This literature review focuses on the use of metal- or metalloid-based reagents to generate ortho-arynes from stable precursors via organometallic intermediates or to generate organometallic complexes of ortho-arynes. The review also encompasses the capture of arynes by organometallics to generate new complexes, with interesting reactivity in their own right, or as intermediates in catalytic systems. The purpose of the review is to highlight the novelty, utility and versatility of the interaction of organometallic species with arynes and their precursors. These points are illustrated through a number of examples of the application of such methods in the preparation of complex organic molecules. The review contains some 197 references and covers the literature up to May 2006.