Electrostatic polarization of nonpolar substrates: a study of interactions between simple cations and Mo-bound N2.

Although a great deal of catalytic studies have focused on covalent interactions between substrates and catalyst centers, recognition of the importance of noncovalent and ionic interactions is driving new approaches to catalyst design. Electrostatic interactions with simple cations (those with little covalency, such as alkali metals) play crucial roles in many catalytic processes, but these effects are challenging to study due to their complicated solvation and speciation behaviour. These effects are particularly difficult to study during cation-mediated reactions with weakly-polar or non-polar substrates. Dinitrogen is one of the most nonpolar substrates known to be affected by electrostatic interactions in both heterogeneous and homogeneous reactions but understanding the significance of these effects requires further exploration. To examine these effects systematically, a new multidentate ligand framework bearing pendent crown ethers has been developed and incorporated into a series of Mo(0)-based dinitrogen complexes. Prepared via both reduction and ligand substitution routes, the strength and impact of cation-N2 interactions have been studied experimentally (IR spectroscopy) and computationally. Although the smallest cation (Li+) has the largest impact on the ground-state heterobimetallic activation of N2, solvation interactions are highly competitive and result in low Li+-(N2)Mo binding affinities. Thus, although smaller cations can have the largest electronic impact on substrates, these interactions are also the least persistent.

Tridentate Phosphine Ligands Bearing Aza-Crown Ether Lariats.

Crown ethers are useful macrocycles that act as size-selective binding sites for alkali metals. These frameworks have been incorporated into a number of macromolecular assemblies that use simple cations as reporters and/or activity triggers. Incorporating crown ethers into secondary coordination sphere ligand frameworks for transition metal chemistry will lead to new potential methods for controlling bond formation steps, and routes that couple traditional ligand frameworks with these moieties are highly desirable. Herein we report the syntheses of a family of tridentate phosphine complexes bearing tethered aza-crown ethers (lariats) designed to modularize the variation of aza-crown size, lariat length, and distal phosphine substituents, followed by the synthesis and solid-state structures of Mo(III) complexes bearing cations in the pendent crown ethers.

Chirality Inversion of CdSe and CdS Quantum Dots without Changing the Stereochemistry of the Capping Ligand.

L-cysteine derivatives induce and modulate the optical activity of achiral cadmium selenide (CdSe) and cadmium sulfide (CdS) quantum dots (QDs). Remarkably, N-acetyl-L-cysteine-CdSe and L-homocysteine-CdSe as well as N-acetyl-L-cysteine-CdS and L-cysteine-CdS showed "mirror-image" circular dichroism (CD) spectra regardless of the diameter of the QDs. This is an example of the inversion of the CD signal of QDs by alteration of the ligand's structure, rather than inversion of the ligand's absolute configuration. Non-empirical quantum chemical simulations of the CD spectra were able to reproduce the experimentally observed sign patterns and demonstrate that the inversion of chirality originated from different binding arrangements of N-acetyl-L-cysteine and L-homocysteine-CdSe to the QD surface. These efforts may allow the prediction of the ligand-induced chiroptical activity of QDs by calculating the specific binding modes of the chiral capping ligands. Combined with the large pool of available chiral ligands, our work opens a robust approach to the rational design of chiral semiconducting nanomaterials.