The ability of platinum and gold catalysts to effect powerful atom-economic transformations has led to a marked increase in their utilization. The quite remarkable correlation of their catalytic behavior with the available structural data, coordination chemistry, and organometallic reactivity patterns, including relativistic effects, allows the underlying principles of catalytic carbophilic activation by π acids to be formulated. The spectrum of reactivity extends beyond their utility as catalytic and benign alternatives to conventional stoichiometric π acids. The resulting reactivity profile allows this entire field of catalysis to be rationalized, and brings together the apparently disparate electrophilic metal carbene and nonclassical carbocation explanations. The advances in coupling, cycloisomerization, and structural reorganization—from the design of new transformations to the improvement to known reactions—are highlighted in this Review. The application of platinum- and gold-catalyzed transformations in natural product synthesis is also discussed.

Catalytic Carbophilic Activation: Catalysis by Platinum and Gold π Acids

Transition-metal catalysts containing gold present new opportunities for chemical synthesis, and it is therefore not surprising that these complexes are beginning to capture the attention of the chemical community. Cationic phosphine-gold(i) complexes are especially versatile and selective catalysts for a growing number of synthetic transformations. The reactivity of these species can be understood in the context of theoretical studies on gold; relativistic effects are especially helpful in rationalizing the reaction manifolds available to gold catalysts. This Review draws on experimental and computational data to present our current understanding of homogeneous gold catalysis, focusing on previously unexplored reactivity and its application to the development of new methodology.

Relativistic effects in homogeneous gold catalysis

Frustrated Lewis pairs (FLPs) are combinations of Lewis acids and Lewis bases in solution that are deterred from strong adduct formation by steric and/or electronic factors. This opens pathways to novel cooperative reactions with added substrates. Small-molecule binding and activation by FLPs has led to the discovery of a variety of new reactions through unprecedented pathways. Hydrogen activation and subsequent manipulation in metal-free catalytic hydrogenations is a frequently observed feature of many FLPs. The current state of this young but rapidly expanding field is outlined in this Review and the future directions for its broadening sphere of impact are considered.

Frustrated Lewis pair chemistry: development and perspectives.

The Complete Active Space Self‐Consistent Field Method and its Applications in Electronic Structure Calculations

In the present study we have introduced a new scheme for chemical bond analysis by combining the Extended Transition State (ETS) method [Theor. Chim. Acta 1977, 46, 1] with the Natural Orbitals for Chemical Valence (NOCV) theory [J. Phys. Chem. A 2008, 112, 1933; J. Mol. Model. 2007, 13, 347]. The ETS-NOCV charge and energy decomposition scheme based on the Kohn−Sham approach makes it not only possible to decompose the deformation density, Δρ, into the different components (such as σ, π, δ, etc.) of the chemical bond, but it also provides the corresponding energy contributions to the total bond energy. Thus, the ETS-NOCV scheme offers a compact, qualitative, and quantitative picture of the chemical bond formation within one common theoretical framework. Although, the ETS-NOCV approach contains a certain arbitrariness in the definition of the molecular subsystems that constitute the whole molecule, it can be widely used for the description of different types of chemical bonds. The applicability of the ETS-...

L. A. Duncanson

Papers

586. Olefin co-ordination compounds. Part III. Infra-red spectra and structure: attempted preparation of acetylene complexes