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Issue 40, 2020
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Reversible addition of ethylene to a pincer-based boryl-iridium unit with the formation of a bridging ethylidene

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Abstract

This report examines reactions of a series of Ir complexes supported by the diarylboryl/bis(phosphine) PBP pincer ligand with ethylene: (PBP)IrH4 (1), (PBP)IrH2(CO) (2), and (PBP)Ir(CO)2 (3). The outcomes of these reactions differ from those typical for Ir complexes supported by other pincer ligands and do not give rise to simple ethylene adducts or products of insertion of Ir into the C–H bond of ethylene. Instead, the elements of ethylene are incorporated into the molecules to result in B–C bonds. In the case of 2 and 3, ethylene addition results in the formation of B/Ir bridging ethylidene complexes 5 and 6. For 6, the addition of ethylene (and the analogous addition of 1-hexene) is shown to be partially reversible. Addition of ethylene to 2 and 3 is remarkable because they are saturated at Ir and yet the net outcome is such that ethylene binds without replacing any ligands already present. A mechanistic inquiry suggests that dissociation of CO from 3 or 6 is necessary in order for the addition or loss of ethylene to proceed.

Graphical abstract: Reversible addition of ethylene to a pincer-based boryl-iridium unit with the formation of a bridging ethylidene

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Article information


Submitted
29 Aug 2020
Accepted
04 Oct 2020
First published
05 Oct 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 10998-11002
Article type
Edge Article

Reversible addition of ethylene to a pincer-based boryl-iridium unit with the formation of a bridging ethylidene

Y. Cao, W. Shih, N. Bhuvanesh and O. V. Ozerov, Chem. Sci., 2020, 11, 10998
DOI: 10.1039/D0SC04748A

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