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Cyclopentadienyl Complexes of Ir-III for Attempted C-D Bond Activation
Journal article   Open access   Peer reviewed

Cyclopentadienyl Complexes of Ir-III for Attempted C-D Bond Activation

Robert D. Robinson Jr, Werner Kaminsky and Jeremiah J. Scepaniak
European journal of inorganic chemistry
28 Jul 2023
url
https://doi.org/10.1002/ejic.202300369View
Published, Version of Record (VoR)Maybe Open Access (Publisher Bronze) Open

Abstract

Chemistry Chemistry, Inorganic & Nuclear Physical Sciences Science & Technology
The complexes Cp(MeIm)IrI2 and Cp-Me4(MeIm)IrCl2 have been prepared and subsequently methylated to form Cp(MeIm)IrMe2 and Cp-Me4(MeIm)IrMe2 (Cp=& eta;(5)-C5H5, Cp-Me4=& eta;(5)-C5HMe4, MeIm=1,3-dimethylimidazol-2-ylidene). We attempted unsuccessfully to use the dimethyl complexes to study C-D bond activation via methyl-group abstraction. Protonation with one equivalent of a weak acid, such as 2,6-dimethylpyridinium chloride, affords methane and Ir-III methyl chloride complexes. H-1-NMR experiments show addition of pyridinium [BArF20](-) (BArF20=[B(C6F5)(4)](-)) to the dimethyl species forms [Cp(MeIm)IrMe(py)](+)[BArF20](-) (py=pyridine) or [Cp-Me4(MeIm)IrMe(py)](+)[BArF20](-) respectively, alongside methane, while use of the [BArF20](-) salts of more bulky 2,6-dimethylpyridinium and 2,6-di-tert-butylpyridinium gave an intractable mixture. Likewise, the generation of 16 e(-) species [Cp-Me4(MeIm)IrMe](+)[BArF20](-) or [Cp(MeIm)IrMe](+)[BarF(20)](-) at low temperature using 2,6-dimethylpyridinium or 2,6-di-tert-butylpyridinium in thawing C6D6 or toluene-d(8) formed an intractable mixture and did not lead to C-D bond activation. X-ray structures of several Ir-III complexes show similar sterics as that found for the previously reported Cp* analogue.

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Collaboration types
Domestic collaboration
Web of Science research areas
Chemistry, Inorganic & Nuclear
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