Unlike isolable tin(II) hydrides supported by bulky ligands reported in the literature, this research describes the synthesis and characterization of thermally stable tin(II) hydrides L^PhSnH (1-H) and ^MeLSnH (2-H) stabilized by sterically undemanding N,N,N-coordinating pincer-type ligands (L^Ph = 2,5-dipyridyl-3,4-diphenylpyrrolato; ^MeL = 2,5-bis(6-methylpyridyl)pyrrolato). The results from previous reports reveal that attempts to access tin(II) hydrides containing less-bulky ligands have had limited success, and decomposition to tin(I) distannynes often occurs. The key to the successful isolation of 1-H and 2-H is the identification of the role of Lewis acidic B^sBu₃, generated upon delivering hydride from commonly used hydride reagents M[B^sBu₃H] ("selectrides", M = Li or K). This study details compelling experimental evidence and theoretical results of the role played by B^sBu₃, which catalyzes the dehydrocoupling reactions of 1-H and 2-H to yield tin(I) distannynes L^PhSn-SnL^Ph (1₂) and ^MeLSn-Sn^MeL (2₂) with the liberation of H₂. To avoid the interference of B^sBu₃, 1-H and 2-H can be isolated in pure forms using pinacolborane as the hydride donor with L^PhSnOMe (1-OMe) and ^MeLSnOMe (2-OMe) as reactants, respectively. DFT calculations and experimental observations indicate that the coordination of the Sn-H bond of 1-H to B^sBu₃ leaves an electrophilic tin center, rendering the nucleophilic attack by the second equivalent of 1-H forming a Sn-Sn bond.

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