Cooperative Bond Activation and Facile Intramolecular Aryl Transfer of Nickel–Aluminum Pincer-type Complexes

Brendan J Graziano; Matthew V. Vollmer; Connie C. Lu

doi:10.1002/anie.202104050

Cooperative Bond Activation and Facile Intramolecular Aryl Transfer of Nickel–Aluminum Pincer-type Complexes

Brendan J Graziano, Matthew V. Vollmer, Connie C. Lu

Chemistry (Twin Cities)

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35 Scopus citations

Abstract

Pincer-type nickel–aluminum complexes were synthesized using two equivalents of the phosphinoamide, [PhNCH₂PⁱPr₂]⁻. The Ni⁰–Al^III complexes, {(^MesPAlP)Ni}₂(μ-N₂) and {(^MesPAlP)Ni}₂(μ-COD), where ^MesPAlP is (Mes)Al(NPhCH₂PⁱPr₂)₂, were structurally characterized. The (PAlP)Ni system exhibited cooperative bond cleavage mediated by the two-site Ni–Al unit, including oxidative addition of aryl halides, H₂ activation, and ortho-directed C−H bond activation of pyridine N-oxide. One intriguing reaction is the reversible intramolecular transfer of the mesityl ring from the Al to the Ni site, which is evocative of the transmetalation step during cross-coupling catalysis. The aryl-transfer product,(THF)Al(NPhCH₂PⁱPr₂)₂Ni(Mes), is the first example of a first-row transition metal–aluminyl pincer complex. The addition of a judicious donor enables the Al metalloligand to convert reversibly between the alane and aluminyl forms via aryl group transfer to and from Ni, respectively. Theoretical calculations support a zwitterionic Ni^δ−–Al^δ+ electronic structure in the nickel–aluminyl complex.

Original language	English (US)
Pages (from-to)	15087-15094
Number of pages	8
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	27
DOIs	https://doi.org/10.1002/anie.202104050
State	Published - Jun 25 2021

Bibliographical note

Funding Information:
The authors thank Dr. Bianca L. Ramirez for initial metalloligand synthesis, Dr. Victor G. Young, Jr. for crystallographic assistance, and Dr. Letitia J. Yao for assistance with NMR spectroscopy. This work was supported by the NSF (CHE‐1954751). X‐ray diffraction experiments were performed using a crystal diffractometer acquired through an NSF‐MRI award (CHE‐1229400). The computational resources were provided by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota.

Funding Information:
The authors thank Dr. Bianca L. Ramirez for initial metalloligand synthesis, Dr. Victor G. Young, Jr. for crystallographic assistance, and Dr. Letitia J. Yao for assistance with NMR spectroscopy. This work was supported by the NSF (CHE-1954751). X-ray diffraction experiments were performed using a crystal diffractometer acquired through an NSF-MRI award (CHE-1229400). The computational resources were provided by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota.

Publisher Copyright:
© 2021 Wiley-VCH GmbH

Keywords

Lewis acids
aluminum
cooperative effects
metal–metal interactions
nickel

PubMed: MeSH publication types

Journal Article

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10.1002/anie.202104050

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title = "Cooperative Bond Activation and Facile Intramolecular Aryl Transfer of Nickel–Aluminum Pincer-type Complexes",

abstract = "Pincer-type nickel–aluminum complexes were synthesized using two equivalents of the phosphinoamide, [PhNCH2PiPr2]−. The Ni0–AlIII complexes, {(MesPAlP)Ni}2(μ-N2) and {(MesPAlP)Ni}2(μ-COD), where MesPAlP is (Mes)Al(NPhCH2PiPr2)2, were structurally characterized. The (PAlP)Ni system exhibited cooperative bond cleavage mediated by the two-site Ni–Al unit, including oxidative addition of aryl halides, H2 activation, and ortho-directed C−H bond activation of pyridine N-oxide. One intriguing reaction is the reversible intramolecular transfer of the mesityl ring from the Al to the Ni site, which is evocative of the transmetalation step during cross-coupling catalysis. The aryl-transfer product,(THF)Al(NPhCH2PiPr2)2Ni(Mes), is the first example of a first-row transition metal–aluminyl pincer complex. The addition of a judicious donor enables the Al metalloligand to convert reversibly between the alane and aluminyl forms via aryl group transfer to and from Ni, respectively. Theoretical calculations support a zwitterionic Niδ−–Alδ+ electronic structure in the nickel–aluminyl complex.",

keywords = "Lewis acids, aluminum, cooperative effects, metal–metal interactions, nickel",

author = "Graziano, {Brendan J} and Vollmer, {Matthew V.} and Lu, {Connie C.}",

note = "Funding Information: The authors thank Dr. Bianca L. Ramirez for initial metalloligand synthesis, Dr. Victor G. Young, Jr. for crystallographic assistance, and Dr. Letitia J. Yao for assistance with NMR spectroscopy. This work was supported by the NSF (CHE‐1954751). X‐ray diffraction experiments were performed using a crystal diffractometer acquired through an NSF‐MRI award (CHE‐1229400). The computational resources were provided by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota. Funding Information: The authors thank Dr. Bianca L. Ramirez for initial metalloligand synthesis, Dr. Victor G. Young, Jr. for crystallographic assistance, and Dr. Letitia J. Yao for assistance with NMR spectroscopy. This work was supported by the NSF (CHE-1954751). X-ray diffraction experiments were performed using a crystal diffractometer acquired through an NSF-MRI award (CHE-1229400). The computational resources were provided by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota. Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

year = "2021",

month = jun,

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doi = "10.1002/anie.202104050",

language = "English (US)",

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T1 - Cooperative Bond Activation and Facile Intramolecular Aryl Transfer of Nickel–Aluminum Pincer-type Complexes

AU - Graziano, Brendan J

AU - Vollmer, Matthew V.

AU - Lu, Connie C.

N1 - Funding Information: The authors thank Dr. Bianca L. Ramirez for initial metalloligand synthesis, Dr. Victor G. Young, Jr. for crystallographic assistance, and Dr. Letitia J. Yao for assistance with NMR spectroscopy. This work was supported by the NSF (CHE‐1954751). X‐ray diffraction experiments were performed using a crystal diffractometer acquired through an NSF‐MRI award (CHE‐1229400). The computational resources were provided by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota. Funding Information: The authors thank Dr. Bianca L. Ramirez for initial metalloligand synthesis, Dr. Victor G. Young, Jr. for crystallographic assistance, and Dr. Letitia J. Yao for assistance with NMR spectroscopy. This work was supported by the NSF (CHE-1954751). X-ray diffraction experiments were performed using a crystal diffractometer acquired through an NSF-MRI award (CHE-1229400). The computational resources were provided by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota. Publisher Copyright: © 2021 Wiley-VCH GmbH

PY - 2021/6/25

Y1 - 2021/6/25

N2 - Pincer-type nickel–aluminum complexes were synthesized using two equivalents of the phosphinoamide, [PhNCH2PiPr2]−. The Ni0–AlIII complexes, {(MesPAlP)Ni}2(μ-N2) and {(MesPAlP)Ni}2(μ-COD), where MesPAlP is (Mes)Al(NPhCH2PiPr2)2, were structurally characterized. The (PAlP)Ni system exhibited cooperative bond cleavage mediated by the two-site Ni–Al unit, including oxidative addition of aryl halides, H2 activation, and ortho-directed C−H bond activation of pyridine N-oxide. One intriguing reaction is the reversible intramolecular transfer of the mesityl ring from the Al to the Ni site, which is evocative of the transmetalation step during cross-coupling catalysis. The aryl-transfer product,(THF)Al(NPhCH2PiPr2)2Ni(Mes), is the first example of a first-row transition metal–aluminyl pincer complex. The addition of a judicious donor enables the Al metalloligand to convert reversibly between the alane and aluminyl forms via aryl group transfer to and from Ni, respectively. Theoretical calculations support a zwitterionic Niδ−–Alδ+ electronic structure in the nickel–aluminyl complex.

AB - Pincer-type nickel–aluminum complexes were synthesized using two equivalents of the phosphinoamide, [PhNCH2PiPr2]−. The Ni0–AlIII complexes, {(MesPAlP)Ni}2(μ-N2) and {(MesPAlP)Ni}2(μ-COD), where MesPAlP is (Mes)Al(NPhCH2PiPr2)2, were structurally characterized. The (PAlP)Ni system exhibited cooperative bond cleavage mediated by the two-site Ni–Al unit, including oxidative addition of aryl halides, H2 activation, and ortho-directed C−H bond activation of pyridine N-oxide. One intriguing reaction is the reversible intramolecular transfer of the mesityl ring from the Al to the Ni site, which is evocative of the transmetalation step during cross-coupling catalysis. The aryl-transfer product,(THF)Al(NPhCH2PiPr2)2Ni(Mes), is the first example of a first-row transition metal–aluminyl pincer complex. The addition of a judicious donor enables the Al metalloligand to convert reversibly between the alane and aluminyl forms via aryl group transfer to and from Ni, respectively. Theoretical calculations support a zwitterionic Niδ−–Alδ+ electronic structure in the nickel–aluminyl complex.

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KW - cooperative effects

KW - metal–metal interactions

KW - nickel

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JO - Angewandte Chemie - International Edition

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ER -

Cooperative Bond Activation and Facile Intramolecular Aryl Transfer of Nickel–Aluminum Pincer-type Complexes

Abstract

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