CHAPTER 27. Noncovalent Interactions in Key Metal-centred Catalytic Intermediates: Structure–Electronic Relationship

This chapter covers the most recent advances in investigations of the most critical intermediates in transition metal-promoted processes with a main emphasis on metal-to-H–E bonding (mainly E = C, Si) interactions. After several decades of descriptive research on the interactions of C–H and Si–H bonds with coordinatively unsaturated metal centres, it is only recently that interest has risen in the role played by noncovalent interactions. It appears that recent advances in the understanding of so-called agostic interactions with metal centres demonstrate some control of the London force that the Dewar–Chatt–Duncanson model cannot sense. It is suggested that similar efforts should be generalized to other metal-to-H–E bonding interactions.