The Synthesis and Catalytic Activity of New Mixed NHC-Phosphite Nickel(0) Complexes

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Abstract

Herein we describe the synthesis and isolation of the first low-valent NHC-phosphite nickel complexes of general formula Ni(NHC)[P(OAr)3]2. These three-coordinate Ni(0) compounds were fully characterized, including by X-ray crystallography that highlighted their trigonal planar geometry. The representative complex Ni(IMes)[P(OPh)3]2 was used to show that a phosphite ligand is readily substituted in the presence of an aldehyde or nitrile. These stoichiometric studies then led to an investigation of their catalytic properties in the Suzuki-Miyaura cross-coupling reactions between aryl tosylates and aryl boronic acids, a first for such a NHC-Ni catalyst. Finally, mechanistic investigations led to the isolation of a well-defined oxidative addition product.

Original languageEnglish
Pages (from-to)105-115
JournalOrganometallics
Volume39
DOIs
Publication statusPublished - 13 Jan 2020

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Phosphites
Nickel
catalytic activity
Catalyst activity
isolation
nickel
Boronic Acids
Nitriles
X ray crystallography
cross coupling
nitriles
synthesis
aldehydes
Aldehydes
crystallography
Ligands
catalysts
ligands
acids
Catalysts

Cite this

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title = "The Synthesis and Catalytic Activity of New Mixed NHC-Phosphite Nickel(0) Complexes",
abstract = "Herein we describe the synthesis and isolation of the first low-valent NHC-phosphite nickel complexes of general formula Ni(NHC)[P(OAr)3]2. These three-coordinate Ni(0) compounds were fully characterized, including by X-ray crystallography that highlighted their trigonal planar geometry. The representative complex Ni(IMes)[P(OPh)3]2 was used to show that a phosphite ligand is readily substituted in the presence of an aldehyde or nitrile. These stoichiometric studies then led to an investigation of their catalytic properties in the Suzuki-Miyaura cross-coupling reactions between aryl tosylates and aryl boronic acids, a first for such a NHC-Ni catalyst. Finally, mechanistic investigations led to the isolation of a well-defined oxidative addition product.",
author = "Jeremy Duczynski and Sobolev, {Alexandre N.} and Moggach, {Stephen A.} and Reto Dorta and Stewart, {Scott G.}",
year = "2020",
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doi = "10.1021/acs.organomet.9b00672",
language = "English",
volume = "39",
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journal = "Organometallics",
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publisher = "American Chemical Society",

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TY - JOUR

T1 - The Synthesis and Catalytic Activity of New Mixed NHC-Phosphite Nickel(0) Complexes

AU - Duczynski, Jeremy

AU - Sobolev, Alexandre N.

AU - Moggach, Stephen A.

AU - Dorta, Reto

AU - Stewart, Scott G.

PY - 2020/1/13

Y1 - 2020/1/13

N2 - Herein we describe the synthesis and isolation of the first low-valent NHC-phosphite nickel complexes of general formula Ni(NHC)[P(OAr)3]2. These three-coordinate Ni(0) compounds were fully characterized, including by X-ray crystallography that highlighted their trigonal planar geometry. The representative complex Ni(IMes)[P(OPh)3]2 was used to show that a phosphite ligand is readily substituted in the presence of an aldehyde or nitrile. These stoichiometric studies then led to an investigation of their catalytic properties in the Suzuki-Miyaura cross-coupling reactions between aryl tosylates and aryl boronic acids, a first for such a NHC-Ni catalyst. Finally, mechanistic investigations led to the isolation of a well-defined oxidative addition product.

AB - Herein we describe the synthesis and isolation of the first low-valent NHC-phosphite nickel complexes of general formula Ni(NHC)[P(OAr)3]2. These three-coordinate Ni(0) compounds were fully characterized, including by X-ray crystallography that highlighted their trigonal planar geometry. The representative complex Ni(IMes)[P(OPh)3]2 was used to show that a phosphite ligand is readily substituted in the presence of an aldehyde or nitrile. These stoichiometric studies then led to an investigation of their catalytic properties in the Suzuki-Miyaura cross-coupling reactions between aryl tosylates and aryl boronic acids, a first for such a NHC-Ni catalyst. Finally, mechanistic investigations led to the isolation of a well-defined oxidative addition product.

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U2 - 10.1021/acs.organomet.9b00672

DO - 10.1021/acs.organomet.9b00672

M3 - Article

VL - 39

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JO - Organometallics

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