Cp* Noninnocence Leads to a Remarkably Weak C–H Bond via Metallocene Protonation

Metallocenes, including their permethylated variants, are extremely important in organometallic chemistry. In particular, many are synthetically useful either as oxidants (e.g., Cp_2Fe^+) or as reductants (e.g., Cp_2Co, Cp*_2Co, and Cp*_2Cr). The latter have proven to be useful reagents in the reductive protonation of small-molecule substrates, including N_2. As such, understanding the behavior of these metallocenes in the presence of acids is paramount. In the present study, we undertake the rigorous characterization of the protonation products of Cp*_2Co using pulse electron paramagnetic resonance (EPR) techniques at low temperature. We provide unequivocal evidence for the formation of the ring-protonated isomers Cp*(exo/endo-η^4-C_5Me_5H)Co^+. Variable temperature Q-band (34 GHz) pulse EPR spectroscopy, in conjunction with density functional theory (DFT) predictions, are key to reliably assigning the Cp*(exo/endo-η^4-C_5Me_5H)Co^+ species. We also demonstrate that exo-protonation selectivity can be favored by using a bulkier acid and suggest this species is thus likely a relevant intermediate during catalytic nitrogen fixation given the bulky anilinium acids employed. Of further interest, we provide physical data to experimentally assess the C–H bond dissociation free energy (BDFE_(C–H)) for Cp*(exo-η^4-C_5Me_5H)Co^+. These experimental data support our prior DFT predictions of an exceptionally weak C–H bond (<29 kcal mol^(–1)), making this system among the most reactive (with respect to C–H bond strength) to be thoroughly characterized. These data also point to the propensity of Cp*(exo-η^4-C_5Me_5H)Co to mediate hydride (H–) transfer. Our findings are not limited to the present protonated metallocene system. Accordingly, we outline an approach to rationalizing the reactivity of arene-protonated metal species, using decamethylnickelocene as an additional example

Gait biofeedback training in people with Parkinson’s disease : A pilot study

Background People with Parkinson’s disease (PD) are at a high risk of falls, with ~ 60% experiencing a fall each year. Greater mediolateral head and pelvis motion during gait are known to increase the risk of falling in PD, however the ability to modify these aspects of gait has not been examined. Thus, this study aimed to examine whether mediolateral trunk, head and pelvis motion during walking could be successfully decreased in people with PD using real-time biofeedback. Methods Participants were provided with real-time biofeedback regarding their mediolateral trunk lean via a visual projection whilst walking along an 8-m indoor walkway. Using the feedback provided, they were asked to reduce the magnitude of their mediolateral trunk lean. Gait was recorded for four conditions (i) Baseline, (ii) Intervention, (iii) immediately Post-Intervention, and (iv) 1-week Follow-Up. Biomechanical variables associated with falls risk were compared between conditions, including normalised mediolateral motion, gait velocity and stride length. Results A reduction in mediolateral trunk lean, step length and gait velocity from Baseline to the Intervention and Post-intervention conditions was observed. Contrary to this, increased normalised ML pelvis and trunk motion was observed between the Baseline and Intervention conditions, but returned to Baseline levels in the Post-Intervention condition. Conclusions Results from the current study suggest that real-time visual biofeedback may be effective at modifying specific gait characteristics that are associated with falls in PD. Further research is required to better understand the influence of this intervention approach on falls incidence. Trial registration Australian New Zealand Clinical Trials Registry ACTRN12620000994987. Registered 10 June 2020 - Retrospectively registered, https://anzctr.org.au/Trial/Registration/TrialReview.aspx?id=38032

Constraints on visual exploration of youth football players during 11v11 match-play : The influence of playing role, pitch position and phase of play

Visual exploratory action, in which football players turn their head to perceive their environment, improves prospective performance with the ball during match-play. This scanning action, however, is relevant for players throughout the entire match, as the information perceived through visual exploration is needed to guide movement around the pitch during both offensive and defensive play. This study aimed to understand how a player’s on-pitch position, playing role and phase of play influenced the visual exploratory head movements of players during 11v11 match-play. Twenty-two competitive-elite youth footballers (M = 16.25 years) played a total of 1,623 minutes (M = 73.8). Inertial measurement units, global positioning system units and notational analysis were used to quantify relevant variables. Analyses revealed that players explored more extensively when they were in possession of the ball, and less extensively during transition phases, as compared to team ball-possession and opposition ball-possession phases of play. Players explored most extensively when in the back third of the pitch, and least when they were in the middle third of the pitch. Playing role, pitch position and phase of play should be considered as constraints on visual exploratory actions when developing training situations aimed at improving the scanning actions of players

Using microtechnology to quantify torso angle during match-play in field hockey

Warman, GE, Cole, MH, Johnston, RD, Chalkley, D, and Pepping, GJ. Using microtechnology to quantify torso angle during match-play in field hockey. J Strength Cond Res 33(10): 2648–2654, 2019—Field hockey is played in a dynamic environment placing specific postural demands on athletes. Little research has been devoted to understanding the nature of a player's torso postures in field hockey match-play and its relationship with the perceptuomotor demands of the sport. We used commercially available microtechnology worn by 16 athletes during a 6-match national tournament to quantify torso flexion/extension angles. Orientation was derived using the inertial and magnetic sensors housed within global positioning system devices, assessing torso angle in the sagittal plane from 91 individual match files. The main independent variable was playing position, whereas the dependent variable was torso flexion/extension, presented as a percentage of playing time spent in 15 × 10° torso postural bands ranging from ≥40° extension to ≥90° flexion. It was shown that athletes spent 89.26% of their playing time in various torso postures, ranging from 20 to 90° of flexion. Defenders spent more time than midfielders (p = 0.004, effect size [ES] = 0.43) and strikers (p = 0.004; ES = 0.44) in the posture band of 10–20° torso flexion, whereas midfielders spent more time between 20 and 30° of torso flexion (p = 0.05; ES = 0.32) than strikers. Conversely, strikers spent more time between 30 and 40° of flexion than defenders (p < 0.001; ES = 0.74). These results reflect the sport-specific and role-specific torso angles adopted by field hockey athletes during match-play. Coaching staff can use these data to gain insight into the postural demands of their sport and inform the preparation of athletes for the perception-action demands of competition

Visual exploration when surrounded by affordances : Frequency of head movements is predictive of response speed

Little is known about the actions supporting exploration and their relation to subsequent actions in situations when participants are surrounded by opportunities for action. Here, the movements that support visual exploration were related to performance in an enveloping football (soccer) passing task. Head movements of experienced football players were quantified with inertial measurement units. In a simulated football scenario, participants completed a receiving–passing task that required them to indicate pass direction to one of four surrounding targets, as quickly as they could after they gained simulated ball possession. The frequency of head movements before and after gaining ball possession and the pass response times were recorded. We controlled exploration time—the time before gaining simulated ball possession—to be 1, 2, or 3 seconds. Exploration time significantly influenced the frequency of head movements, and a higher frequency of head turns before gaining ball possession resulted in faster pass responses. Exploratory action influenced subsequent performatory action. That is, higher frequencies of head movements resulted in faster decisions. Implications for research and practice are discussed

Principles of the guidance of exploration for orientation and specification of action

To control movement of any type, the neural system requires perceptual information to distinguish what actions are possible in any given environment. The behavior aimed at collecting this information, termed “exploration”, is vital for successful movement control. Currently, the main function of exploration is understood in the context of specifying the requirements of the task at hand. To accommodate for agency and action-selection, we propose that this understanding needs to be supplemented with a function of exploration that logically precedes the specification of action requirements with the purpose of discovery of possibilities for action—action orientation. This study aimed to provide evidence for the delineation of exploration for action orientation and exploration for action specification using the principles from “General Tau Theory.” Sixteen male participants volunteered and performed a laboratory-based exploration task. The visual scenes of different task-specific situations were projected on five monitors surrounding the participant. At a predetermined time, the participant received a simulated ball and was asked to respond by indicating where they would next play the ball. Head movements were recorded using inertial sensors as a measure of exploratory activity. It was shown that movement guidance characteristics varied between different head turns as participants moved from exploration for orientation to exploration for action specification. The first head turn in the trial, used for action-orientation, showed later peaks in the velocity profile and harder closure of the movement gap (gap between the start and end of the head-movement) in comparison to the later head turns. However, no differences were found between the first and the final head turn, which we hypothesized are used mainly for action orientation and specification respectively. These results are in support of differences in the function and control of head movement for discovery of opportunities for action (orientation) vs. head movement for specification of task requirements. Both are important for natural movement, yet in experimental settings,orientation is often neglected. Including both orientation and action specification in an experimental design should maximize generalizability of an experiment to natural behavior. Future studies are required to study the neural bases of movement guidance in order to better understand exploration in anticipation of movement

Cp* Noninnocence Leads to a Remarkably Weak C–H Bond via Metallocene Protonation

Metallocenes, including their permethylated variants, are extremely important in organometallic chemistry. In particular, many are synthetically useful either as oxidants (e.g., Cp_2Fe^+) or as reductants (e.g., Cp_2Co, Cp*_2Co, and Cp*_2Cr). The latter have proven to be useful reagents in the reductive protonation of small-molecule substrates, including N_2. As such, understanding the behavior of these metallocenes in the presence of acids is paramount. In the present study, we undertake the rigorous characterization of the protonation products of Cp*_2Co using pulse electron paramagnetic resonance (EPR) techniques at low temperature. We provide unequivocal evidence for the formation of the ring-protonated isomers Cp*(exo/endo-η^4-C_5Me_5H)Co^+. Variable temperature Q-band (34 GHz) pulse EPR spectroscopy, in conjunction with density functional theory (DFT) predictions, are key to reliably assigning the Cp*(exo/endo-η^4-C_5Me_5H)Co^+ species. We also demonstrate that exo-protonation selectivity can be favored by using a bulkier acid and suggest this species is thus likely a relevant intermediate during catalytic nitrogen fixation given the bulky anilinium acids employed. Of further interest, we provide physical data to experimentally assess the C–H bond dissociation free energy (BDFE_(C–H)) for Cp*(exo-η^4-C_5Me_5H)Co^+. These experimental data support our prior DFT predictions of an exceptionally weak C–H bond (<29 kcal mol^(–1)), making this system among the most reactive (with respect to C–H bond strength) to be thoroughly characterized. These data also point to the propensity of Cp*(exo-η^4-C_5Me_5H)Co to mediate hydride (H–) transfer. Our findings are not limited to the present protonated metallocene system. Accordingly, we outline an approach to rationalizing the reactivity of arene-protonated metal species, using decamethylnickelocene as an additional example

Exploring the Limits of Dative Boratrane Bonding: Iron as a Strong Lewis Base in Low-Valent Non-Heme Iron-Nitrosyl Complexes

We previously reported the synthesis and preliminary characterization of a unique series of low-spin (ls) {FeNO}⁸⁻¹⁰ complexes supported by an ambiphilic trisphosphineborane ligand, [Fe(TPB)(NO)]^(+/0/−). Herein, we use advanced spectroscopic techniques and density functional theory (DFT) calculations to extract detailed information as to how the bonding changes across the redox series. We find that, in spite of the highly reduced nature of these complexes, they feature an NO+ ligand throughout with strong Fe−NO π-backbonding and essentially closed-shell electronic structures of their FeNO units. This is enabled by an Fe−B interaction that is present throughout the series. In particular, the most reduced [Fe(TPB)(NO)]− complex, an example of a ls-{FeNO}¹⁰ species, features a true reverse dative Fe → B bond where the Fe center acts as a strong Lewis-base. Hence, this complex is in fact electronically similar to the ls-{FeNO}⁸ system, with two additional electrons “stored” on site in an Fe−B single bond. The outlier in this series is the ls-{FeNO}⁹ complex, due to spin polarization (quantified by pulse EPR spectroscopy), which weakens the Fe−NO bond. These data are further contextualized by comparison with a related N₂ complex, [Fe(TPB)(N₂)]⁻, which is a key intermediate in Fe(TPB)-catalyzed N₂ fixation. Our present study finds that the Fe → B interaction is key for storing the electrons needed to achieve a highly reduced state in these systems, and highlights the pitfalls associated with using geometric parameters to try to evaluate reverse dative interactions, a finding with broader implications to the study of transition metal complexes with boratrane and related ligands

Exploring the Limits of Dative Boratrane Bonding: Iron as a Strong Lewis Base in Low-Valent Non-Heme Iron-Nitrosyl Complexes

We previously reported the synthesis and preliminary characterization of a unique series of low-spin (ls) {FeNO}⁸⁻¹⁰ complexes supported by an ambiphilic trisphosphineborane ligand, [Fe(TPB)(NO)]^(+/0/−). Herein, we use advanced spectroscopic techniques and density functional theory (DFT) calculations to extract detailed information as to how the bonding changes across the redox series. We find that, in spite of the highly reduced nature of these complexes, they feature an NO+ ligand throughout with strong Fe−NO π-backbonding and essentially closed-shell electronic structures of their FeNO units. This is enabled by an Fe−B interaction that is present throughout the series. In particular, the most reduced [Fe(TPB)(NO)]− complex, an example of a ls-{FeNO}¹⁰ species, features a true reverse dative Fe → B bond where the Fe center acts as a strong Lewis-base. Hence, this complex is in fact electronically similar to the ls-{FeNO}⁸ system, with two additional electrons “stored” on site in an Fe−B single bond. The outlier in this series is the ls-{FeNO}⁹ complex, due to spin polarization (quantified by pulse EPR spectroscopy), which weakens the Fe−NO bond. These data are further contextualized by comparison with a related N₂ complex, [Fe(TPB)(N₂)]⁻, which is a key intermediate in Fe(TPB)-catalyzed N₂ fixation. Our present study finds that the Fe → B interaction is key for storing the electrons needed to achieve a highly reduced state in these systems, and highlights the pitfalls associated with using geometric parameters to try to evaluate reverse dative interactions, a finding with broader implications to the study of transition metal complexes with boratrane and related ligands