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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.

Efficient olefin aziridination has been achieved with a tris(triazolyl)methane copper catalyst supported onto polystyrene. Aryl, alkyl and methoxycarbonyl-substituted olefins are converted into N-tosylaziridines in good to high yields. The solid catalyst is readily separated by filtration and recycled, allowing its reuse with no significant loss of the catalytic activity.

Polymeric materials bearing polar groups constitute a class of macromolecules with interest in a number of uses. Because the direct synthesis employing polymerization strategies from polar monomers is very often precluded by catalyst poisoning or uncontrolled side reactions, the alternative postpolymerization route consisting in modifying a previously prepared polymer is continuously progressing. However, such a posteriori modification depends on the existence of potential reaction sites in the polymer. Because of this, polyolefins are the most challenging substrates to work with and, among them, the saturated ones. In this contribution, the current state of the art of the metal-catalyzed modification of polyolefins and subsequent polar group incorporation is provided., We acknowledge financial support from the Ministerio de Ciencia e Innovacion (CTQ2017-82893-C2-1-R), Junta de Andalucia (P18-RT-1536), and Universidad de Huelva (P.O.Feder UHU-1260216 and UHU-1254043). DYNASOL SLU is also highly appreciated for financial support. Funding for open access charge: Universidad de Huelva / CBUA

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)

For years, metal–nitrene-transfer reactions have been mainly directed toward C=C bond aziridination or C–H bond amidation reactions. In the last decade, multiple efforts have been made to develop new synthetic approaches to expand the applicability of this powerful tool, resulting in the synthesis of complex structures from relatively simple starting materials. Here, we present our contributions to the area with several novel and, to some degree, unexpected transformations developed by our research group. The catalysts for these nitrene-transfer reactions are copper or silver complexes bearing hydrotrispyrazolyl (scorpionate) ligands. These transformations have contributed to an expansion of the scope of organic compounds accessible by nitrene-transfer reactions and to an understanding of the reactivity of metallonitrene species toward the oxidation of less-explored organic substrates.1 Introduction2 Synthesis of 1,2-Dihydropyridines from Furans3 Regio- and Stereoselective Aziridination of Dienes4 Chemoselective Synthesis of Aminimides from Amines5 Synthesis of Sulfinamides and Isothiazoles from Alkynes6 Formation of Azetidines and Methylene Aziridines from Allenes7 Conclusion

En los últimos años ha aumentado el interés por el estudio de la ciberviolencia en la pareja, sin embargo es necesario examinar la metodología de investigación que sustenta las evidencias obtenidas hasta el momento. Este artículo presenta una revisión sistemática de la literatura científica que analiza 30 instrumentos de medida de ciberviolencia en la pareja de adolescentes y jóvenes adultos utilizados a lo largo de estos años. Los principales resultados muestran una elevada pluralidad metodológica, conceptual y terminológica, observándose un reducido número de instrumentos con suficientes garantías psicométricas. Predominan los trabajos de procedencia estadounidense y, entre los instrumentos aplicados en muestras españolas, destaca una infrarrepresentación de indicadores de ciberviolencia de tipo sexual, lo que limita la comprensión de esta problemática. Esta investigación aporta información sobre el estado actual en el estudio de la ciberviolencia en la pareja y pone de relieve deficiencias metodológicas en la construcción del conocimiento en este campo de estudio. Este trabajo permite una mejor comprensión de la disparidad de resultados señalada por investigaciones previas, especialmente referidas a prevalencia, frecuencia y diferencias de género en este tipo de comportamientos violentos, además de sentar las bases para abordar el fenómeno desde el rigor científico. The interest for the study of the cyber dating abuse has increased in the last years; however, it is necessary to examine the research methodology that supports the evidence obtained so far. This paper presents a systematic review of the scientific literature that analyzes 30 measuring instruments of cyber dating abuse in adolescent and young adults used along these years. The main results show a methodological, conceptual and terminological plurality, observing a small number of instruments with sufficient psychometric guarantees. The instruments come mostly from the United States, and of the instruments applied to Spanish samples, few include indicators of sexual cyber dating abuse, which limits the understanding of this problem. This research provides information on the current status of the study of cyber dating abuse and highlights methodological shortcomings in the construction of knowledge in this field of study. This study allows a better understanding of the disparity of results indicated by previous research, especially referring to prevalence, frequency and gender differences in this type of violent behavior, as well as laying the foundations for addressing the phenomenon from scientific rigor.

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.

The catalytic functionalization of pyrroles by incorporation of a nitrene group is reported. The Cα‐H bond of 1H‐pyrrole is amidated upon the formal insertion of the NTs (Ts=p‐toluenesulfonyl) group catalyzed by TpBr3Cu(NCMe) (TpBr3=hydrotris(3,4,5‐tribromo‐pyrazolyl)borate). N‐substituted pyrroles also verify the same transformation. The mechanism proposal is similar to that previously described for benzene amidation with the same catalyst and PhI=NTs, which takes place through aziridine formation, ring opening and 1,2‐hydrogen shift. A cascade reaction involving the coupling of 2,5‐dimethylfuran, 1,2,3‐trimethyl‐pyrrole and a nitrene NTs group is also described, leading to a 1,2‐dihydropyridine‐imine compound., Support for this work was provided by the MINECO (CTQ2017‐82893‐C2‐1‐R and PO FEDER 2014‐2020, UHU‐1254043). AMR and MRR thanks MEC for a FPU fellowships.

A first quantitative model for calculating the nucleophilicity of alkanes is described. A statistical treatment was applied to the analysis of the reactivity of 29 different alkane C−H bonds towards in situ generated metal carbene electrophiles. The correlation of the recently reported experimental reactivity with two different sets of descriptors comprising a total of 86 parameters was studied, resulting in the quantitative descriptor‐based alkane nucleophilicity (QDEAN) model. This model consists of an equation with only six structural/topological descriptors, and reproduces the relative reactivity of the alkane C−H bonds. This reactivity can be calculated from parameters emerging from the schematic drawing of the alkane and a simple set of sums., We thank MINECO for support with Grants CTQ2017-82893-C2- 1-R, CTQ2015-73693-JIN, CTQ2017-87792-R and Red Intecat (CTQ2016-81923-REDC). Junta de Andalucía is also acknowledged for Grant P12-FQM-1765. R. G. and A. O. thank MINECO for FPI and Juan de la Cierva fellowships, respectively.

The oxidation of C–H bonds by copper centres in enzymes with molecular oxygen takes place in nature under ambient conditions. Herein we report a similar transformation in which under ambient pressure and temperature (1 atm, 25 °C) the complex TpMsCu(THF) (TpMs = hydrotris(3-mesityl-pyrazol-1-yl)borate) undergoes the intramolecular oxidation of an alkylic C–H bond with O2, leading to the formation of a trinuclear compound where alkoxy and hydroxyl ligands are bonded to the copper centres, as inferred from X-ray studies. The presence of adventitious Cu(0) derived from the partial decomposition of initial TpMsCu(THF) facilitates the formation of such a trinuclear compound. DFT studies support the reaction taking place through a Cu(III) alkoxy-hydroxyl copper intermediate., Support for this work was provided by the MINECO (CTQ2017- 82893-C2-1-R CTQ2017-87889-P and CTQ2017-89132-P) and P.O. FEDER 2014-2020, UHU-1260216. MA thanks Ministerio de Economía y Competitividad for an FPI predoctoral fellowship.

Many transition-metal complexes MLn decompose diazo compounds N2-CR1R2 generating metal-carbenes LnM-CR1R2 which transfer the carbene group to other substrates, constituting an important tool in organic synthesis. All previous reports have shown that the CR1R2 fragment at the metal-carbene remains intact from the parent diazo compound. Herein we report the detection and isolation of a monosubstituted copper carbene where the CR1R2 ligand has undergone a modification from the initial diazo reagent. When TpMsCu(THF) (TpMs = hydrotris(3-mesityl)pyrazolylborate ligand) was reacted with N,N-diethyl diazoacetamide [N2-C(H)(CONEt2)], the stable copper carbene TpMsCu-C(H)(NEt2) was isolated, resulting from a decarbonylation process, with carbon monoxide being trapped as TpMsCu(CO). The simultaneous observation of products derived from the intramolecular carbene insertion reaction into C–H bonds demonstrates that the expected TpMsCu-C(H)(CONEt2) complex is also formed. Experimental data, DFT calculations, and microkinetic models allow us to propose that the latter undergoes CO loss en route to the former., Funding for open access charge: Universidad de Huelva / CBUA, Funding for open access charge: Universidad de Huelva / CBUAWe dedicate this work to the memory of Professor Victor Riera, one of the pioneers of organometallic chemistry in Spain. We acknowledge financial support from the Ministerio de Ciencia e Innovación (CTQ2017-82893-C2-1-R, CTQ2017- 87792-R, P. O. Feder UHU-1260216 and P. O. Feder UHU- 1254043, and Red Intecat CTQ2016-81923-REDC)

The copper complex Tp(CF3)2,BrCu(NCMe) efficiently catalyses the aziridination of olefins in water using PhI=NTs as the nitrene source, with identical activity than that observed when using dichloromethane as the solvent, under the same experimental conditions. No specific modification of catalyst or substrates are required, nor the presence of additional phase transfer catalyst. Competition experiments and Hammett plots show that the behaviour of the metal centre is the same in both reaction media. This is the first example of a catalytic system employing PhI=NTs for olefin aziridination in water., We thank financial support from the Ministerio de Ciencia e Innovación (PID2020-113797RB-C21), Junta de Andalucía (P18- RT-1536) and Universidad de Huelva (P.O.Feder UHU-1260216). Funding for open access charges is given by Universidad de Huelva/CBUA.

The use of graphenic materials as support for transition metal-based catalysts in reactions involving the functionalization of carbon-hydrogen bonds is reviewed. In many cases, the catalytic activities reported are comparable or better than the homogeneous counterparts, a feature which adds to a substantial degree of recyclability of the materials., Support for this work was provided by the MINECO (CTQ2017-82893-C2-1-R, Junta de Andalucía (P18-RT-1536) and PO FEDER 2014-2020, UHU-1260216). JM thanks MINECO for a FPI fellowship.

The aim of this study was to analyze the main leisure habits of students at the University of Huelva and the relationship with perceived health by grouping the various activities into components whilst also evaluating possible gender differences. The sample was selected through random cluster sampling and was composed of 903 students from various courses and degrees. Of the sample, 73.8% were female and 26.2% were male, with a mean age of 20.82 years. The participants responded to items measuring perceived health and the inventory of leisure activities extracted from the INJUVE (Spanish Youth Observatory) survey. The results obtained offered a solution of four components, grouping the activities into passive leisure, festive leisure, sports&ndash, competitive leisure and cultural leisure. Passive leisure was the most practiced and cultural leisure the least practiced. Statistically significant differences were observed between men and women in terms of the sports&ndash, competitive component and in the perception of health. In addition, a direct relationship was found between the sports&ndash, competitive dimension and health perception. These results support the existence of a &ldquo, techno-active&rdquo, profile in males and should be considered in the creation of university policies linked to health promotion or the prevention of risk behaviors.

Background: Various authors have described the elements of impulsive approach and inhibitory control in drug users. These two components have been studied in terms of personality traits, performance on tasks that measure impulsive behavior, and neurophysiology. However, few studies have analyzed the association between these constructs. Thus, the aim of the present study is to analyze the associations between personality traits and performance on impulsivity tasks. Methods: A follow-up study was conducted with a baseline assessment at the beginning and end of treatment. The sample was composed of 121 patients undergoing treatment in therapeutic communities. Personality domains were evaluated through the PID-5. The impulsivity tasks employed were the Iowa Gambling Task (IGT), Delay Discounting Test (DDT), Go/No-Go and Stroop test. Results: A correlation was found between DDT scores and the domains of detachment (r = -.315; p

Under silver catalysis conditions, using [Tp*,BrAg]2 as the catalyst precursor, allenes react with PhI═NTs in the first example of efficient metal-mediated intermolecular nitrene transfer to such substrates. The nature of the substituent at the allene seems crucial for the reaction outcome since arylallenes are converted into azetidine derivatives, whereas methylene aziridines are the products resulting from alkylallenes. Mechanistic studies allow proposing that azetidines are formed through unstable cyclopropylimine intermediates, which further incorporate a second nitrene group, both processes being silver-mediated. Methylene aziridines from alkylallenes derive from catalytic nitrene addition to the allene double bonds. Both routes have resulted to be productive for further synthetic transformations affording aminocyclopropanes., Support for this work was provided by the MINECO (CTQ2017-82893-C2-1-R, CTQ2017-87792-R and Red Intecat CTQ2016-81923-REDC) and Universidad de Huel va (PO FEDER 2014-2020-UHU-1254043). MR thanks MINECO for a predoctoral fellowship.

Background: Interpretation bias tasks such as word association tests have shown a moderate relation with substance use, but most studies have been conducted in nonclinical samples and these tasks a...

The functionalization of methane in water as the reaction medium (where it is nearly insoluble) at room temperature using micellar catalysis is described. Aggregates are formed from surfactant molecules and act as methane concentrators, also trapping the catalyst (a silver-based complex) and the diazo reagent (ethyl diazoacetate, EDA), providing yields of ethyl propionate up to 14% (referred to as EDA). This is the first example of methane being functionalized in water at room temperature., We thank MINECO for support with Grants CTQ2014-52769- C03-01, CTQ2017-82893-C2-1-R and CTQ2014-62234-EXP and Junta de Andalucía for Grant P12-FQM-1765. R. G. also thanks MINECO for a FPI fellowship.

International audience; To analyze the relationship between suicide in men and stratified measures of religiosity.Methods: We studied 192 suicides and 81 controls (nonsuicide, sudden, or accidental death). We employed the psychological autopsy method to compile diagnoses based on DSM-IV criteria. Overall, religiosity and participation in religious associations were determined using a Likert-type scale. Given the limited participation of women in the religious associations of southern Spain, only male subjects were included.Results: Religious participants had decreased risk of suicide compared to nonparticipants (OR = 0.148, 95% CI = 0.049-0.447). This lower risk was further associated with the degree of involvement in religious activity. Suicides accounted for 73.47% of subjects with no religious participation, 61.17% of those with some participation, and 56.52% of frequent participants (linear trend test Z = -2.0329, p = .042). Membership in a religious association was also associated with a lower rate of suicide compared to nonmembers (OR = 0.356, 95% CI = 0.172-0.736). This effect was similarly associated with the degree of involvement in the association. Suicides accounted for 74.67% of subjects who never participated in the activities of a religious association, 69.23% of those who sometimes participated, and 42.86% of frequent participants (linear trend test Z = -3.4082, p < .001).Conclusions: Religiosity, either as general participation or through a religious association, was associated with protection against suicide proportional to the degree of involvement in religious activities.

A multigram method for the preparation of thallium trispyrazolylborate complexes is described., The authors wish to thank MINECO for financial support (CTQ2014-52769-C03-01 and CTQ2015-73693-JIN). A.P. thanks MEC for the FPU fellowship.

This article analyses the effect of the teaching-learning methods used in Spanish universities on three measures of educational output: average mark, graduates’ assessment of their professional per...

A novel, highly enantio- and diastereoselective synthesis of 1-boryl-2,3-disubstituted cyclopropanes has been developed by means of the cyclopropanation of alkenylboronates with ethyl diazoacetate in the presence of catalytic amounts of a chiral copper(I) complex. The products can also be directly accessed from alkynes through an operationally simple, sequential hydroboration–cyclopropanation protocol. The resulting enantioenriched 1-boryl-2,3-disubstituted cyclopropanes are versatile synthetic intermediates that undergo further transformations at the carbon–boron bond., We thank MINECO for financial support (CTQ2014-52769- C03-01-R and Juan de la Cierva fellow for J.C.) and Junta de Andaluc a (P12-FQM-1765). We also thank Riccardo Gava and Cristina Gonzalez for additional experiments and Francisco Molina for X-ray diffraction studies.

The effect of a series of hydrotris(pyrazolyl)borate ligands (Tpx) in the regioselectivity of the catalytic functionalization of the secondary carbon-hydrogen bonds of hexane with ethyl diazoacetate and TpxCuL as the catalysts has led to the definition of the relative steric parameter SPR. The validity of the parameter has been assessed upon its correlation with the regioselectivity observed in several transformations (olefin cyclopropanation, C−H functionalization, C−H amidation), in all cases a good degree of fitting being observed.

Two iridium(III) complexes containing a C,N-bidentate pyridyl-triazolylidene ligand were prepared that are structurally very similar but differ in their pendant substituent. Whereas complex 1 contains a non-coordinating pyridyl unit, complex 2 has a phenyl group on the triazolylidene substituent. The presence of the basic pyridyl unit has distinct effects on the catalytic activity of the complex in the oxidative dehydrogenation of benzylic amines, inducing generally higher rates, higher selectivity towards formation of imines versus secondary amines, and notable quantities of tertiary amines when compared to the phenyl-functionalized analogue. The role of the pyridyl functionality has been elucidated from a set of stoichiometric experiments, which demonstrate hydrogen bonding between the pendant pyridyl unit and the amine protons of the substrate. Such Npyr···H-N interactions are demonstrated by X-ray diffraction analysis, 1H NMR, and IR spectroscopy, and suggest a pathway of substrate bond-activation that involves concerted substrate binding through the Lewis acidic iridium center and the Lewis basic pyridyl site appended to the triazolylidene ligand, in agreement with ligand–metal cooperative substrate activation.