New Phosphoranylideneketenes and Phosphoranylidenethioketenes‐Synthesis, Structure, Spectroscopy, and Lewis Base Properties

Brar, Amandeep; Nadella, Kiran; Unruh, Daniel K.; Bouley, Bailey; Krempner, Clemens

doi:10.1002/chem.202502777

New Phosphoranylideneketenes and Phosphoranylidenethioketenes‐Synthesis, Structure, Spectroscopy, and Lewis Base Properties

Journal Article · Wed Nov 19 19:00:00 EST 2025 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.202502777· OSTI ID:3010286

Brar, Amandeep ^[1]; Nadella, Kiran ^[1]; Unruh, Daniel K. ^[1]; Bouley, Bailey ^[1]; ^[1]

Texas Tech University, Lubbock, TX (United States)

Posphoranylideneketene Ph₃PCCO and its sulfur analogue, Ph₃PCCS, are cumulated ylides that exhibit diverse reactivity and distinct structural features. Herein, we present the first systematic study of substituent effects on the structures and bonding of a series of aryl- and alkyl-substituted phosphoranylideneketenes, R₃PCCO [R = Et, cyclohexyl, NMe₂, 4-Me₂N-C₆H₄, 4-MeO-C₆H₄, 4-CF₃-C₆H₄, 3,5-(CF₃)₂-C₆H₃], prepared from the corresponding phosphonium salts, [R₃PCH₂COOEt]X (X = Br, I) and two equivalents of Na[N(SiMe₃)₂]. Multinuclear NMR and IR spectroscopy, supported by single-crystal X-ray diffraction, revealed that the bond strength within the central P═C═C═O fragment increases with the electron-deficiency of the aryl substituents at phosphorus. The corresponding phosphoranylidenethioketenes, R₃PCCS (R = Et, cyclohexyl, NMe₂, 4-Me₂N-C₆H₄, 4-MeO-C₆H₄, 4-CF₃-C₆H₄), were obtained by reactions of R₃PCCO with CS₂. Here, the rate of conversion of R₃PCCO into R₃PCCS decreases with increasing electron deficiency at phosphorus. Both R₃PCCO and R₃PCCS act as relatively weak ambidentate Lewis donors, yet they form stable acid-base adducts with strong Lewis acids such as B(C₆F₅)₃ and Al(C₆F₅)₃.

View Accepted Manuscript (DOE)

Research Organization:: Texas Tech University, Lubbock, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019094

OSTI ID:: 3010286

Alternate ID(s):: OSTI ID: 3005732

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 71 Vol. 31; ISSN 0947-6539; ISSN 1521-3765

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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