P. L. Pauson

Bio: P. L. Pauson is an academic researcher from Duquesne University. The author has contributed to research in topics: Anhydrous & Chloride. The author has an hindex of 1, co-authored 1 publications receiving 1288 citations.

A New Type of Organo-Iron Compound

Abstract: NUMEROUS investigators have studied the reaction of Grignard reagents with anhydrous ferric chloride, but have failed to isolate any organo-iron compounds or to produce any definite evidence for their formation in such reactions.

Recent applications of chiral ferrocene ligands in asymmetric catalysis.

Abstract: Despite the impressive progress achieved in asymmetric catalysis during the last decade, an increasing number of new catalysts, ligands, and applications are reported every year to satisfy the need to embrace a wider range of reactions and to improve the efficiency of existing processes. Because of their availability, unique stereochemical aspects, and wide variety of coordination modes and possibilities for the fine-tuning of the steric and electronic properties, ferrocene-based ligands constitute one of the most versatile ligand architectures in the current scenario of asymmetric catalysis. Over the last few years ferrocene catalysts have been successfully applied in an amazing variety of enantioselective processes. This Review documents these recent advances, with special emphasis on the most innovative asymmetric processes and the development of novel, efficient types of ferrocene ligands.

Energy decomposition analysis

Abstract: The energy decomposition analysis (EDA) is a powerful method for a quantitative interpretation of chemical bonds in terms of three major components. The instantaneous interaction energy ΔEint between two fragments A and B in a molecule A–B is partitioned in three terms, namely (1) the quasiclassical electrostatic interaction ΔEelstat between the fragments; (2) the repulsive exchange (Pauli) interaction ΔEPauli between electrons of the two fragments having the same spin, and (3) the orbital (covalent) interaction ΔEorb which comes from the orbital relaxation and the orbital mixing between the fragments. The latter term can be decomposed into contributions of orbitals with different symmetry which makes it possible to distinguish between σ, π, and δ bonding. After a short introduction into the theoretical background of the EDA we present illustrative examples of main group and transition metal chemistry. The results show that the EDA terms can be interpreted in chemically meaningful way thus providing a bridge between quantum chemical calculations and heuristic bonding models of traditional chemistry. The extension to the EDA–Natural Orbitals for Chemical Valence (NOCV) method makes it possible to breakdown the orbital term ΔEorb into pairwise orbital contributions of the interacting fragments. The method provides a bridge between MO correlations diagrams and pairwise orbital interactions, which have been shown in the past to correlate with the structures and reactivities of molecules. There is a link between frontier orbital theory and orbital symmetry rules and the quantitative charge- and energy partitioning scheme that is provided by the EDA–NOCV terms. The strength of the pairwise orbital interactions can quantitatively be estimated and the associated change in the electronic structure can be visualized by plotting the deformation densities. For further resources related to this article, please visit the WIREs website.

Chiral Cyclopentadienyls: Enabling Ligands for Asymmetric Rh(III)-Catalyzed C–H Functionalizations

Abstract: ConspectusTransition-metal catalyzed C–H functionalizations became a complementary and efficient bond-forming strategy over the past decade. In this respect, Cp*Rh(III) complexes have emerged as powerful catalysts for a broad spectrum of reactions giving access to synthetically versatile building blocks. Despite their high potential, the corresponding catalytic enantioselective transformations largely lag behind. The targeted transformations require all the remaining three coordination sites of the central rhodium atom of the catalyst. In consequence, the chiral information on a competent catalyst can only by stored in the cyclopentadienyl unit. The lack of suitable enabling chiral cyclopentadienyl (Cpx) ligands is the key hurdle preventing the development of such asymmetric versions. In this respect, an efficient set of chiral Cpx ligands useable with a broad variety of different transition-metals can unlock substantial application potential. This Account provides a description of our developments of two...