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Abstract: Two novel, thioether containing benzannulated enediyne ligands, 1,2-bis(3-(quinolin-8-ylsulfanyl)prop-1-ynyl)benzene (1), and 1,2-bis(3-(pyridin-2-ylmethylsulfanyl)prop-1-ynyl)benzene (2) have been synthesized and characterized along with their corresponding Cu(I), Ag(I), Cu(II), and Pd(II) metalloenediyne complexes (3–10). Single crystal X-ray structures of the d10 and d8 N2S2 complexes show thioether coordination leading to distorted tetrahedral and trans square planar geometries about the metal centers, respectively. Based on their X-ray structures, all complexes are expected to exhibit high Bergman cyclization temperatures (>200 °C), and indeed this is the case for the Cu(I) and Ag(I) complexes (211–218 °C). In contrast, the corresponding divalent, tetragonal and trans square planar complexes of Cu(II) and Pd(II) exhibit more facile reactivity and lower solid state Bergman cyclization temperatures (186–190 °C) which more closely resemble values expected for cis-complexes. The unusual order in the thermal reactivities of these constructs can be attributed to a previously evaluated mechanism by which weak thioether coordination permits an elevated temperature trans-to-cis geometric rearrangement prior to Bergman cyclization. [Copyright &y& Elsevier]