A closed Ir₄ carbonyl cluster, 1, comprising a tetrahedral metal frame and three sterically bulky tert-butyl-calix[4]arene(OPr)₃(OCH₂PPh₂) (Ph = phenyl; Pr = propyl) ligands at the basal plane, was characterized with variable-temperature ¹³C NMR spectroscopy, which show the absence of scrambling of the CO ligands at temperatures up to 313 K. This demonstration of distinct sites for the CO ligands was found to extend to the reactivity and catalytic properties, as shown by selective decarbonylation in a reaction with trimethylamine N-oxide (TMAO) as an oxidant, which, reacting in the presence of ethylene, leads to the selective bonding of an ethyl ligand at the apical Ir site. These clusters were supported intact on porous silica and found to catalyze ethylene hydrogenation, and a comparison of the kinetics of the single-hydrogenation reaction and steady-state hydrogenation catalysis demonstrates a unique single-site catalyst-with each site having the same catalytic activity. Reaction orders in the catalytic ethylene hydrogenation reaction of approximately 1/2 and 0 for H₂ and C₂H₄, respectively, nearly match those for conventional noble-metal catalysts. In contrast to oxidative decarbonylation, thermal desorption of CO from silica-supported cluster 1 occurred exclusively at the basal plane, giving rise to sites that do not react with ethylene and are catalytically inactive for ethylene hydrogenation. The evidence of distinctive sites on the cluster catalyst leads to a model that links to hydrogen-transfer catalysis on metals-involving some surface sites that bond to both hydrocarbon and hydrogen and are catalytically engaged (so-called "*" sites) and others, at the basal plane, which bond hydrogen and CO but not hydrocarbon and are reservoir sites (so-called "S" sites).

Movement in response to music represents one of the natural social environments in which physical activity occurs. The study of music and movement, including dance, requires a careful, holistic consideration of many features, which may include music, physical activity, motor learning, social engagement, emotion, and creativity. The overarching goal of this manuscript is to examine qualitative characteristics of and individual responses to a music and movement intervention (Creatively Able) for children with Autism Spectrum Disorder (ASD). We provide a description of Creatively Able, illustrating how the program design and physical and social environment were informed by children's needs and preferences in order to provide an enriched environment in which to promote multiple systems in children with ASD. Using data from two pilot studies with 20 children with ASD, we illustrate how researchers can use observational research methods to measure important aspects of the social environment (e.g., children's engagement during intervention sessions) as well as engagement of potential underlying behavioral mechanisms (e.g., self-regulation) that might reduce clinical symptoms. We further illustrate how individual responses to intervention (e.g., improvements in behaviors or symptoms) can be studied in physically active interventions. Our pilot study results showed group-level reductions in Stereotyped and Compulsive behaviors of 8% and 4%, respectively; posthoc analysis revealed that there were substantial individual differences in children's responses to the intervention. This research illustrates robust methods that can be applied to intervention research to improve our understanding of important features of interventions that might help promote development in various domains, including executive functions and self-regulation.

Although oxygen is a common ligand in supported metal catalysts, its coordination has been challenging to elucidate. We now characterize a diiridium complex that has been previously shown by X-ray diffraction crystallography to incorporate a μ-η¹:η¹-peroxo ligand. We observe markedly enhanced intensity at 788 cm^-1 in the Raman spectrum of this complex, which is a consequence of bonding of the peroxo ligand but does not shift upon ¹⁸O labeling. Electronic structure calculations at the density functional theory level suggest that this increase in Raman intensity results from bands associated with rocking of CH₂ substituents directly attached to P(Ph)₂ groups coupling with the O-O band. These results provide part of the foundation for understanding oxygen ligands on a silica-supported tetrairidium carbonyl cluster stabilized with bulky electron-donating phosphine ligands [p-tert-butyl-calix[4]arene(OPr)₃(OCH₂PPh₂) (Ph = phenyl; Pr = propyl)]. Reaction of the cluster with O₂ also led to the growing in of a Raman band at 788 cm^-1, similar to that in the diiridium complex and also assigned to the bonding of a bridging peroxo ligand. Infrared spectra recorded as the supported cluster reacted in sequential exposures to (i) H₂, (ii) O₂, (iii) H₂, and (iv) CO indicate that two bridging peroxo ligands were bonded irreversibly per tetrairidium cluster, replacing bridging carbonyl ligands without altering either the cluster frame or the phosphine ligands. X-ray absorption near edge and infrared spectra include isosbestic points signifying a stoichiometrically simple reaction of the cluster with O₂, and mass spectra of the effluent gas show that CO₂ formed by oxidation of one terminal CO ligand per cluster as H₂ (and not H₂O) formed, evidence that hydride ligands had been present on the cluster following treatment (i). The understanding of how O₂ reacts with the metal polyhedron provides a foundation for understanding of how oxidation catalysis may proceed on the surfaces of noble metals.