Open AccessComparing Metal–Halide and −Oxygen Adducts in Oxidative C/O–H Activation: AuIII–Cl versus AuIII–OH
Author(s) -
Marta Lovisari,
Robert Gericke,
Brendan Twamley,
Aidan R. McDonald
Publication year - 2021
Publication title -
inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 233
eISSN - 1520-510X
pISSN - 0020-1669
DOI - 10.1021/acs.inorgchem.1c02222
Subject(s) - chemistry , adduct , halide , metal , ligand (biochemistry) , oxygen , oxidative addition , medicinal chemistry , oxygen atom , metal halides , inorganic chemistry , photochemistry , terpyridine , molecule , catalysis , organic chemistry , biochemistry , receptor
High-valent metal-halides have come to prominence as highly effective oxidants. A direct comparison of their efficacy against that of traditional metal-oxygen adducts is needed. [Au III (Cl)(terpy)](ClO 4 ) 2 ( 1 ; terpy = 2,2':6',2-terpyridine) readily oxidized substrates bearing O-H and C-H bonds via a hydrogen atom transfer mechanism. A direct comparison with [Au III (OH)(terpy)](ClO 4 ) 2 ( 2 ) showed that 1 was a kinetically superior oxidant with respect to 2 for all substrates tested. We ascribe this to the greater thermodynamic driving force imbued by the Cl ligand versus the OH ligand.