The polarized optical spectra of the ions Ti3+, V3+, Cr3+, Mn3+, Co3+, and Ni3+ in corundum single crystals have been studied at temperatures from 4.2° to 1200°K. A theory of the band strength based on the point‐charge model and p‐d mixing has been developed and applied to the data with results in fair agreement with experiment. The effects of temperature show that the vibrational‐electronic contribution to band strength is quite small at low temperature but may be appreciable at high temperatures. The crystal‐field parameters have been calculated as convergent lattice sums. The observed trigonal‐field parameter has the opposite sign from that calculated by the point‐charge model if the impurity ion is assumed to occupy an Al3+ ion position in the lattice, but has the same sign as calculated for an ion 0.1 A displaced along the c3 axis toward the empty octahedral site. Details of the spectra have been interpreted as showing that the surroundings of an ion are distorted in some electronic states.

Optical spectra of transition-metal ions in corundum

Homochiral catalysts that can effect asymmetric transformations are invaluable in the production of optically active molecules. Researchers are actively pursuing the design of new ligands and organocatalysts by exploiting concepts derived from the application of bifunctional and C2-symmetric catalysts. Many homochiral catalysts containing amines, ethers, alcohols, and phosphines as electron-pair donors have been successfully developed.Amine N-oxides are highly polar substances. Despite their pronounced capacity as electron-pair donors, N-oxides have been underutilized in asymmetric reactions; they have only made a visible impact on the field in the preceding decade. Systematic studies have instead largely focused on pyridine- or quinoline-based scaffolds in organosilicon and coordination chemistry. The application of chiral tertiary amine N-oxides has not been widely pursued because of the difficulty of controlling the chirality at the tetrahedral nitrogen of the N-oxide moiety. In this Account, we outlin...

Chiral N,N′-Dioxides: New Ligands and Organocatalysts for Catalytic Asymmetric Reactions

The number and relative energies of nitrate combination frequencies in the 1700–1800 cm−1 region of the infrared spectrum may be used as an aid to distinguish the various coordination modes of the ...

Infrared Combination Frequencies in Coordination Complexes containing Nitrate Groups in various Coordination Environments. A Probe for the Metal–Nitrate Interaction

A class of conformationally flexible ligands composed of a tertiary amino oxide–amide backbone and a straight-chain alkyl spacer was developed. These C2-symmetric chiral N,N′-dioxide ligands could be straightforwardly synthesized from readily available amino acids and amines. They act as neutral tetradentate ligands to bind a wide variety of metal ions. Non-planar cis-α M(N,N′-dioxide) complexes enable an intriguing and easily fine-tuned chiral platform for a number of asymmetric reactions. Privileged N,N′-dioxide ligands frequently show wide substrate generality and exceptional levels of stereocontrol for a specific catalytic reaction. We describe approaches to the ligand design and synthesis, structure and bonding in coordination complexes, and the recent developments in asymmetric catalysis.

C.M. Mikulski

Papers

(Diethyl methylene diphosphonato) (diethyl hydrogen methylene diphosphonato)-vanadium (III)

Mixed ligand (diisobutoxyphosphato-chloro) titanium(III), uranium(IV) and thorium(IV) complexes

Cobalt(II), copper(II) and zinc(II) chloride complexes involving both neutral and monoanionic guanine ligands

Reactions of ethyl dichlorophosphate with MCl3 (M = Al, Cr) and UCl4

Organotin(IV) chalcogenides as ligands