Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

2015

Journal or Book Title

Organometallics

Volume

34

Issue

16

First Page

4023

Last Page

4031

DOI

10.1021/acs.organomet.5b00428

Abstract

Phosphine chalcogenides are useful reagents in chalcogen atom transfer reactions and nanocrystal syntheses. Understanding the strength and electronic structure of these bonds is key to optimizing their use, but a limited number of experimental and computational studies probe these issues. Using density functional theory (DFT), we computationally screen multiple series of trisubstituted phosphine chalcogenide molecules with a variety of phosphorus substituents and examine how these affect the strength of the phosphorus-chalcogen bond. DFT provides valuable data on these compounds including P-E bond dissociation energies, P-E bond order,Löwdin charge on phosphorus and chalcogen atoms, and molecular geometries. Experimentally monitoring the 31P and 77Se NMR chemical shifts and published Hammett constants provides good estimates and confirmation of the relative magnitude of electronic shielding around these nuclei and confirms the predictive value of the computational results.

Comments

Reprinted (adapted) with permission from Organometallics 34 (2015): 4023, doi: 10.1021/acs.organomet.5b00428. Copyright 2015 American Chemical Society.

Copyright Owner

American Chemical society

Language

en

File Format

application/pdf

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