Heteroleptic rhodium NHC complexes with pyridine-derived ligands: Synthetic accessibility and reactivity towards oxygen

Olena V. Zenkina; Eric C. Keske; Gurpaul S. Kochhar; Ruiyao Wang; Cathleen M. Crudden

doi:10.1039/c2dt32095a

Heteroleptic rhodium NHC complexes with pyridine-derived ligands: Synthetic accessibility and reactivity towards oxygen

Olena V. Zenkina, Eric C. Keske, Gurpaul S. Kochhar, Ruiyao Wang, Cathleen M. Crudden^*

^*Corresponding author for this work

Queen's University Kingston

Research output: Contribution to journal › Article › peer-review

25 Citations (Scopus)

Abstract

The synthesis, structure determination and oxidative stability of novel Rh-NHC complexes which feature pyridine-derived ligands have been described. All complexes described herein were synthesized from common dinuclear precursors of general structure [Rh(NHC)(L)Cl]₂, where L is a monodentate olefin. We demonstrate that the use of these precursors is critical for the formation of all complexes since related cyclooctadiene containing precursors ([Rh(NHC)(COD)Cl]) were completely unreactive under identical conditions. We further demonstrate that complexes with the general formula [Rh(NHC)(olefin)(Py) Cl] or ([Rh(NHC)(BiPy/Phen)Cl]) are extremely sensitive to oxygen, reacting initially to give an adduct with dioxygen, and then decomposing further. The series of compounds and their oxidation products gave a remarkable range of colours which may be useful in the preparation of colourometric oxygen sensors.

Original language	English
Pages (from-to)	2282-2293
Number of pages	12
Journal	Dalton Transactions
Volume	42
Issue number	6
DOIs	https://doi.org/10.1039/c2dt32095a
Publication status	Published - 14 Feb 2013
Externally published	Yes

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title = "Heteroleptic rhodium NHC complexes with pyridine-derived ligands: Synthetic accessibility and reactivity towards oxygen",

abstract = "The synthesis, structure determination and oxidative stability of novel Rh-NHC complexes which feature pyridine-derived ligands have been described. All complexes described herein were synthesized from common dinuclear precursors of general structure [Rh(NHC)(L)Cl]2, where L is a monodentate olefin. We demonstrate that the use of these precursors is critical for the formation of all complexes since related cyclooctadiene containing precursors ([Rh(NHC)(COD)Cl]) were completely unreactive under identical conditions. We further demonstrate that complexes with the general formula [Rh(NHC)(olefin)(Py) Cl] or ([Rh(NHC)(BiPy/Phen)Cl]) are extremely sensitive to oxygen, reacting initially to give an adduct with dioxygen, and then decomposing further. The series of compounds and their oxidation products gave a remarkable range of colours which may be useful in the preparation of colourometric oxygen sensors.",

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T1 - Heteroleptic rhodium NHC complexes with pyridine-derived ligands

T2 - Synthetic accessibility and reactivity towards oxygen

AU - Zenkina, Olena V.

AU - Keske, Eric C.

AU - Kochhar, Gurpaul S.

AU - Wang, Ruiyao

AU - Crudden, Cathleen M.

PY - 2013/2/14

Y1 - 2013/2/14

N2 - The synthesis, structure determination and oxidative stability of novel Rh-NHC complexes which feature pyridine-derived ligands have been described. All complexes described herein were synthesized from common dinuclear precursors of general structure [Rh(NHC)(L)Cl]2, where L is a monodentate olefin. We demonstrate that the use of these precursors is critical for the formation of all complexes since related cyclooctadiene containing precursors ([Rh(NHC)(COD)Cl]) were completely unreactive under identical conditions. We further demonstrate that complexes with the general formula [Rh(NHC)(olefin)(Py) Cl] or ([Rh(NHC)(BiPy/Phen)Cl]) are extremely sensitive to oxygen, reacting initially to give an adduct with dioxygen, and then decomposing further. The series of compounds and their oxidation products gave a remarkable range of colours which may be useful in the preparation of colourometric oxygen sensors.

AB - The synthesis, structure determination and oxidative stability of novel Rh-NHC complexes which feature pyridine-derived ligands have been described. All complexes described herein were synthesized from common dinuclear precursors of general structure [Rh(NHC)(L)Cl]2, where L is a monodentate olefin. We demonstrate that the use of these precursors is critical for the formation of all complexes since related cyclooctadiene containing precursors ([Rh(NHC)(COD)Cl]) were completely unreactive under identical conditions. We further demonstrate that complexes with the general formula [Rh(NHC)(olefin)(Py) Cl] or ([Rh(NHC)(BiPy/Phen)Cl]) are extremely sensitive to oxygen, reacting initially to give an adduct with dioxygen, and then decomposing further. The series of compounds and their oxidation products gave a remarkable range of colours which may be useful in the preparation of colourometric oxygen sensors.

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DO - 10.1039/c2dt32095a

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JO - Dalton Transactions

JF - Dalton Transactions

IS - 6

ER -

Heteroleptic rhodium NHC complexes with pyridine-derived ligands: Synthetic accessibility and reactivity towards oxygen

Abstract

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