Nucleophilicity and Electrophilicity in the Gas Phase: Silane Hydricity

Abstract

Hydricity is of great import as hydride transfer reactions are prominent in many processes, including organic synthesis, photoelectrocatalysis, and hydrogen activation. Herein, the kinetic hydricity of a series of silanes is examined in the gas phase. Most of these reactions have not heretofore been studied in vacuo and provide valuable data that can be compared to condensed-phase hydricity, to reveal the effects of solvent. Both experiments and computations are used to gain insight into mechanism and reactivity. In a broader sense, these studies also represent a first step toward systematically understanding nucleophilicity and electrophilicity in the absence of a solvent.

Molecular Determinants of Efficient Cobalt-Substituted Hemoprotein Production in E. coli

“…Proteins bearing unnatural metallocofactors are useful tools to study the metalloprotein function, expand the reactivity of natural proteins, and catalyze abiological reactions. , In particular, metal-substituted hemoproteins have been explored extensively because they have unique reactivity, − may serve as spectroscopic probes, − and have unique imaging properties. While there are diverse methods to generate proteins loaded with unnatural metalloporphyrin cofactors both in vivo and in vitro, ,− many of these strategies require exogenous synthesis of the unnatural metalloporphyrin and rely on low-efficiency methods for inserting the cofactor into the protein.…”