Synthesis and Characterisation of tetrahedro-Tetraphosphorus Complexes of Rhenium - Evidence for the First Bridging Complex of White Phosphorus

While the primary motivation of fundamental studies on carbonylhalotriruthenium complexes was to understand the promoter effect of halides on certain ruthenium-based catalytic systems of industrial relevance, such complexes have gained significance in their own right due to their remarkable ability to provide low-activation energy pathways for the coordination of organic substrates. Limitations inherent to the fragility of these prototypes led to the design and development of a related family of more sophisticated derivatives where an aminopyridyl group serves as an alternate hemilabile ancillary ligand. Studies of their reactivity have revealed the possibility of achieving a number of stoichiometric or moderately catalytic "cluster-mediated" transformations of organic substrates under very mild conditions. Yet, the viability of these systems is still limited to a narrow low-energy domain. By contrast, halotriruthenium derivatives are still seen to function as catalyst precursors under the actual conditions of certain catalytic reactions where they act as sources of ruthenium(II) halide complexes that become the active components of the system. The second part of the review focuses on novel aspects of their fascinating chemistry.