanism. Experimental evidences support the proposal of a concerted mechanism and the absence of radical intermediates, which are the commonly proposed species involved in these nitrene transfer reactions., We thank to Ministerio de Ciencia e Innovación for Grant PID2020-113797RB-C21, also financed by FEDER “Una manera de hacer Europa”. We also thank Junta de Andalucía (P20-00348) and Universidad de Huelva (P.O.Feder UHU-202016).

The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp3)−H bond has been achieved for the first time during a silver-catalyzed carbene/alkyne metathesis (CAM) process. A Tpx-containing silver complex first promotes the generation of a donor-acceptor silver carbene which triggers CAM, generating a subsequent donor-donor vinyl silver carbene species, which then undergoes a selective vinylogous C(sp3)−H bond insertion, leading to the synthesis of a new family of benzoazepines. Density functional theory (DFT) calculations unveil the reaction mechanism, which allows proposing that the C−H bond insertion reaction takes place in a stepwise manner, with the hydrogen shift being the rate determining step., We are grateful for financial support from the Ministerio de Ciencia e Innovación (PGC2018-097722-B-I00, PID2020113797RB-C21 and PID2020-113711GB-I00 MCIN/AEI/ 10.13039/501100011033 and FPU grants to A.D.-J. and R.M.-C.) and the Generalitat de Catalunya (Project 2017SGR-39). We also thank Junta de Andalucía (P18-1536) and Universidad de Huelva (P.O.Feder UHU202024). A.P.Q. and A.P. are Serra Húnter Fellows and A.P. thanks ICREA Academia Prize 2019. M.A. thanks Junta de Andalucia for a postdoctoral fellowship. E.B. thanks Cátedra Cepsa-Universidad de Huelva for financial support.

The direct oxidation of benzene into phenol using molecular oxygen at very mild temperatures can be promoted in the presence of the copper complex TpBr3Cu(NCMe) in the homogeneous phase in the presence of ascorbic acid as the source of protons and electrons. The stoichiometric nature, relative to copper, of this transformation prompted a thorough DFT study in order to understand the reaction pathway. As a result, the dinuclear species TpBr3CuII(μ-O•)(μ-OH)CuIITpBr3 is proposed as the relevant structure which is responsible for activating the arene C−H bond leading to phenol formation., We thank the Spanish Ministerio de Ciencia e Innovación for Grants PID2020-113797RB-C21 (also financed by FEDER “Una manera de hacer Europa”) and PID2020 116861GB-I00. We also thank Junta de Andaluci ́ a (P18-RT-1536), the Universidad de Huelva (P.O.Feder UHU-1260216,) and Cátedra CEPSA for funding. E.B. thanks CEPSA for a Ph. D. fellowship. L.T.-S. thanks the Spanish Ministerio de Uni- versidades (grant FPU18/05895)

The complete regioselective incorporation of carbene units to nonactivated arene rings has been achieved employing gold(I) catalysts bearing alkoxydiaminophosphine ligands, with readily available, nonelaborated ethyl 2-phenyldiazoacetate as the carbene source. These results are in contrast with the scarce precedents which required highly elaborated diazo substrates. Density functional theory (DFT) calculations have revealed the important role of the R group in the C(R)CO

Gold nanoparticles stabilized by NHC ligands and supported onto reduced graphene oxide (rGO) catalyse the functionalization of cyclohexane and benzene C–H bonds upon insertion of carbene CHCO2Et (from N2[double bond, length as m-dash]CHCO2Et) groups. This is the first example in which such Csp3-H or Csp2-H bonds are functionalized with this strategy with nanoparticulated gold. This Au-NP@rGO material shows an exceptional activity, providing TON values 5–10 times higher than those already reported for molecular gold catalysts. Recyclability is also effective, reaching an accumulated TON value of 1400 after six consecutive uses., We thank Ministerio de Ciencia e Innovación for Grants PID2020-113797RB-C21, RTI2018-098237-B-C22 and PID2019-105881RB-I00 also financed by the FEDER “Una manera de hacer Europa”. We also thank Junta de Andalucía (P18-RT-1536) and Universidad de Huelva (P.O.Feder UHU-1260216). JML thanks Ministerio de Ciencia e Innovación for the FPI fellowship. A. M-C. thanks Generalitat Valenciana for grant ACIF/2019/100. S. M. acknowledges DGA/fondos FEDER (Construyendo Europa desde Aragón) for funding the research group Platón (E31_20R). The authors thank ‘Servei Central d'Instrumentació Científica (SCIC) de la Universitat Jaume I′ and Dr G. Antorrena for the technical support in XPS studies.