Diphenylamido Precursors to Bisalkoxide Molybdenum Olefin Metathesis Catalysts

We have found that Mo(NAr)(CHR')(NPh(2))(2) (R' = t-Bu or CMe(2)Ph) and Mo(NAr')(CHCMe(2)Ph)(NPh(2))(2) (Ar = 2,6-i-Pr(2)C(6)H(3); Ar' = 2,6-Me(2)C(6)H(3)) can be prepared through addition of two equivalents of LiNPh(2) to Mo(NR″)(CHR')(OTf)(2)(dme) species (R″ = Ar or Ar' dme = 1,2-dimethoxyethane), although yields are low. A high yield route consists of addition of LiNPh(2) to bishexafluro-t-butoxide species. An X-ray structure of Mo(NAr)(CHCMe(2)Ph)(NPh(2))(2) reveals that the two diphenylamido groups are oriented in a manner that allows an 18 electron count to be achieved. The diphenylamido complexes react readily with t-BuOH and (CF(3))(2)MeCOH, but not readily with the sterically demanding biphenol H(2)[Biphen] (Biphen(2-) = 3,3'-Di-t-butyl-5,5',6,6'-tetramethyl-1,1'-Biphenyl-2,2'-diolate). The diphenylamido complexes do react with various 3,3'-disubstituted binaphthols to yield binaphtholate catalysts that can be prepared in situ and employed for a simple asymmetric ring-closing metathesis reaction. In several cases conversions and enantioselectivities were comparable to reactions in which isolated catalysts were employed.