C–C σ-Bond Oxidative Addition and Hydrofunctionalization by a Macrocycle-Supported Diiron Complex

• DOI: 10.1021/jacs.2c06266
• Publication Date: 2022-07-26T17:16:14Z
• Authors: Tianchang Liu; Ryan P. Murphy; Patrick J. Carroll; Michael R. Gau; Neil C. Tomson
• Keywords: Hydroboration; Stoichiometry; Oxidative addition; Surface Modification

This report describes the first examples of unassisted C(sp)–C(sp2) and C(sp)–C(sp3) bond oxidative addition reactions to give thermodynamically favorable products. Treatment a diiron complex supported by geometrically electronically flexible macrocyclic ligand, (3PDI2)Fe2(μ-N2)(PPh3)2 ([Fe2N2]0), with stoichiometric amounts various 4,4′-disubstituted diphenylacetylenes (ArX–C≡C–ArX; X = OMe, H, F, CF3) yielded When Ph–C≡C–R substrates were used as (R Me, Et, iPr, tBu), products either or activation obtained, less sterically encumbering alkynes exclusively undergoing activation. C–C species H2 HBpin was found form σ-bond hydrofunctionalization. In both hydrogenation hydroboration schemes, observed return [Fe2N2]0, thereby completing synthetic cycles for functionalization.