Evidence for Iron-Catalyzed α-Phosphinidene Elimination with Phenylphosphine

Justin K Pagano; Brandon J Ackley; Rory Waterman

doi:10.1002/chem.201704954

Evidence for Iron-Catalyzed α-Phosphinidene Elimination with Phenylphosphine

Chemistry. 2018 Feb 21;24(11):2554-2557. doi: 10.1002/chem.201704954. Epub 2017 Dec 11.

Authors

Justin K Pagano^{1

2}, Brandon J Ackley¹, Rory Waterman¹

Affiliations

¹ Department of Chemistry, University of Vermont, Discovery Hall, USA.
² Current Address: Chemistry Division, Los Alamos National Laboratory, Mail Stop J-514, Los Alamos, NM, 87545, USA.

PMID: 29194820
DOI: 10.1002/chem.201704954

Abstract

The ubiquitous half-sandwich iron complex [CpFe(CO)₂ Me] (Cp=η⁵ -C₅ H₅ ) appears to be a catalyst for α-phosphinidene elimination from primary phosphines. Dehydrocoupling reactions provided initial insight into this unusual reaction mechanism, and trapping reactions with organic substrates gave products consistent with an α elimination mechanism, including a rare example of a three-component reaction. The substrate scope of this reaction is consistent with generation of a triplet phosphinidene. In all, this study presents catalytic phosphinidene transfer to unsaturated organic substrates.

Keywords: homogeneous catalysis; iron; phosphinidenes; phosphorus; trapping reactions.