Cyclometalated phosphine-based pincer complexes: Mechanistic insight in catalysis, coordination, and bond activation

Ligand design is becoming an increasingly important part of the synthetic activity in chemistry. This is of course because of the subtle control that ligands exert on the metal center to which they are coordinated. Ligands which contain significantly different chemical functionalities, such as hard and soft donors, are often called hybrid ligands and find increasing use in molecular chemistry. Although the interplay between electronic and steric properties has long been recognized as essential in determining the chemical or physical properties of a complex, predictions remain very difficult, not only because of the considerable diversity encountered within the Periodic Table-different metal centers will behave differently towards the same ligand and different ligands can completely modify the chemistry of a given metal-but also because of the small energy differences involved. New systems may-even through serendipity-allow the emergence of useful concepts that can gain general acceptance and help design molecular structures orientated towards a given property. The concept of ligand hemilability, which finds numerous illustrations with hybrid ligands, has gained increased acceptance and been found to be very useful in explaining the properties of metal complexes and in designing new systems for molecular activation, homogeneous catalysis, functional materials, or small-molecule sensing. In the field of homogeneous enantioselective catalysis, in which steric and/or electronic control of a metal-mediated process must occur in such a way that one stereoisomer is preferentially formed, ligands containing one or more chiral oxazoline units have been found to be very valuable for a wide range of metal-catalyzed reactions. The incorporation of oxazoline moieties in multifunctional ligands of increasing complexity makes such ligands good candidates to display hemilabile properties, which until recently, had not been documented in oxazoline chemistry. Herein, we briefly recall the definition and scope of hemilabile ligands, present the main classes of ligands containing one or more oxazoline moieties, with an emphasis on hybrid ligands, and finally explain why the combination of these two facets of ligand design appears particularly promising.

Hemilability of Hybrid Ligands and the Coordination Chemistry of Oxazoline‐Based Systems

Additions to Metal-Activated Organonitriles†

Synthetic routes to N-heterocyclic carbene precursors.

The activation of alkane C−H bonds by oxidative addition and its reverse reaction, reductive elimination, are believed to occur via transient σ-alkane complexes. This Account summarizes how isotope effects can be used to probe the nature of these intermediates and points out some pitfalls in interpreting kinetic data. Comparisons are made with arene C−H activation and other activation systems.

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Isotope effects in C-H bond activation reactions by transition metals.

Metal-Metal Multiply-Bonded Complexes of Technetium. 2. Preparation and Characterization of the Fully Solvated Ditechnetium Cation [Tc2(CH3CN)10]4+

Structural studies of formamidine compounds: from neutral to anionic and cationic species

Reversible carbon monoxide reactions of cationic rhodium(I) and -(II) complexes

Crystallographic disorder in the orthorhombic form of carbonyl(chlorobis(triphenylphosphine)rhodium: relevance to the reported structure of the paramagnetic impurity in Wilkinson's catalyst

Our current research interests is the coordination chemistry of solvated polynuclear metal cations, especially the recently reported rhodium(II,II) complex, (Rh{sub 2}(CH{sub 3}CH){sub 4})(F{sub 4}){sub 4}. In order to circumvent the problems associated with preparing and handling aqua species, we have developed a convenient synthesis for the CH{sub 3}CN derivative of RH{sub 2} (vide supra), a compound that allows easy access to other monomeric and polynuclear compounds of Rh(II). We now also report the synthesis of a pseudo-octahedral rhodium(II) monomer stabilized only by two bulky phosphine ligands.

Steven C. Haefner

Papers

Metal-Metal Multiply-Bonded Complexes of Technetium. 2. Preparation and Characterization of the Fully Solvated Ditechnetium Cation [Tc2(CH3CN)10]4+

Structural studies of formamidine compounds: from neutral to anionic and cationic species

Reversible carbon monoxide reactions of cationic rhodium(I) and -(II) complexes

Crystallographic disorder in the orthorhombic form of carbonyl(chlorobis(triphenylphosphine)rhodium: relevance to the reported structure of the paramagnetic impurity in Wilkinson's catalyst

Isolation, structure, and magnetic properties of a novel mononuclear rhodium(II) complex