Impact of Halide (Cl vs I) Identity on the Preferred Positioning of Substituents between Al and M (M = Co, Rh, Ir) in PAlP Pincer Complexes.

Protolysis of AlMe or AlEt with 2-diisopropylphosphinopyrrole () resulted in alane/bis(phosphine) pincer ligands containing two flanking phosphines and a central Al-Me (), Al-Et () unit. Reactions of with [(COD)MI] (COD = 1,5-cyclooctadiene; M = Rh or Ir) in the presence of pyridine produced pincer complexes ( and ) with M supported by the PAlP tridentate ligand, and pyridine, methyl, and iodide as monodentate ligands for Al or M. The analogous reaction of with [(COD)MI] and pyridine resulted in the formation of the analogous compounds and with hydride in place of methyl.

Case-Base Neural Network: Survival analysis with time-varying, higher-order interactions.

In the context of survival analysis, data-driven neural network-based methods have been developed to model complex covariate effects. While these methods may provide better predictive performance than regression-based approaches, not all can model time-varying interactions and complex baseline hazards. To address this, we propose Case-Base Neural Networks (CBNNs) as a new approach that combines the case-base sampling framework with flexible neural network architectures.

Accounting for genetic effect heterogeneity in fine-mapping and improving power to detect gene-environment interactions with SharePro.

Classical gene-by-environment interaction (GxE) analysis can be used to characterize genetic effect heterogeneity but has a high multiple testing burden in the context of genome-wide association studies (GWAS). We adapt a colocalization method, SharePro, to account for effect heterogeneity in fine-mapping and identify candidates for GxE analysis with reduced multiple testing burden. SharePro demonstrates improved power for both fine-mapping and GxE analysis compared to existing methods as well as well-controlled false type I error in simulations.

C-H Activation of Pyridines by Boryl Pincer Complexes: Elucidation of Boryl-Directed C-H Oxidative Addition to Ir and Discovery of Transition Metal-Assisted Reductive Elimination from Boron at Rh.

Experimental and theoretical techniques were used to investigate the mechanism of pyridine C-H activation by diarylboryl/bis(phosphine) PBP pincer complexes of Ir. The critical intermediate (PBP)IrCO () contains a three-coordinate, Ir-bound boron that retains Lewis acidity in the perpendicular direction. Coordination of pyridine to this boron center in leads to fast insertion of Ir into the 2-CH bond of pyridine, providing a different topology of direction than the conventional directed C-H activation where both the directing group coordination and C-H activation happen at the same metal center.

Flash Communication: Rhodium Complexes of Acetamide-Derived PAlP Pincer.

The new alane/bis(phosphine) PAlP pincer-type ligands and have been prepared by protolysis reactions of -(diisopropylphoshino)acetamide with MeAl or EtAl in a 2:1 ratio. Upon reaction with a "RhCl" source and pyridine, gave rise to a (PAlP)RhMe(py) compound (), while led to the analogous hydride complex (PAlP)RhH(py) (), with a migration of the chloride from Rh to Al. and possess the shortest Rh-Al bonds to date.