Protic NHC Iridium Complexes with β-H Reactivity-Synthesis, Acetonitrile Insertion, and Oxidative Self-Activation

Mark K. Rong; Andrei Chirila; David Franciolus; Martin Lutz; Martin Nieger; Andreas W. Ehlers; J. Chris Slootweg; Koop Lammertsma

doi:10.1021/acs.organomet.9b00584

Protic NHC Iridium Complexes with β-H Reactivity-Synthesis, Acetonitrile Insertion, and Oxidative Self-Activation

Mark K. Rong
, Andrei Chirila
, David Franciolus
, Martin Lutz
, Martin Nieger
, Andreas W. Ehlers
, J. Chris Slootweg^*
, Koop Lammertsma

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

Protic NHC iridium complexes, obtained from the corresponding azido-phenylene-isocyanide precursor complexes, were investigated for ligand-based reactivity. Under redox-neutral conditions, acetonitrile inserts into the N-H bonds to provide κ²-NHC-imidoyl ligand-based complexes, while under reductive conditions the complex also expels one N-H proton to provide the corresponding deprotonated analogues. Using zinc as a reductor activates the NHC-iridium complex to form an asymmetric bimetallic iridium hydrido complex, in which two anionic N-deprotonated NHCs bridge the bimetallic core. X-ray crystal structures are reported for the azido-phenylene-isocyanide precursor complex, the protic NHC complex, and the asymmetric bimetallic iridium hydride complex. Density functional computations and a QTAIM analysis of the bimetallic iridium hydrido complex are provided.

Original language	English
Pages (from-to)	4543-4553
Number of pages	11
Journal	Organometallics
Volume	38
Issue number	23
DOIs	https://doi.org/10.1021/acs.organomet.9b00584
Publication status	Published - 9 Dec 2019

Funding

This work was supported by the Council for Chemical Sciences of The Netherlands Organization for Scientific Research (NWO/CW). We thank T. van Dijk for measuring high-resolution mass spectra. 2-Azidophenyl isonitrile was kindly provided by Carolin A. Dumke and F. Ekkehardt Hahn (Institut für Anorganische und Analytische Chemie, WWU Münster, Corrensstr. 28/30, D-48149 Münster, Germany).

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 6 Clean Water and Sanitation

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10.1021/acs.organomet.9b00584

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@article{71f653ae290b4fde8506912eb9da9edf,

title = "Protic NHC Iridium Complexes with β-H Reactivity-Synthesis, Acetonitrile Insertion, and Oxidative Self-Activation",

abstract = "Protic NHC iridium complexes, obtained from the corresponding azido-phenylene-isocyanide precursor complexes, were investigated for ligand-based reactivity. Under redox-neutral conditions, acetonitrile inserts into the N-H bonds to provide κ2-NHC-imidoyl ligand-based complexes, while under reductive conditions the complex also expels one N-H proton to provide the corresponding deprotonated analogues. Using zinc as a reductor activates the NHC-iridium complex to form an asymmetric bimetallic iridium hydrido complex, in which two anionic N-deprotonated NHCs bridge the bimetallic core. X-ray crystal structures are reported for the azido-phenylene-isocyanide precursor complex, the protic NHC complex, and the asymmetric bimetallic iridium hydride complex. Density functional computations and a QTAIM analysis of the bimetallic iridium hydrido complex are provided.",

author = "Rong, \{Mark K.\} and Andrei Chirila and David Franciolus and Martin Lutz and Martin Nieger and Ehlers, \{Andreas W.\} and \{Chris Slootweg\}, J. and Koop Lammertsma",

year = "2019",

month = dec,

day = "9",

doi = "10.1021/acs.organomet.9b00584",

language = "English",

volume = "38",

pages = "4543--4553",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "23",

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T1 - Protic NHC Iridium Complexes with β-H Reactivity-Synthesis, Acetonitrile Insertion, and Oxidative Self-Activation

AU - Rong, Mark K.

AU - Chirila, Andrei

AU - Franciolus, David

AU - Lutz, Martin

AU - Nieger, Martin

AU - Ehlers, Andreas W.

AU - Chris Slootweg, J.

AU - Lammertsma, Koop

PY - 2019/12/9

Y1 - 2019/12/9

N2 - Protic NHC iridium complexes, obtained from the corresponding azido-phenylene-isocyanide precursor complexes, were investigated for ligand-based reactivity. Under redox-neutral conditions, acetonitrile inserts into the N-H bonds to provide κ2-NHC-imidoyl ligand-based complexes, while under reductive conditions the complex also expels one N-H proton to provide the corresponding deprotonated analogues. Using zinc as a reductor activates the NHC-iridium complex to form an asymmetric bimetallic iridium hydrido complex, in which two anionic N-deprotonated NHCs bridge the bimetallic core. X-ray crystal structures are reported for the azido-phenylene-isocyanide precursor complex, the protic NHC complex, and the asymmetric bimetallic iridium hydride complex. Density functional computations and a QTAIM analysis of the bimetallic iridium hydrido complex are provided.

AB - Protic NHC iridium complexes, obtained from the corresponding azido-phenylene-isocyanide precursor complexes, were investigated for ligand-based reactivity. Under redox-neutral conditions, acetonitrile inserts into the N-H bonds to provide κ2-NHC-imidoyl ligand-based complexes, while under reductive conditions the complex also expels one N-H proton to provide the corresponding deprotonated analogues. Using zinc as a reductor activates the NHC-iridium complex to form an asymmetric bimetallic iridium hydrido complex, in which two anionic N-deprotonated NHCs bridge the bimetallic core. X-ray crystal structures are reported for the azido-phenylene-isocyanide precursor complex, the protic NHC complex, and the asymmetric bimetallic iridium hydride complex. Density functional computations and a QTAIM analysis of the bimetallic iridium hydrido complex are provided.

UR - https://www.scopus.com/pages/publications/85075654469

UR - https://www.scopus.com/pages/publications/85075654469#tab=citedBy

U2 - 10.1021/acs.organomet.9b00584

DO - 10.1021/acs.organomet.9b00584

M3 - Article

AN - SCOPUS:85075654469

SN - 0276-7333

VL - 38

SP - 4543

EP - 4553

JO - Organometallics

JF - Organometallics

IS - 23

ER -

Protic NHC Iridium Complexes with β-H Reactivity-Synthesis, Acetonitrile Insertion, and Oxidative Self-Activation

Abstract

Funding

UN SDGs

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Persistent URL (handle)

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CCDC 1915713: Experimental Crystal Structure Determination

CCDC 1921152: Experimental Crystal Structure Determination

CCDC 1915715: Experimental Crystal Structure Determination

Cite this

Protic NHC Iridium Complexes with β-H Reactivity-Synthesis, Acetonitrile Insertion, and Oxidative Self-Activation

Abstract

Funding

UN SDGs

Access to Document

Persistent URL (handle)

Other files and links

Fingerprint

Datasets

CCDC 1915713: Experimental Crystal Structure Determination

CCDC 1921152: Experimental Crystal Structure Determination

CCDC 1915715: Experimental Crystal Structure Determination

Cite this