TY - GEN
T1 - Water and benzene H/D exchange by a cyclometallated Ir(III) bishydroxo pyridyl complex
AU - Periana, Roy A.
AU - Meier, Steven K.
AU - Young, Kenneth J.H.
AU - Tenn, William J.
AU - Oxgaard, Jonas
AU - Goddard, William A.
PY - 2007/12/31
Y1 - 2007/12/31
N2 - The well known Catalytica system, Pt(bipyrimidine)Cl2 in liquid sulfuric acid, selectively converts methane to methylbisulfate in good yields. However, the expensive methanol separation and strong inhibition of the electrophilic Pt(II) center by water makes the system impractical. To design more effective catalysts that can operate in less acidic solvents such as water we have been exploring the design of more electron-rich complexes such as Ir(NNC)(OH)2Py, where NNC = 6-phenyl-4,4′-di-tert-butyl-2,2′-bipyridine, that could be active for CH activation in the presence of water and also be thermally stable to protic, oxidizing media. We now report that this complex catalyzes H/D exchange between benzene and water with an activation barrier of ∼33 (± 2) kcals/mol at 160 °C. Experimental results and DFT calculations provide insight into the mechanism of CH activation with this system.
AB - The well known Catalytica system, Pt(bipyrimidine)Cl2 in liquid sulfuric acid, selectively converts methane to methylbisulfate in good yields. However, the expensive methanol separation and strong inhibition of the electrophilic Pt(II) center by water makes the system impractical. To design more effective catalysts that can operate in less acidic solvents such as water we have been exploring the design of more electron-rich complexes such as Ir(NNC)(OH)2Py, where NNC = 6-phenyl-4,4′-di-tert-butyl-2,2′-bipyridine, that could be active for CH activation in the presence of water and also be thermally stable to protic, oxidizing media. We now report that this complex catalyzes H/D exchange between benzene and water with an activation barrier of ∼33 (± 2) kcals/mol at 160 °C. Experimental results and DFT calculations provide insight into the mechanism of CH activation with this system.
UR - https://www.scopus.com/pages/publications/37349003768
M3 - Conference contribution
AN - SCOPUS:37349003768
SN - 0841269556
SN - 9780841269552
T3 - ACS National Meeting Book of Abstracts
BT - 234th ACS National Meeting, Abstracts of Scientific Papers
T2 - 234th ACS National Meeting
Y2 - 19 August 2007 through 23 August 2007
ER -