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 October 11, 2010 | Supplemental Material
Journal Article Open

Protonolysis of Platinum(II) and Palladium(II) Methyl Complexes: A Combined Experimental and Theoretical Investigation


The protonolysis of platinum(II) and palladium(II) methyl complexes has been investigated by both experiment and computation. Previously the protonolysis of (COD)Pt^(II)(CH_3)_2 by CF_3COOY or (dppe)Pd^(II)(CH_3)_2 by CF_3CY_2OY (Y = H, D) was found to be accompanied by abnormally large and highly temperature-dependent kinetic isotope effects (KIEs), suggesting the involvement of tunneling. Here we find normal KIEs and no evidence of tunneling for protonolysis of (tmeda)Pt^(II)(CH_3)Cl by CF_3COOY (Y = H, D). Density functional theory (DFT) calculations indicate that protonation at the metal center followed by reductive coupling to the methane σ adduct (stepwise pathway) is favored for Pt complexes with good electron donor ligands, whereas direct protonation of the M−CH_3 bond to generate the methane σ adduct (concerted pathway) is favored for Pt with electron-withdrawing ligands as well as for Pd. We suggest that KIE behavior consistent with tunneling may be an experimental indicator of the concerted pathway.

Additional Information

© 2010 American Chemical Society. Received July 6, 2010. Publication Date (Web): September 10, 2010. This work was generously supported by BP through the MC2 program. An NSF Graduate Research Fellowship to G.S.C. is gratefully acknowledged.

Attached Files

Supplemental Material - om100655w_si_001.pdf


Files (492.7 kB)
Name Size Download all
492.7 kB Preview Download

Additional details

August 19, 2023
October 20, 2023