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We present a series of borane‐tethered cyclic (alkyl)(amino)carbene (cAAC)‐copper complexes, including a borane‐capped Cu(I) hydride. This hydride is unusually hydridic and reacts rapidly with both CO2 and 2,6‐dimethylphenol at room temperature. Its reactivity is distinct from variants without a tethered borane, and the underlying principles governing the enhanced hydricity were evaluated experimentally and theoretically. These stoichiometric results were extended to catalytic CO2 hydrogenation, and the borane‐tethered (intramolecular) system exhibits ~3‐fold enhancement relative to an intermolecular system. 

Abstract Heterogeneity in brain activity can give rise to heterogeneity in behavior, which in turn comprises our distinctive characteristics as individuals. Studying the path from brain to behavior, however, often requires making assumptions about how similarity in behavior scales with similarity in brain activity. Here, we expand upon recent work (Finn et al., 2020) which proposes a theoretical framework for testing the validity of such assumptions. Using intersubject representational similarity analysis in two independent movie-watching functional MRI (fMRI) datasets, we probe how brain-behavior relationships vary as a function of behavioral domain and participant sample. We find evidence that, in some cases, the neural similarity of two individuals is not correlated with behavioral similarity. Rather, individuals with higher behavioral scores are more similar to other high scorers whereas individuals with lower behavioral scores are dissimilar from everyone else. Ultimately, our findings motivate a more extensive investigation of both the structure of brain-behavior relationships and the tacit assumption that people who behave similarly will demonstrate shared patterns of brain activity. 

Cognition and attention arise from the adaptive coordination of neural systems in response to external and internal demands. The low-dimensional latent subspace that underlies large-scale neural dynamics and the relationships of these dynamics to cognitive and attentional states, however, are unknown. We conducted functional magnetic resonance imaging as human participants performed attention tasks, watched comedy sitcom episodes and an educational documentary, and rested. Whole-brain dynamics traversed a common set of latent states that spanned canonical gradients of functional brain organization, with global desynchronization among functional networks modulating state transitions. Neural state dynamics were synchronized across people during engaging movie watching and aligned to narrative event structures. Neural state dynamics reflected attention fluctuations such that different states indicated engaged attention in task and naturalistic contexts, whereas a common state indicated attention lapses in both contexts. Together, these results demonstrate that traversals along large-scale gradients of human brain organization reflect cognitive and attentional dynamics. 

As we comprehend narratives, our attentional engagement fluctuates over time. Despite theoretical conceptions of narrative engagement as emotion-laden attention, little empirical work has characterized the cognitive and neural processes that comprise subjective engagement in naturalistic contexts or its consequences for memory. Here, we relate fluctuations in narrative engagement to patterns of brain coactivation and test whether neural signatures of engagement predict subsequent memory. In behavioral studies, participants continuously rated how engaged they were as they watched a television episode or listened to a story. Self-reported engagement was synchronized across individuals and driven by the emotional content of the narratives. In functional MRI datasets collected as different individuals watched the same show or listened to the same story, engagement drove neural synchrony, such that default mode network activity was more synchronized across individuals during more engaging moments of the narratives. Furthermore, models based on time-varying functional brain connectivity predicted evolving states of engagement across participants and independent datasets. The functional connections that predicted engagement overlapped with a validated neuromarker of sustained attention and predicted recall of narrative events. Together, our findings characterize the neural signatures of attentional engagement in naturalistic contexts and elucidate relationships among narrative engagement, sustained attention, and event memory.