Addition of N-H bonds to iridium: Synthesis and characterization of N-Ir-H complexes and the observation that an iridium N-bonded indole ring becomes activated for Michael addition to alkynes

Folami T. Ladipo; Joseph S. Merola

doi:10.1016/j.poly.2015.02.002

Addition of N-H bonds to iridium: Synthesis and characterization of N-Ir-H complexes and the observation that an iridium N-bonded indole ring becomes activated for Michael addition to alkynes

Folami T. Ladipo, Joseph S. Merola

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

1 Scopus citations

Abstract

The thermal reaction between the electron-rich iridium complex, [IrCOD(PMe₃)₃]Cl, 1a, and pyrrolic or anilinic N-H bonds results in the oxidative addition of the N-H bond and the formation of an amido iridium hydride complex, HIr(amido)(Cl)(PMe₃)₃ with loss of COD. The only isomer formed in this reaction has a meridional arrangement of PMe₃ ligands, with H trans to Cl and the amido group trans to PMe₃. The reaction products of 1a with pyrrole, indole and 3-methyl indole were fully characterized included by single crystal X-ray diffraction. Attachment of the pyrrolic ring nitrogen to the iridium results in an electron rich ring system that is activated and adds to alkynes in a Michael addition reaction under mild conditions without a catalyst.

Original language	English
Pages (from-to)	131-138
Number of pages	8
Journal	Polyhedron
Volume	90
DOIs	https://doi.org/10.1016/j.poly.2015.02.002
State	Published - Apr 18 2015

Bibliographical note

Funding Information:
Financial support for this work was provided by ACS, PRF (Grant # 23961-C1 ) and by the National Science Foundation ( CHE-902244 ). Support for the server upon which Gaussian is run came from NSF Grant No. CHE-0741927 . Dr. Carla Slebodnick provided excellent advice on the use of RIGU to help model the disorder found in complex 4a .

Publisher Copyright:
© 2015 Elsevier Ltd. All rights reserved.

Keywords

Indole
Iridium
Michael addition
NH activation
Oxidative addition

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.poly.2015.02.002

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title = "Addition of N-H bonds to iridium: Synthesis and characterization of N-Ir-H complexes and the observation that an iridium N-bonded indole ring becomes activated for Michael addition to alkynes",

abstract = "The thermal reaction between the electron-rich iridium complex, [IrCOD(PMe3)3]Cl, 1a, and pyrrolic or anilinic N-H bonds results in the oxidative addition of the N-H bond and the formation of an amido iridium hydride complex, HIr(amido)(Cl)(PMe3)3 with loss of COD. The only isomer formed in this reaction has a meridional arrangement of PMe3 ligands, with H trans to Cl and the amido group trans to PMe3. The reaction products of 1a with pyrrole, indole and 3-methyl indole were fully characterized included by single crystal X-ray diffraction. Attachment of the pyrrolic ring nitrogen to the iridium results in an electron rich ring system that is activated and adds to alkynes in a Michael addition reaction under mild conditions without a catalyst.",

keywords = "Indole, Iridium, Michael addition, NH activation, Oxidative addition",

author = "Ladipo, {Folami T.} and Merola, {Joseph S.}",

note = "Funding Information: Financial support for this work was provided by ACS, PRF (Grant # 23961-C1 ) and by the National Science Foundation ( CHE-902244 ). Support for the server upon which Gaussian is run came from NSF Grant No. CHE-0741927 . Dr. Carla Slebodnick provided excellent advice on the use of RIGU to help model the disorder found in complex 4a . Publisher Copyright: {\textcopyright} 2015 Elsevier Ltd. All rights reserved.",

year = "2015",

month = apr,

day = "18",

doi = "10.1016/j.poly.2015.02.002",

language = "English",

volume = "90",

pages = "131--138",

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T2 - Synthesis and characterization of N-Ir-H complexes and the observation that an iridium N-bonded indole ring becomes activated for Michael addition to alkynes

AU - Ladipo, Folami T.

AU - Merola, Joseph S.

N1 - Funding Information: Financial support for this work was provided by ACS, PRF (Grant # 23961-C1 ) and by the National Science Foundation ( CHE-902244 ). Support for the server upon which Gaussian is run came from NSF Grant No. CHE-0741927 . Dr. Carla Slebodnick provided excellent advice on the use of RIGU to help model the disorder found in complex 4a . Publisher Copyright: © 2015 Elsevier Ltd. All rights reserved.

PY - 2015/4/18

Y1 - 2015/4/18

N2 - The thermal reaction between the electron-rich iridium complex, [IrCOD(PMe3)3]Cl, 1a, and pyrrolic or anilinic N-H bonds results in the oxidative addition of the N-H bond and the formation of an amido iridium hydride complex, HIr(amido)(Cl)(PMe3)3 with loss of COD. The only isomer formed in this reaction has a meridional arrangement of PMe3 ligands, with H trans to Cl and the amido group trans to PMe3. The reaction products of 1a with pyrrole, indole and 3-methyl indole were fully characterized included by single crystal X-ray diffraction. Attachment of the pyrrolic ring nitrogen to the iridium results in an electron rich ring system that is activated and adds to alkynes in a Michael addition reaction under mild conditions without a catalyst.

AB - The thermal reaction between the electron-rich iridium complex, [IrCOD(PMe3)3]Cl, 1a, and pyrrolic or anilinic N-H bonds results in the oxidative addition of the N-H bond and the formation of an amido iridium hydride complex, HIr(amido)(Cl)(PMe3)3 with loss of COD. The only isomer formed in this reaction has a meridional arrangement of PMe3 ligands, with H trans to Cl and the amido group trans to PMe3. The reaction products of 1a with pyrrole, indole and 3-methyl indole were fully characterized included by single crystal X-ray diffraction. Attachment of the pyrrolic ring nitrogen to the iridium results in an electron rich ring system that is activated and adds to alkynes in a Michael addition reaction under mild conditions without a catalyst.

KW - Indole

KW - Iridium

KW - Michael addition

KW - NH activation

KW - Oxidative addition

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DO - 10.1016/j.poly.2015.02.002

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SN - 0277-5387

VL - 90

SP - 131

EP - 138

JO - Polyhedron

JF - Polyhedron

ER -

Addition of N-H bonds to iridium: Synthesis and characterization of N-Ir-H complexes and the observation that an iridium N-bonded indole ring becomes activated for Michael addition to alkynes

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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