skip to main content

Search for: All records

Award ID contains: 1856674

Note: When clicking on a Digital Object Identifier (DOI) number, you will be taken to an external site maintained by the publisher. Some full text articles may not yet be available without a charge during the embargo (administrative interval).
What is a DOI Number?

Some links on this page may take you to non-federal websites. Their policies may differ from this site.

  1. Abstract

    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−Carenebond. 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 either13‐tBuTHFor13‐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 between13‐tBu/AdTHFand14.

    more » « less
  2. null (Ed.)
  3. null (Ed.)