Metal–Organic Frameworks as Versatile Platforms for Organometallic Chemistry

Metal–organic frameworks (MOFs) are emerging porous materials with highly tunable structures developed in the 1990s, while organometallic chemistry is of fundamental importance for catalytic transformation in the academic and industrial world for many decades. Through the years, organometallic chemistry has been incorporated into functional MOF construction for diverse applications. Here, we will focus on how organometallic chemistry is applied in MOF design and modifications from linker-centric and metal-cluster-centric perspectives, respectively. Through structural design, MOFs can function as a tailorable platform for traditional organometallic transformations, including reaction of alkenes, cross-coupling reactions, and C–H activations. Besides, an overview will be made on other application categories of organometallic MOFs, such as gas adsorption, magnetism, quantum computing, and therapeutics.

True and masked three-coordinate T-shaped platinum(II) intermediates

Although four-coordinate square-planar geometries, with a formally 16-electron counting, are absolutely dominant in isolated Pt(II) complexes, three-coordinate, 14-electron Pt(II) complexes are believed to be key intermediates in a number of platinum-mediated organometallic transformations. Although very few authenticated three-coordinate Pt(II) complexes have been characterized, a much larger number of complexes can be described as operationally three-coordinate in a kinetic sense. In these compounds, which we have called masked T-shaped complexes, the fourth position is occupied by a very weak ligand (agostic bond, solvent molecule or counteranion), which can be easily displaced. This review summarizes the structural features of the true and masked T-shaped Pt(II) complexes reported so far and describes synthetic strategies employed for their formation. Moreover, recent experimental and theoretical reports are analyzed, which suggest the involvement of such intermediates in reaction mechanisms, particularly C–H bond-activation processes.

Connecting catalytic cycles by organometallic transformations in situ: Novel perspectives in the olefin metathesis field

Tandem sequences consisting of an olefin metathesis step and a subsequent non-metathesis reaction become accessible by organometallic transformations of the Ru-carbene species in situ. This contribution highlights some tandem sequences that rely on the conversion of the metathesis catalyst to Ru-hydrides, with special emphasis on the tandem ring-closing metathesis (RCM)-double-bond isomerization sequence.