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

5.7. [32π + 32σ] Cycloadditions 74 5.8. [44π + 22π] Cycloadditions 75 6. Seven-Membered Ring Formation 78 6.1. [44π + 32σ] Cycloadditions 78 6.2. [52π+2σ + 22π] Cycloadditions 79 7. Eight-Membered Ring Formation 79 7.1. [22π + 22π + 22π + 22π] Cycloadditions 80 7.2. [44π + 22π + 22π] Cycloadditions 80 7.3. [44π + 44π] Cycloadditions 81 7.4. [66π + 22π] Cycloadditions 83 8. Ten-Membered Ring Formation 85 9. Conclusion and Remarks 87

Transition Metal-Mediated Cycloaddition Reactions

Katalytische carbophile Aktivierung: Platin- und Gold-π-Säuren als Katalysatoren

Organometallic molecular wires and other nanoscale-sized devices: An approach using the organoiron (dppe)Cp*Fe building block

Chemists today are increasingly fascinated by gold’s unique position in the family of elements. In this review, the author looks at important new results emerging from recent research in gold chemistry.

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The fascinating implications of new results in gold chemistry

The structure of (C5H52W(CO)2 a compound containing a bent trihapto-cyclopentadienyl ligand

Bis(1-methyluracilato-N3)-cis-diammineplatinum(II) tetrahydrate and bis(.mu.-1-methyluracilato-N3,O4)-cis-diammineplatinum(II)diaquacopper(II) sulfate 4.5-hydrate (head-head). Preparation, crystal structures, and implications for the formation of heteronuclear platinum-metal complexes

Simultaneous binding of two different transition metals to the DNA model base 1-methylthymine: The x-ray structure of Bis[bis(μ-1-methylthyminato-N3, O4)cis-diammine platinum(II)] silver nitrate pentahydrate

Dietmar Neugebauer

Papers

The structure of (C5H52W(CO)2 a compound containing a bent trihapto-cyclopentadienyl ligand

Bis(1-methyluracilato-N3)-cis-diammineplatinum(II) tetrahydrate and bis(.mu.-1-methyluracilato-N3,O4)-cis-diammineplatinum(II)diaquacopper(II) sulfate 4.5-hydrate (head-head). Preparation, crystal structures, and implications for the formation of heteronuclear platinum-metal complexes

Simultaneous binding of two different transition metals to the DNA model base 1-methylthymine: The x-ray structure of Bis[bis(μ-1-methylthyminato-N3, O4)cis-diammine platinum(II)] silver nitrate pentahydrate

Photochemische addition konjugierter diene an tricarbonyl-η-1,3,5-cycloheptatrien-chrom(0) ☆

A heteronuclear (Pt4,Ag) complex of 1-methyluracil and its conversion into a crystalline platinum blue