N-Heterocyclic Carbene, High Oxidation State Molybdenum Alkylidene Complexes: Functional-Group-Tolerant Cationic Metathesis Catalysts

摘要

We synthesized the first N-heterocyclic carbene (NHC) complexes of Schrock's molybdenum imido alkylidene his(triflate) complexes. Unlike existing bis(triflate) complexes, the novel 16-electron complexes represent metathesis active, functional-group-tolerant catalysts. Single-crystal X-ray structures of two representatives of this novel class of Schrock catalysts are presented and reactivity is discussed in view of their structural peculiarities. In the presence of monomer Isubstrate), these catalysts form cationic species and can be employed in ring-closing metathesis (RCM), ring-opening metathesis polymerization (ROMP), as well as in the cyclo-nolvmerization of α,ω-diynes. Monomers containing functional groups, which are not tolerated by the existing variations of Schrock's catalyst, e.g., sec-amine, hydroxy, and carboxylic acid moieties, can be used. These catalysts therefore hold great nromise in both organic and polymer chemistry, where they allow for the use of protic monomers.