Cp* Noninnocence Leads to a Remarkably Weak C-H Bond via Metallocene Protonation

Journal of the American Chemical Society
Matthew J ChalkleyJonas C Peters

Abstract

Metallocenes, including their permethylated variants, are extremely important in organometallic chemistry. In particular, many are synthetically useful either as oxidants (e.g., Cp2Fe+) or as reductants (e.g., Cp2Co, Cp*2Co, and Cp*2Cr). The latter have proven to be useful reagents in the reductive protonation of small-molecule substrates, including N2. As such, understanding the behavior of these metallocenes in the presence of acids is paramount. In the present study, we undertake the rigorous characterization of the protonation products of Cp*2Co using pulse electron paramagnetic resonance (EPR) techniques at low temperature. We provide unequivocal evidence for the formation of the ring-protonated isomers Cp*( exo/ endo-η4-C5Me5H)Co+. Variable temperature Q-band (34 GHz) pulse EPR spectroscopy, in conjunction with density functional theory (DFT) predictions, are key to reliably assigning the Cp*( exo/ endo-η4-C5Me5H)Co+ species. We also demonstrate that exo-protonation selectivity can be favored by using a bulkier acid and suggest this species is thus likely a relevant intermediate during catalytic nitrogen fixation given the bulky anilinium acids employed. Of further interest, we provide physical data to experimentally asse...Continue Reading

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Citations

Mar 4, 2020·Chemical Communications : Chem Comm·Trevor D LohreyJohn Arnold
May 1, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Karthika J KadasseryDavid C Lacy
Jul 1, 2020·Nature Chemistry·Matthias ReinersMarc D Walter
Sep 25, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·C O Bartulovich, R A Flowers
Jan 16, 2021·Angewandte Chemie·Macarena G AlférezJesús Campos
Feb 24, 2021·Journal of the American Chemical Society·Daniel A KurtzJillian L Dempsey
Jul 9, 2021·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Niklas von Wolff, Marc Robert
Dec 11, 2020·Journal of the American Chemical Society·Jonathan L Kuo, Karen I Goldberg
Nov 22, 2019·Journal of the American Chemical Society·Quinton J BruchAlexander J M Miller
May 1, 2020·Chemical Reviews·Matthew J ChalkleyJonas C Peters
May 28, 2020·Chemical Reviews·Sangmin KimPaul J Chirik
Aug 14, 2019·Journal of the American Chemical Society·Amy L SpeelmanPatrick L Holland
Jun 11, 2019·Journal of the American Chemical Society·Ke-Yin YeSong Lin
Sep 22, 2021·Journal of the American Chemical Society·Evan J GardnerTimothy H Warren
Nov 5, 2021·Inorganic Chemistry·Práxedes SánchezDemyan E Prokopchuk
Dec 21, 2021·Chemical Reviews·Rishi G AgarwalJames M Mayer

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