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Published June 10, 2013 | Supplemental Material
Journal Article Open

Kinetics and Mechanism of Indene C–H Bond Activation by [(COD)Ir(μ_2-OH)]_2


The hydroxy-bridged dimer [(COD)Ir(μ_2-OH)]_2 (COD = 1,5-cyclooctadiene) cleanly cleaves C–H bonds in indene and cyclopentadiene to produce (COD)Ir(η^3-indenyl) and (COD)Ir(η^5-C_(5)H_5), respectively. The kinetics of the formation of (COD)Ir(η^3-indenyl) are consistent with a mechanism that involves coordination of indene to [(COD)Ir(μ_2-OH)]_2 followed by rate-determining C–H activation from the iridium dimer–indene unit. Transition-state analysis of the Ir and Rh hydroxy dimers indicates that the C–H activation proceeds through a direct deprotonation of indene by the M–OH unit rather than a stepwise oxidative addition/reductive elimination mechanism. The crystal structure of [(COD)Ir]_5(μ_4-O)(μ_3-O)(μ_2-OH), a dehydration product of [(COD)Ir(μ_2-OH)]_2, is presented.

Additional Information

© 2013 American Chemical Society. Received: March 18, 2013; Published: May 23, 2013. We thank Lawrence Henling and Dr. Michael Day for assistance with the X-ray studies. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF: MU award to the California Institute of Technology, CHE-0639094. This work has been supported by USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-85ER13431) and by the Caltech Summer Undergraduate Research Fellowship program (T.S.A.).

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Supplemental Material - om400230j_si_001.pdf

Supplemental Material - om400230j_si_002.cif


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