TY - JOUR
T1 - Redox-switched oxidation of dihydrogen using a non-innocent ligand
AU - Ringenberg, Mark R.
AU - Kokatam, Swarna Latha
AU - Heiden, Zachariah M.
AU - Rauchfuss, Thomas B.
PY - 2008/1/23
Y1 - 2008/1/23
N2 - Organometallic complexes containing non-innocent ligands of the type Cp*Ir(tBAFPh)(1), where H2tBAFPh is 2-(2-trifluoromethyl)anilino-4,6-di-tert-butylphenol, were found to activate H2 in a redox-switchable manner. The 16e- complex 1 was inert with respect to H2, CO, as well as conventional basic substrates until oxidation. Oxidation of 16-electron 1 with 1 equiv of Ag+ resulted in ligand-centered oxidation affording salts of [1]+, which were characterized by crystallographically, EPR, and elemental analyses. [1]+ was reduced to 1 in the presence of H2 and the sterically hindered base, 2,6-(tBu)2C5H3N, via a pathway that is first-order in both metal and dihydrogen. Compound [1]+ forms adducts with MeCN, which inhibits catalysis. The catalytic oxidation of H2 was established by electrochemical methods to be associated with the monocation.
AB - Organometallic complexes containing non-innocent ligands of the type Cp*Ir(tBAFPh)(1), where H2tBAFPh is 2-(2-trifluoromethyl)anilino-4,6-di-tert-butylphenol, were found to activate H2 in a redox-switchable manner. The 16e- complex 1 was inert with respect to H2, CO, as well as conventional basic substrates until oxidation. Oxidation of 16-electron 1 with 1 equiv of Ag+ resulted in ligand-centered oxidation affording salts of [1]+, which were characterized by crystallographically, EPR, and elemental analyses. [1]+ was reduced to 1 in the presence of H2 and the sterically hindered base, 2,6-(tBu)2C5H3N, via a pathway that is first-order in both metal and dihydrogen. Compound [1]+ forms adducts with MeCN, which inhibits catalysis. The catalytic oxidation of H2 was established by electrochemical methods to be associated with the monocation.
UR - https://www.scopus.com/pages/publications/38349173628
UR - https://www.scopus.com/inward/citedby.url?scp=38349173628&partnerID=8YFLogxK
U2 - 10.1021/ja076801k
DO - 10.1021/ja076801k
M3 - Article
C2 - 18163627
AN - SCOPUS:38349173628
SN - 0002-7863
VL - 130
SP - 788
EP - 789
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 3
ER -