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Acting as a bridge between the heterogeneous and homogeneous realms, the use of discrete, well-defined, solid-state organometallic complexes for synthesis and catalysis is a remarkably undeveloped field. Here, we present a review of this topic, focusing on describing the key transformations that can be observed at a transition-metal centre, as well as the use of well-defined organometallic complexes in the solid state as catalysts. There is a particular focus upon gas-solid reactivity/catalysis and single-crystal-to-single-crystal transformations.

A Rh-catalyst system based on the asymmetric ligand tBu2PCH2P(o-C6H4OMe)2 is reported that allows for the hydroacylation of challenging internal alkenes with β-substituted aldehydes. Mechanistic studies point to the stabilizing role of both excess alkene and the OMe-group.

A novel ruthenium catalyzed cross-coupling reaction between the title substrates, which shows good functional group tolerance, is developed.

A highly linear-selective alkyne hydroacylation protocol, covering a range of electron-rich and electron-poor aromatic aldehydes, alkyl aldehydes, and enal substrates, is reported.

Intermolecular hydroacylation of a wide variety of unactivated alkenes, allenes and alkynes with aromatic and aliphatic aldehydes is efficiently catalyzed by rhodium catalysts containing diphosphine ligands with small bite angles.

The optimized Rh(I)-catalyzed reaction of aryl methyl sulfides such as (I) with terminal alkynes affords arylvinyl methyl sulfides.

It's all in the ligand: By choice of the appropriate diphosphine ligand a previously linear-selective alkyne hydroacylation process can be "switched" to be highly branched-selective (see scheme, l=linear, b=branched). Structural data for the ortho-iPr-dppe-rhodium catalyst suggest restricted rotation of the phosphine aryl units may be responsible for the observed selectivity. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The complex [(PPh3)Ag(CB11H6Br6)] 1 is an effective and selective catalyst (0.1 mol% loading) for a hetero-Diels–Alder reaction, which shows a marked dependence on the presence of trace amounts of water, while addition of Ag[Y] [Y = CB11H12, CB11H6Br6, O3SCF3] to a phosphine functionalised support gives an efficient and recyclable Lewis acid catalyst for this transformation.

The interaction of hydrogen with metal surfaces is one of the most important and fundamental processes in the chemical industry. Hydrogen is also strongly tipped to play a central role in new challenges that are emerging in terms of climate change and energy supply, and the reversible binding of H2 to suitable materials will play a keystone role in the realisation of the hydrogen economy. The reversible interaction of hydrogen with multimetallic centres is also an important theme in biological processes; the role of hydrogenases in the metabolism of H2 is an example. Thus the reversible interaction of H2 with multimetallic metal complexes is an area that spans considerable breadth. This review is concerned

Facile, metal-mediated, (acceptorless) dehydrogenation of tricyclopentyl phosphine directly affords rhodium chelating phosphine-olefin complexes, some of which are catalytically active for 1,4-additions.