Home
Resources
Publications
Calculations Find That Tunneling Plays a Major Role in the Reductive Elimination of Methane From Hydridomethylbis(trimethylphosphine)platinum: How to Confirm This Computational Prediction Experimentally

Calculations Find That Tunneling Plays a Major Role in the Reductive Elimination of Methane From Hydridomethylbis(trimethylphosphine)platinum: How to Confirm This Computational Prediction Experimentally

Ayan Datta, David A Hrovat, Weston Thatcher Borden

J Am Chem Soc. 2008 Mar 5;130(9):2726-7.

PMID: 18266369

Abstract:

DFT calculations, including the effects of small curvature tunneling, have been performed on the reductive elimination of methane from hydridomethylbis(trimethylphosphine)platinum (1d). The calculations find that at 250 K tunneling results in an increase in the rate constant for reductive elimination by a factor of 4, a lowering of Ea by 1.7 kcal/mol, and a decrease in A by a factor of nearly 10. Tunneling is also calculated to increase the primary H/D kinetic isotope effect (KIE) from k(1d)/k(1f) = 2.26 to k(1d)/k(1f) = 4.12 and to result in a large secondary KIE of k(1d)/k(1e) = 1.35. In addition, tunneling is predicted to result in a violation of the rule of the geometric mean, so that the secondary KIE for reductive elimination of methane-d1 from 1f is calculated to be k(1f)/k(1g) = 1.06, which is much smaller than the secondary KIE of k(1d)/k(1e) = 1.35 for reductive elimination of methane from 1d. Comparison of the measured values of k(1d)/k(1e) and k(1f)/k(1g) is therefore proposed as an experimental test of the prediction that tunneling plays an important role in the reductive elimination of methane from 1d.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP676493	Methane-d1		676-49-3	Price

As a specialist in analytical chemical Products, Alfa Chemistry offers consumers a wealth of raw materials and a full range of technologies and services.

QUICK LINKS

HEADQUARTERS

Tel:

Fax:

Email: