Centenary Lecture. Reactivities of carbon disulphide, carbon dioxide, and carbonyl sulphide towards some transition-metal systems

This brief excursion into the reactivities of CS₂, CO ₂, and COS towards transition metals demonstrates the diversity of the individual chemistries. Although. CS₂ is a very reactive molecule, CO₂ is not. Cleavage of the C-O bond in CO₂ ⁷⁸ and the C-S bond in CS₂ play only minor roles in the chemistries, whereas C-S bond cleavage in COS is the important aspect of the chemistry. Thus far, the study of COS chemistry has not proved directly helpful in the activation of CO₂. Nor has the use of liquid CO₂ led to new, stable CO₂ complexes. Yet COS chemistry has proved to be interesting and diverse in its own right, with potential applications to carbonylation reactions. And the use of liquid CO₂ has proved to be valuable as a screening technique for reactivity of transition-metal systems towards CO₂. The chemistry of these molecules is in an early stage of development. Much remains to be explored, including a wider range of transition metals, kinetics and mechanisms of the reactions, and theoretical studies of the bonding. I am optimistic that the increased interest in this area, engendered in part by the potential utilization of CO₂ as a source for C₁ chemistry, will lead to rapid development of the chemistry of these fascinating molecules.