An efficient method for the preparation of oxo molybdenum salalen complexes and their unusual use as hydrosilylation catalysts.
A number of molybdenum(VI) dioxo salalen complexes were prepared from the reaction of Mo(CO)(6) and salen ligands containing bulky substituents, providing a novel and facile entry to Mo-salalen compounds. Two of the complexes were characterized by single-crystal X-ray diffraction. Reduction with organic phosphines or silanes afforded the monooxo molybdenum(IV) complexes, along with dinuclear molybdenum(V) species featuring a bridged oxo ligand (mu-O). One of the dinuclear complexes as well as a molybdenum(VI) dioxo salan complex was characterized structurally. All of the molybdenum compounds except the monooxo molybdenum(IV) were fully characterized by NMR, mass spectrometry, and elemental analyses. Investigations of acetophenone and 4-Ph-2-butanone reduction with PhSiH(3) showed that all of these molybdenum oxo complexes could serve as catalysts at reasonably low loading (1 mol % Mo) and approximately 110 degrees C. The time profiles and efficacy of catalysis varied depending on the precursor form of the catalyst, Mo(VI)(O)(2) vs (O)Mo(V)-O-Mo(V)(O) vs Mo(IV)(O). Solvent effects, radical scavenger probes, and other mechanistic considerations reveal that the monooxo molybdenum(IV) is the most likely active form of the catalyst.
Ziegler
Jeanette E
JE
Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
Du
Guodong
G
Fanwick
Philip E
PE
Abu-Omar
Mahdi M
MM