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Manuscript.pdf (2.86 MB)
H2 Evolution from H2O via O–H Oxidative Addition Across a 9,10-Diboraanthracene
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submitted on 02.08.2020 and posted on 03.08.2020by Jordan W. Taylor, William Harman
The boron-centered water reactivity of the boroauride complex
([Au(B2P2)][K(18-c-6)]; (B2P2, 9,10-bis(2-(diisopropylphosphino)-
phenyl)-9,10-dihydroboranthrene) and its corresponding twoelectron oxidized complex, Au(B2P2)Cl, are presented. The
tolerance of Au(B2P2)Cl towards H2O was demonstrated and
subsequent hydroxide/chloride exchange was acheived in the
presence of H2O and triethylamine to afford Au(B2P2)OH.
Au(B2P2)]Cl and [Au(B2P2)]OH are poor Lewis acids as judged by the
Gutmann-Becket method, with [Au(B2P2)]OH displaying facile
hydroxide exchange between B atoms of the DBA ring as evidenced
by variable temperature 31P NMR and low temperature 1H and 11B
NMR. The reaction of the reduced boroauride complex [Au(B2P2)]–
with 1 equivalent of H2O produces a hydride/hydroxide product,
[Au(B2P2)(H)(OH)]–, that, upon addition of a second equivalent of
H2O, rapidly evolves H2 to yield the dihydroxide compound,
[Au(B2P2)(OH)2]–. [Au(B2P2)]Cl can be regenerated from
[Au(B2P2)(OH)2]– via HCl·Et2O, providing a synthetic cycle for H2
evolution from H2O enabled by O–H oxidative addition at a