Metal-ligand cooperativity enables zero-valent metal transfer.

ABSTRACT: Group 13 aminoxy complexes of the form (L)E(TEMPO)₃ (TEMPO = 2,2,6,6-tetramethylpiperidine 1-oxyl; L = THF (tetrahydrofuran) or Py (pyridine); E = Al, Ga, In) were prepared and structurally characterized. The complexes (THF)Ga(TEMPO)₃ (1·THF) and (Py)In(TEMPO)₃ (2·Py) are shown to heterolytically cleave H₂ under mild conditions (3 atm, 20 °C, t ≤ 1 h). 1·THF reacts reversibly with H₂ to form a formal H₂-adduct that bears a Ga(iii) hydride site and a protonated TEMPO ligand with concomitant loss of THF, consistent with Ga(iii) and TEMPO functioning as Lewis acid and base, respectively. Conversely, 2·Py is reduced by H₂ to form an intermediate dimer complex of monovalent {In(TEMPO)}₂, which undergo

SUBMITTER: Riu MY 

PROVIDER: S-EPMC11777705 | biostudies-literature | 2025 Feb

REPOSITORIES: biostudies-literature