The synthesis, spectroscopic, and electrochemical characterization of transition metalloligand complexes of the type Cp*2Ti(C2-2-py)2 (1), Cp*2Ti(C2-2-thio)2 (2), and (p-cymene)Ru(PMe3)(C2-2-py)2 (3) (where H-C2-2-py = 2-ethynylpyridine and H-C2-2-thio = 2-ethynylthiophene) are reported. All were characterized by multinuclear NMR and IR spectroscopy, as well as cyclic voltammetry. A single-crystal X-ray structure of compound 2 confirmed the cis-coordinated C2-2-thio ligands. Complexes 1-3 were prepared via the reaction of Cp*2Ti(Cl)2 or (p-cymene)Ru(PMe3)(Cl)2 with H-C2-2-py or H-C2-2-thio in the presence of excess n-BuLi. Of note, we found compound 2 can coordinate Cu(I) between its alkynes to form Cp*2Ti(C2-2-thio)2(CuI), as observed by X-ray crystallography. The utilization of these complexes in C-C coupling reactions, such as the Heck reaction, and other model systems for trans-bidentate ligands will be presented.

Synthesis, characterization, and reactivity of transition metal hinged complexes for trans-bidentate ligand coordination

ACS Spring 2022

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