Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published January 15, 2007 | Accepted Version + Supplemental Material
Journal Article Open

Reactions of Indene and Indoles with Platinum Methyl Cations: Indene C−H Activation, Indole π versus Nitrogen Lone-Pair Coordination


Reactions of indene and various substituted indoles with [(diimine)Pt^(II)(Me)(TFE)]^+ cations have been studied (diimine = ArNC(Me)−C(Me)NAr; TFE = 2,2,2-trifluoroethanol). Indene displaces the TFE ligand from platinum to form a stable π coordination complex that, upon heating, undergoes C−H activation with first-order kinetics, ΔH^⧧ = 29 kcal/mol, ΔS^⧧ = 10 eu, and a kinetic isotope effect of 1.1 at 60 °C. Indoles also initially form coordination complexes through the C_2=C_3 olefin, but these undergo rearrangement to the corresponding N-bound complexes. The relative rates of initial coordination and rearrangement are affected by excess acid or methyl substitution on indole.

Additional Information

© 2007 American Chemical Society. Received July 25, 2006. Publication Date (Web): December 10, 2006. This work was supported by the BP MC2 program and by the NIH (NRSA fellowship GM075691 to T.J.W.). These sponsors are gratefully acknowledged. We thank Dr. Tom G. Driver for helpful discussions, especially regarding the preparation and use of BF_3−TFE-d_3. A preliminary X-ray structure for 8a has recently been obtained. This is a preliminary, low-resolution structure from a poorly diffracting crystal. Connectivity is unambiguous although distance and angle measurements have large errors. These data, CCDC 628218, can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

Attached Files

Accepted Version - nihms61740.pdf

Supplemental Material - om0606643si20060926_021616.pdf


Files (1.7 MB)
Name Size Download all
607.2 kB Preview Download
1.1 MB Preview Download

Additional details

August 19, 2023
October 23, 2023