Comparison of the X-ray crystal structures of four closely related Mo(CO)5(R2PXR′) (R2 = OCH2CMe2CH2O, XR′ = S-2-Pr, NHC6H4-4-Me; R2 = Ph2, XR′ = NHC6H4-2-Me, OC6H4-4-SMe) complexes

The X-ray crystal structures of four closely related Mo(CO)₅(R₂PXR) (R₂ = OCH₂CMe₂CH₂O, XR = S-2-Pr, NHC₆H₄-4-Me; R₂ = Ph₂, XR = NHC₆H₄-2-Me, OC₆H₄-4-SMe) complexes have been determined. The R₂PXR ligands are oriented so that the P—X bond and one of the Mo—C bonds are nearly eclipsed. This results in the distortion of the octahedral coordination geometry via tilting of the Mo(CO)₅ group away from the XR group. As observed in related complexes, the Mo—C bond of the carbonyl trans to the phosphorus-donor group is shorter than are the Mo—C bonds of the carbonyls trans to carbonyls. In contrast, no significant differences were observed between the Mo—C bonds of carbonyls trans to phosphites and the Mo—C bonds of carbonyls trans to phosphinites. The conformations of the 1,3,2-dioxaphosphorinanes were distorted chairs with the P end of the chair significantly flattened relative to the seat of the chair. This conformation is similar to that which has been observed for 1,3,2-dioxaphosphorinanes in other transition metal complexes.     

Solvent‐free synthesis of propargylamines catalyzed by an efficient recyclable ZnO‐supported CuO/Al2O3 nanocatalyst

An efficient nanocatalyst of ZnO‐supported CuO/Al₂O₃ (CuO/ZnO/Al₂O₃ nanocatalyst) was prepared by the co‐precipitation method and characterized by scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray powder diffraction and Brunauer–Emmett–Teller surface area analysis. CuO/ZnO/Al₂O₃ nanocatalyst proved to be a very efficient catalyst on the synthesis of propargylamines under solvent‐free conditions in high yields. Moreover, the catalyst can be recyclable without reducing catalytic activity up to five times.     

Laminar cortical dynamics of conscious speech perception: neural model of phonemic restoration using subsequent context in noise

How are laminar circuits of neocortex organized to generate conscious speech and language percepts? How does the brain restore information that is occluded by noise, or absent from an acoustic signal, by integrating contextual information over many milliseconds to disambiguate noise-occluded acoustical signals? How are speech and language heard in the correct temporal order, despite the influence of contexts that may occur many milliseconds before or after each perceived word? A neural model describes key mechanisms in forming conscious speech percepts, and quantitatively simulates a critical example of contextual disambiguation of speech and language; namely, phonemic restoration. Here, a phoneme deleted from a speech stream is perceptually restored when it is replaced by broadband noise, even when the disambiguating context occurs after the phoneme was presented. The model describes how the laminar circuits within a hierarchy of cortical processing stages may interact to generate a conscious speech percept that is embodied by a resonant wave of activation that occurs between acoustic features, acoustic item chunks, and list chunks. Chunk-mediated gating allows speech to be heard in the correct temporal order, even when what is heard depends upon future context.