Mechanism of the Stereomutation of an Azaplatinacyclobutane Complex

Journal Article (Journal Article)

The diastereomerically pure azaplatinacyclobutane complex, bearing a single deuterium atom at Cα, undergoes stereomutation about the Cα-Cβ bond of the azaplatinacyclobutane moiety at 30 °C with a half-life of 3.0 h. Kinetic analysis of the stereomutation of cis-6-α-d1 established the activation parameters ΔH‡ = 26 ± 2 kcal mol-1 and ΔS‡ = 6 ± 6 eu and a deuterium kinetic isotope effect resulting from deuteration of the Cβ atom of kH/kD = 1.32. These and related experiments support a mechanism for stereomutation involving rapid and reversible amine dissociation, reversible β-hydride elimination, and rate-limiting rotation about the Cα-Cβ bond of the resulting platinum enamine complex.

Full Text

Duke Authors

Cited Authors

  • Bender, CF; Widenhoefer, RA

Published Date

  • April 26, 2021

Published In

Volume / Issue

  • 40 / 8

Start / End Page

  • 1071 - 1076

Electronic International Standard Serial Number (EISSN)

  • 1520-6041

International Standard Serial Number (ISSN)

  • 0276-7333

Digital Object Identifier (DOI)

  • 10.1021/acs.organomet.1c00054

Citation Source

  • Scopus