Probing borafluorene B-C bond insertion with gold acetylide and azide.

The reaction of PhPAuN with 9-Ph-9-borafluorene resulted in complexation of the azide to boron while a gold acetylide reacted with 9-Ph-9-borafluorene to insert the acetylide carbon to access a six-membered boracycle with an exocyclic double bond.

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 [ BuOCO]W≡C Bu(THF) (1) with phosphaalkyne (10) results in the formation of [O C( BuC=)W{η -(P,C)-P≡C-Ad}(THF)] (13- Bu ) and [O C(AdC=)W{η -(P,C)-P≡C- Bu}(THF)] (13-Ad ); derived from the formal reductive migratory insertion of the alkylidyne moiety into a W-C bond. Analogous to alkyne metathesis, a stable phosphametallacyclobutadiene complex [ BuOCO]W[κ -C( Bu)PC(Ad)] (14) forms upon loss of THF from the coordination sphere of either 13- Bu or 13-Ad .

A High-Throughput Approach to Repurposing Olefin Polymerization Catalysts for Polymer Upcycling.

Efficient and economical plastic waste upcycling relies on the development of catalysts capable of polymer degradation. A systematic high-throughput screening of twenty-eight polymerization catalyst precursors, belonging to the catalyst families of metallocenes, ansa-metallocenes, and hemi- and post-metallocenes, in cis-1,4-polybutadiene (PB) degradation reveals, for the first time, important structure-activity correlations. The upcycling conditions involve activation of the catalysts (at 0.

SPAAC iClick: progress towards a bioorthogonal reaction in-corporating metal ions.

Combining strain-promoted azide-alkyne cycloaddition (SPAAC) and inorganic click (iClick) reactivity provides access to metal 1,2,3-triazolates. Experimental and computational insights demonstrate that iClick reactivity of the tested metal azides (LM-N, M = Au, W, Re, Ru and Pt) depends on the accessibility of the azide functionality rather than electronic effects imparted by the metal. SPAAC iClick reactivity with cyclooctyne is observed when the azide functionality is sterically unencumbered, [Au(N)(PPh)] (Au-N3), [W(η-allyl)(N)(bpy)(CO)] (W-N3), and [Re(N)(bpy)(CO)] [bpy = 2,2'-bipyridine] (Re-N3).