Rhodium and Iridium complexes with a new scorpionate phosphane ligand

A straightforward synthesis of a new hybrid scorpionate ligand [(allyl)2B(CH2PPh2)(Pz)]− ([A2BPN]−) is reported. Coordination to rhodium resulted in square-planar complexes [Rh(κ2-A2BPN)(L)(L′)] [L = L′ = 1/2cod (1,5-cyclooctadiene), CNtBu, CO (6); L = CO, L′ = NH3, pyridine, PPh3, PMe3] for which spectroscopic data and the molecular structure of [Rh(κ2-A2BPN)(CO)PPh3] (11) indicate the ligand to be κN,κP-bound to rhodium with two dangling free allyl groups. Studies in solution point out that the six-membered Rh–N–N–B–C–P metallacycle undergoes a fast inversion in all of them. The bis(carbonyl) complex 6 easily loses a CO group to give [{Rh(A2BPN)(CO)}2], a dinuclear compound in which two mononuclear subunits are brought together by two bridging allyl groups. Coordination to iridium is dominated by a tripodal κN,κP,η2-C═C binding mode in the TBPY-5 complexes [Ir(κ3-A2BPN)(L)(L′)] [L = L′ = 1/2cod (3), CNtBu (5), CO (7); L = CO, L′ = PPh3 (13), PMe3 (14), H2C═CH2, (17), MeO2CC≡CCO2Me (dmad, 18)], as confirmed by the single-crystal structure determination of complexes 3 and 18. A fast exchange between the two allyl arms is observed for complexes having L = L′ (3, 5, and 7), while those having CO and L ligands (14, 17, and 18) were found to be nonfluxional species. An exception is complex 13, which establishes an equilibrium with the SP-4 configuration. Protonation reactions on complexes 13 and 14 with HCl yielded the hydride complex [Ir(κ2-A2BPN)(CO)(Cl)(H)PPh3] (15) and the C-alkyl compound [Ir{κ3-(allyl)B(CH2CHCH3)(CH2PPh2)(Pz)}(Cl)(CO)PMe3] (16), respectively. The bis(isocyanide) complex 5 reacts with dmad to form [Ir(κ2-A2BPN)(CNtBu)2(dmad)]. On the whole, the electronic density provided to the metal by the [A2BPN]− ligand is very sensitive to the coordination mode. The basicity of the new ligand is similar to that of the TpMe2 ligand in the κN,κP mode but comparable to Tp if coordinated in the κN,κP,η2-C═C mode.This research was supported by the MICINN/FEDER (Project CTQ2011-22516, Spain), Gobierno de Aragón (GA)/FSE (E70), and GA-La Caixa (Grant 2012/GA LC 057). A.L.S. thanks MICINN/FEDER for a fellowship.Peer Reviewe

The Influence of the Coach’s Autonomy Support and Controlling Behaviours on Motivation and Sport Commitment of Youth Soccer Players

The coach is one of the most influential agents in the sport commitment of youth players. Grounded in self-determination theory (SDT), numerous studies have examined the influence of the coach’s autonomy-supportive behaviours on athletes’ motivation. However, fewer studies have examined the influence of the coach’s controlling behaviours. The aim of this cross-sectional study was to analyse the influence of young soccer players’ perception of their coach’s autonomy-supportive and controlling behaviours on the satisfaction and frustration of their basic psychological needs (BPN) and sport commitment. A total of 203 soccer players (86% boys), aged 10–19 years (M = 14.88; SD = 1.54) participated. Coach autonomy support positively predicted BPN satisfaction which, in turn, positively explained sport commitment. Coach intimidation behaviours positively predicted BPN frustration, which, in turn, negatively explained sport commitment. In cross-relationships, autonomy support negatively explained BPN frustration, while intimidation behaviours and the controlling use of rewards negatively predicted BPN satisfaction. To conclude, these results suggest that it is important for the coach not only to support autonomy, but also to avoid the use of controlling behaviours, especially intimidation and controlling use of rewards, because of their influence on the motivational processes and sport commitment of youth soccer players

Finite time singularities for the free boundary incompressible Euler equations

In this paper, we prove the existence of smooth initial data for the 2D free boundary incompressible Euler equations (also known for some particular scenarios as the water wave problem), for which the smoothness of the interface breaks down in finite time into a splash singularity or a splat singularity.Ministerio de Ciencia e InnovaciónEuropean Research CouncilNational Science Foundatio

Structural stability for the splash singularities of the water waves problem

In this paper we show a structural stability result for water waves. The main motivation for this result is that we would like to exhibit a water wave whose interface starts as a graph and ends in a splash. Numerical simulations lead to an approximate solution with the desired behaviour. The stability result will conclude that near the approximate solution to water waves there is an exact solution.Ministerio de Ciencia e InnovaciónInstituto de Ciencias Matemáticas Severo OchoaEuropean Research CouncilNational Science Foundatio

Two color multichannel heterodyne interferometer set up for high spatial resolution electron density profile measurements in TJ-II

Proceedings of: 18th Topical Conference on High-Temperature Plasma Diagnostics, Wildwood, New Jersey (USA), 16-20 May 2010.Expanded-beam multichannel heterodyne interferometer has been installed on the TJ-II stellarator. Careful design of the optical system has allowed complete control on the evolution of both Gaussian beams along the interferometer, as well as the evaluation and optimization of the spatial resolution to be expected in the measurements. Five CO2 (measurement) channels and three Nd:YAG (vibration compensation) channels have been used to illuminate the plasma with a probe beam of 100 mm size. An optimum interpolation method has been applied to recover both interferometric phasefronts prior to mechanical vibration subtraction. The first results of the installed diagnostic are presented in this paper.This work was supported by Spanish Ministry of Education and Science Grant No. ENE2006-13559FTN . The authors would also like to acknowledge the help of Ernesto Garcia Ares and Jose Ramon Lopez Fernandez for setting up the signal conditioning systems

Splash singularity for water waves

We exhibit smooth initial data for the two-dimensional (2D) waterwave equation for which we prove that smoothness of the interface breaks down in finite time. Moreover, we show a stability result together with numerical evidence that there exist solutions of the 2D water-wave equation that start from a graph, turn over, and collapse in a splash singularity (self-intersecting curve in one point) in finite time.Ministerio de Ciencia e InnovaciónEuropean Research CouncilNational Science Foundatio

Finite time singularities for water waves with surface tension

Here we consider the 2D free boundary incompressible Euler equation with surface tension. We prove that the surface tension does not prevent a finite time splash or splat singularity, i.e. that the curve touches itself either in a point or along an arc. To do so, the main ingredients of the proof are a transformation to desingularize the curve and a priori energy estimates.Ministerio de Ciencia e InnovaciónEuropean Research CouncilNational Science Foundatio

Gender and corporal expression activity in physical education: Effect of an intervention on students’ motivational processes

Grounded in Self-Determination Theory and Achievement Goal Theory, the objective of this study was to assess the effectiveness of an intervention programme on a series of motivational variables in a corporal expression teaching unit. An analysis was also conducted in terms of whether the impact of the intervention would be effective in boys and girls, given the social stereotypes inherent to this type of expression activity. A sample of 224 students, with ages varying from 12 to 14 years old (105 boys, 119 girls) participated in 10 sessions. A quasi-experimental design was carried out, dividing the total sample into two groups: control (n = 115) and experimental (n = 109). The intervention programme was applied in the experimental group via specific strategies based on the TARGET areas. In the experimental group, the results showed significantly higher values in perceived task-oriented climate, autonomy, competence, intrinsic motivation, identified regulation and enjoyment, as well as significantly lower values in ego-oriented climate. The intervention programme proved to be effective in boys and girls and the results were even better in boys. The importance of developing and applying specific motivational strategies in corporal expression activities should be stressed in order for this to have an impact on variables such as motivation and enjoyment in boys and girls, thus achieving more positive experiences

Effects of Extending Milk Replacer Feeding during the Fattening Period on the Behaviour and Welfare of Lambs: A Preliminary Study

There is a lack of information on the behavioural and welfare effects of sustaining artificial milk feeding in fattening lambs. Therefore, the present work aimed to study the effects of prolonged artificial milk feeding during fattening with a high concentrate diet on the behaviour of lambs. The behaviour of 16 non castrated male lambs of the Manchega sheep breed (eight lambs were in the group that were fed daily a bottle of milk, and the other eight were in the weaned group) was recorded with four fixed cameras just before bottle feeding (~8:30 a.m.) of the unweaned group till four hours later, every day for 7 weeks. The solid diet (pelleted concentrate plus cereal straw) and housing conditions were the same in both groups. Solid feeds were offered ad libitum. There were no differences between groups in time spent eating nor in drinking, playing, scratching and oral activity behaviours (p > 0.05), but resting episodes were longer in weaned lambs (p < 0.05). Weaned lambs presented a higher frequency of self-grooming behaviour (p < 0.05), while the unweaned group performed a higher frequency of interaction behaviour (p < 0.05). In conclusion, the behaviours of lambs that were fed daily a bottle of milk during the fattening period did not substantially differ from the weaned individuals