Redox Non-Innocent Behavior of a Terminal Iridium Hydrazido(2−) Triple Bond

Adam J. Pearce; Alyssa A. Cassabaum; Grace E. Gast; Renee R. Frontiera; Ian A. Tonks

doi:10.1002/anie.201607648

Redox Non-Innocent Behavior of a Terminal Iridium Hydrazido(2−) Triple Bond

Adam J. Pearce, Alyssa A. Cassabaum, Grace E. Gast, Renee R. Frontiera, Ian A. Tonks

Chemistry (Twin Cities)

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

2 Scopus citations

Abstract

The synthesis of the first terminal Group 9 hydrazido(2-) complex, Cp*IrN(TMP) (6) (TMP=2,2,6,6-tetramethylpiperidine) is reported. Electronic structure and X-ray diffraction analysis indicate that this complex contains an Ir−N triple bond, similar to Bergman's seminal Cp*Ir(N^tBu) imido complex. However, in sharp contrast to Bergman's imido, 6 displays remarkable redox non-innocent reactivity owing to the presence of the N_βlone pair. Treatment of 6 with MeI results in electron transfer from N_βto Ir prior to oxidative addition of MeI to the iridium center. This behavior opens the possibility of carrying out facile oxidative reactions at a formally Ir^IIImetal center through a hydrazido(2−)/isodiazene valence tautomerization.

Original language	English (US)
Pages (from-to)	13169-13173
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	42
DOIs	https://doi.org/10.1002/anie.201607648
State	Published - Oct 10 2016

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Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

hydrazide ligands
iridium complexes
organometallic chemistry
redox non-innocence
triple bonds

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http://europepmc.org/articles/pmc5392362

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title = "Redox Non-Innocent Behavior of a Terminal Iridium Hydrazido(2−) Triple Bond",

abstract = "The synthesis of the first terminal Group 9 hydrazido(2-) complex, Cp*IrN(TMP) (6) (TMP=2,2,6,6-tetramethylpiperidine) is reported. Electronic structure and X-ray diffraction analysis indicate that this complex contains an Ir−N triple bond, similar to Bergman's seminal Cp*Ir(NtBu) imido complex. However, in sharp contrast to Bergman's imido, 6 displays remarkable redox non-innocent reactivity owing to the presence of the Nβlone pair. Treatment of 6 with MeI results in electron transfer from Nβto Ir prior to oxidative addition of MeI to the iridium center. This behavior opens the possibility of carrying out facile oxidative reactions at a formally IrIIImetal center through a hydrazido(2−)/isodiazene valence tautomerization.",

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T1 - Redox Non-Innocent Behavior of a Terminal Iridium Hydrazido(2−) Triple Bond

AU - Pearce, Adam J.

AU - Cassabaum, Alyssa A.

AU - Gast, Grace E.

AU - Frontiera, Renee R.

AU - Tonks, Ian A.

PY - 2016/10/10

Y1 - 2016/10/10

N2 - The synthesis of the first terminal Group 9 hydrazido(2-) complex, Cp*IrN(TMP) (6) (TMP=2,2,6,6-tetramethylpiperidine) is reported. Electronic structure and X-ray diffraction analysis indicate that this complex contains an Ir−N triple bond, similar to Bergman's seminal Cp*Ir(NtBu) imido complex. However, in sharp contrast to Bergman's imido, 6 displays remarkable redox non-innocent reactivity owing to the presence of the Nβlone pair. Treatment of 6 with MeI results in electron transfer from Nβto Ir prior to oxidative addition of MeI to the iridium center. This behavior opens the possibility of carrying out facile oxidative reactions at a formally IrIIImetal center through a hydrazido(2−)/isodiazene valence tautomerization.

AB - The synthesis of the first terminal Group 9 hydrazido(2-) complex, Cp*IrN(TMP) (6) (TMP=2,2,6,6-tetramethylpiperidine) is reported. Electronic structure and X-ray diffraction analysis indicate that this complex contains an Ir−N triple bond, similar to Bergman's seminal Cp*Ir(NtBu) imido complex. However, in sharp contrast to Bergman's imido, 6 displays remarkable redox non-innocent reactivity owing to the presence of the Nβlone pair. Treatment of 6 with MeI results in electron transfer from Nβto Ir prior to oxidative addition of MeI to the iridium center. This behavior opens the possibility of carrying out facile oxidative reactions at a formally IrIIImetal center through a hydrazido(2−)/isodiazene valence tautomerization.

KW - hydrazide ligands

KW - iridium complexes

KW - organometallic chemistry

KW - redox non-innocence

KW - triple bonds

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Redox Non-Innocent Behavior of a Terminal Iridium Hydrazido(2−) Triple Bond

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