Isolation of an Elusive Phosphametallacyclobutadiene and Its Role in Reversible Carbon−Carbon Bond Cleavage

The reactivity of phosphaalkynes, the isolobal and isoelectronic congeners to alkynes, with metal alkylidyne complexes is explored in this work. Treating the tungsten alkylidyne [tBuOCO]W≡CtBu(THF)2 (1) with phosphaalkyne (10) results in the formation of [O2C(tBuC=)W{η2‐(P,C)−P≡C−Ad}(THF)] (13‐tBuTH...

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Veröffentlicht in:Angewandte Chemie International Edition 2022-07, Vol.61 (30), p.e202203073-n/a
Hauptverfasser: Jakhar, Vineet K., Esper, Alec M., Ghiviriga, Ion, Abboud, Khalil A., Ehm, Christian, Veige, Adam S.
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container_issue 30
container_start_page e202203073
container_title Angewandte Chemie International Edition
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creator Jakhar, Vineet K.
Esper, Alec M.
Ghiviriga, Ion
Abboud, Khalil A.
Ehm, Christian
Veige, Adam S.
description The reactivity of phosphaalkynes, the isolobal and isoelectronic congeners to alkynes, with metal alkylidyne complexes is explored in this work. Treating the tungsten alkylidyne [tBuOCO]W≡CtBu(THF)2 (1) with phosphaalkyne (10) results in the formation of [O2C(tBuC=)W{η2‐(P,C)−P≡C−Ad}(THF)] (13‐tBuTHF) and [O2C(AdC=)W{η2‐(P,C)−P≡C−tBu}(THF)] (13‐AdTHF); derived from the formal reductive migratory insertion of the alkylidyne moiety into a W−Carene bond. Analogous to alkyne metathesis, a stable phosphametallacyclobutadiene complex [tBuOCO]W[κ2‐C(tBu)PC(Ad)] (14) forms upon loss of THF from the coordination sphere of either 13‐tBuTHF or 13‐AdTHF. Remarkably, the C−C bonds reversibly form/cleave with the addition or removal of THF from the coordination sphere of the formal tungsten(VI) metal center, permitting unprecedented control over the transformation of a tetraanionic pincer to a trianionic pincer and back. Computational analysis offers thermodynamic and electronic reasoning for the reversible equilibrium between 13‐tBu/AdTHF and 14. The elusive phosphametallacyclobutadiene intermediate is isolated and characterized. This intermediate reveals insights into rapid and reversible C−C bond formation/cleavage, enabling the cycling between a trianionic pincer and a tetraanionic pincer ligand at will.
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Treating the tungsten alkylidyne [tBuOCO]W≡CtBu(THF)2 (1) with phosphaalkyne (10) results in the formation of [O2C(tBuC=)W{η2‐(P,C)−P≡C−Ad}(THF)] (13‐tBuTHF) and [O2C(AdC=)W{η2‐(P,C)−P≡C−tBu}(THF)] (13‐AdTHF); derived from the formal reductive migratory insertion of the alkylidyne moiety into a W−Carene bond. Analogous to alkyne metathesis, a stable phosphametallacyclobutadiene complex [tBuOCO]W[κ2‐C(tBu)PC(Ad)] (14) forms upon loss of THF from the coordination sphere of either 13‐tBuTHF or 13‐AdTHF. Remarkably, the C−C bonds reversibly form/cleave with the addition or removal of THF from the coordination sphere of the formal tungsten(VI) metal center, permitting unprecedented control over the transformation of a tetraanionic pincer to a trianionic pincer and back. Computational analysis offers thermodynamic and electronic reasoning for the reversible equilibrium between 13‐tBu/AdTHF and 14. The elusive phosphametallacyclobutadiene intermediate is isolated and characterized. 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subjects Alkylidynes
Alkynes
Carbon
Computer applications
Congeners
Coordination
Cycloaddition
C−C Activation
Metallacycles
Metathesis
Phosphaalkynes
Tungsten
title Isolation of an Elusive Phosphametallacyclobutadiene and Its Role in Reversible Carbon−Carbon Bond Cleavage
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