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The Varied Frustrated Lewis Pair Reactivity of the Germylene Phosphaketene (CH{(CMe)(2,6-ⁱ Pr₂ C₆ H₃ N)}₂ )GePCO.

ABSTRACT: The germylene species (CH{(CMe)(2,6-iPr₂ C₆ H₃ N)}₂ )GePCO 1 is shown to react with the Lewis acids (E(C₆ F₅ )₃ E=B, Al). Nonetheless, 1 participates in FLP chemistry with electron deficient alkynes or olefins, acting as an intramolecular FLP. In contrast, in the presence of B(C₆ F₅ )₃ and an electron rich alkyne, 1 behaves as Ge-based nucleophile to effect intermolecular FLP addition to the alkyne. This reactivity demonstrates that the reaction pathway is controlled by the nature of the electrophile and nucleophile generated in solution, as revealed by extensive DFT calculations.

SUBMITTER: Wu Y

PROVIDER: S-EPMC9314608 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Alkyl-B(C6F5)2 boranes are markedly ?-CH-acidic. Using DFT we have calculated the pKa-values of a series of examples. Typically, (C6F5)2B-CH3 [pKa (calcd) = 18.3 in DMSO, 16.2 in dichloromethane] is almost as CH-acidic as cyclopentadiene. However, this ?-CH-B(C6F5)2 acidity is in most cases not sufficient to allow for internal proton transfer in vicinal phosphane/borane frustrated Lewis pairs (FLPs). An exception is the slightly endergonic (+0.3 kcal mol-1) tautomerization of the in situ generated indane derived 1,3-P/B FLP 6 to its zwitterionic borata-alkene/phosphonium isomer 7, which was successfully trapped by Piers' borane [HB(C6F5)2] to yield the stable product 8. The pronounced ?-CH[B] carbanion stabilization can be used synthetically. We have found that the dienyl borane E-H2C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C(Me)CHCHB(C6F5)2 undergoes clean, thermally induced 1,4-hydrophosphination reactions with HPR2 (R: phenyl, mesityl, or t-butyl) reagents. ?-CHB(C6F5)2 carbanion (i.e. borata-alkene) stabilization in the respective intermediates probably plays a decisive role in these reactions.

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The Varied Frustrated Lewis Pair Reactivity of the Germylene Phosphaketene (CH{(CMe)(2,6-ⁱ Pr₂ C₆ H₃ N)}₂ )GePCO.

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The Varied Frustrated Lewis Pair Reactivity of the Germylene Phosphaketene (CH{(CMe)(2,6-i Pr2 C6 H3 N)}2 )GePCO.

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OmicsDI is part of the ELIXIR infrastructure

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The Varied Frustrated Lewis Pair Reactivity of the Germylene Phosphaketene (CH{(CMe)(2,6-ⁱ Pr₂ C₆ H₃ N)}₂ )GePCO.