Advancing the Field of Soft Scorpionates Ligated to Carbyne, Aminocarbyne and Tricarbido Complexes

Abstract

Although the first Scorpionate ligand, Tp, was prepared some 56 years prior to the writing of this thesis, Scorpionates continue to be widely used throughout multiple areas of chemistry. In particular, Scorpionates have found broad utility in organometallic and coordination chemistry, due to the ease at which their steric and electronic impacts may be tailored to suit various metal-containing systems. In this regard, they have become a cornerstone within the field, and remain a common feature in new literature publications. Taking all pre-existing literature into account, pyrazole-based Scorpionate ligands, containing hard-donor atoms, feature in the majority of these publications. However, the work detailed in this thesis aims to further bolster the relatively underdeveloped field of Scorpionate ligands featuring soft donor groups, and their incorporation into organometallic systems. Examples of such soft Scorpionate ligands include Bm, Tm, Hbt, and Htt, which coordinate to metal centres via their exocyclic sulfur atoms, situated on their heterocyclic rings. The sections within this thesis describe the methods through which these soft Scorpionate ligands have been successfully incorporated into: tungsten and molybdenum propargylidyne complexes; tungsten and molybdenum metallacarbyne complexes containing polycyclic aromatic hydrocarbons; and, tungsten and molybdenum aminocarbyne complexes. Wherever possible, full spectral characterisation has been carried out and discussed briefly throughout these chapters. However, full details may be found in the Experimental Section, and in the accompanying Supplementary Information.