Tin, Antimony, Bismuth, and Tellurium Lewis Acids in sigma-Accepting Ligands for Transition Metals



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The interactions between ligands and transition metals have been an essential subject in inorganic chemistry. Other than the commonly known L-type (two-electron donors) and X-type ligands (one-electron donors), Z-type ligands (two-electron acceptors) have begun to surface in the past decade. Capable of drawing a pair of d-electrons away from a metal, Z-ligands affect the electronic structures of transition metals leading to fascinating properties as well as reactivity. In particular, recent advance in Z-ligand chemistry have resulted in the discovery of transition metal borane complexes featuring metal ? boron interactions. Owing to the presence of a metal ? boron interaction which stabilizes the low valent state, these complexes have been shown to activate small molecules such as H2, CO2, and CHCl3. Further, the concept of Z-ligand has been extended to s- and d-block Lewis acids. In spite of these achievements, Z-ligands that contain Group 14-16 elements as Lewis acids remain scarce and relatively unexplored.

For this reason, we have launched a series of investigations targeting complexes with transition metal ? Group 14-16 interactions. These investigations have allowed us to synthesize a series of novel complexes with palladium, platinum, or gold as metallobasic late transition metals and tin, antimony, bismuth, and tellurium as Lewis acids. The transition metal ? Lewis acid interactions of these complexes, which are supported by o-phosphinophenylene, 1,8-naphthalenediyl or 8-quinolinyl buttresses, have been established experimentally and theoretically. Further, the reactivity of these complexes toward anions and oxidants has also been explored. These experiments have led to the discovery of tellurium-platinum complexes that sustain reversible two-electron redox processes including the photo-reductive elimination of chlorine. Other noteworthy outcomes of this research include the isolation of the first telluroxanyl-metal complex as well as the discovery of complexes with HgII ? SbV interactions.