Organometallic chemistry, encompassing compounds with direct C-M and N-M bonds, remains one of the core synthetic pillars for the development and synthesis of new metal-organic and bio-active molecules. The application of organometallic reagents in targeting specific molecular frameworks relies on innovative complex design and insights into their structure and reactivity. Our research involves the design of new homo-metallic and hetero-bimetallic ‘ate’ complexes in which unusual deprotonative outcomes and unexpected cleavage reactions can result, all highly dependent on the metal and ligand choice employed. This presentation will highlight some of these reactivity outcomes, rationalising where possible the structure activity relationships that exist with focus on comparative amide, imine and phosphide substrates. In more recent work, extending this active-metal work to Ag(I)amido acid/base partnerships, we have been able to achieve unprecedented catalytic reactivity in a series of hydrofunctionalisation reactions establishing new roles for these active-metal regents in directed synthesis.