Ring-opening of a thorium cyclopropenyl complex generates a transient thorium-bound carbene

Kent, Greggory T.; Yu, Xiaojuan; Wu, Guang; Autschbach, Jochen; Hayton, Trevor W.

doi:10.1039/d2cc01780f

Title: Ring-opening of a thorium cyclopropenyl complex generates a transient thorium-bound carbene

Journal Article · 18 May 2022 · ChemComm

DOI: https://doi.org/10.1039/d2cc01780f · OSTI ID:1978854

Kent, Greggory T. ^[1];

^[2]; Wu, Guang ^[3];

^[2];

^[3]

University of California, Santa Barbara, CA (United States); OSTI
University at Buffalo, State University of New York, NY (United States)
University of California, Santa Barbara, CA (United States)

The reaction of [Cp₃ThCl] with in situ generated 1-lithium-3,3-diphenylcyclopropene results in the formation of [Cp₃Th(3,3-diphenylcyclopropenyl)] (1), in good yields. Thermolysis of 1 results in isomerization to the ring-opened product, [Cp₃Th(3-phenyl-1H-inden-1-yl)] (3) via a hypothesized carbene intermediate. This transformation represents a new mode of reactivity of 3,3-diphenylcyclopropene with the actinides, improving our ability to use this reagent as a carbene source. Here, a combined DFT and ¹³C{¹H} NMR analysis of 1 shows a spin–orbit induced downfield shift at C_α due to participation of the 5f orbitals in the Th–C bond.

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Research Organization:: State University of New York (SUNY), Albany, NY (United States); University of California, Santa Barbara, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0001136; SC0001861

OSTI ID:: 1978854

Journal Information:: ChemComm, Journal Name: ChemComm Journal Issue: 48 Vol. 58; ISSN 1359-7345

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Ring-opening of a thorium cyclopropenyl complex generates a transient thorium-bound carbene

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