Group 14 Metallocene Catalysts for Carbonyl Hydroboration and Cyanosilylation

Authors

Haley J. Robertson, Chapman UniversityFollow
Mallory N. Fujiwara, Chapman University
Allegra L. Liberman-Martin, Chapman UniversityFollow

Document Type

Article

Publication Date

1-10-2024

Abstract

A series of six Group 14 metallocene compounds (M = Ge, Sn, Pb) were studied as catalysts for carbonyl hydroboration and cyanosilylation reactions at room temperature. Both bis(pentamethylcyclopentadienyl) and tetramethyldisiloxa[3]metallocenophane compounds were compared. The tin and lead metallocenophanes exhibited the highest reactivity in hydroboration and cyanosilylation reactions. Hammett analysis of aldehyde hydroboration provided a ρ value of 0.73, suggesting a buildup of negative charge during the turnover-limiting step, consistent with the transition state for hydride transfer to the carbonyl center. NMR studies of Lewis acidity indicate that the Ge, Sn, and Pb tetramethyldisiloxa[3]metallocenophane compounds are weak Lewis acids.

Comments

This article was originally published in Polyhedron, volume 250, in 2024. https://doi.org/10.1016/j.poly.2024.116837

Recommended Citation

H.J. Robertson, M.N. Fujiwara, A.L. Liberman-Martin, Group 14 metallocene catalysts for carbonyl hydroboration and cyanosilylation, Polyhedron. 250 (2024) 116837, https://doi.org/10.1016/j.poly.2024.116837

Copyright

The authors

Creative Commons License

This work is licensed under a Creative Commons Attribution-Noncommercial-No Derivative Works 4.0 License.