Issue 35, 2023

Dynamic-dependent selectivity in a bisphosphine iron spin crossover C–H insertion/π-coordination reaction

Abstract

Reaction pathway selectivity is generally controlled by competitive transition states. Organometallic reactions are complicated by the possibility that electronic spin state changes rather than transition states can control the relative rates of pathways, which can be modeled as minimum energy crossing points (MECPs). Here we show that in the reaction between bisphosphine Fe and ethylene involving spin state crossover (singlet and triplet spin states) that neither transition states nor MECPs model pathway selectivity consistent with experiment. Instead, single spin state and mixed spin state quasiclassical trajectories demonstrate nonstatistical intermediates and that C–H insertion versus π-coordination pathway selectivity is determined by the dynamic motion during reactive collisions. This example of dynamic-dependent product outcome provides a new selectivity model for organometallic reactions with spin crossover.

Graphical abstract: Dynamic-dependent selectivity in a bisphosphine iron spin crossover C–H insertion/π-coordination reaction

Supplementary files

Article information

Article type
Edge Article
Submitted
22 Apr. 2023
Accepted
13 Aug. 2023
First published
21 Aug. 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 9400-9408

Dynamic-dependent selectivity in a bisphosphine iron spin crossover C–H insertion/π-coordination reaction

M. T. Davenport, J. K. Kirkland and D. H. Ess, Chem. Sci., 2023, 14, 9400 DOI: 10.1039/D3SC02078A

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