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Reactions between Mo(N- t -Bu) 2 (CH 2 - t -Bu) 2 or Mo(NAdamantyl) 2 (CH 2 CMe 2 Ph) 2 and 3 equiv of HCl in the presence of 1 equiv of PPh 2 Me yield Mo(NR)(CHR')(PPh 2 Me)Cl 2 complexes, from which Mo(NR)(CHR')(PPh 2 Me)(OAr)Cl complexes (OAr = a 2,6-terphenoxide) can be prepared. The Mo(NR)(CHR')(PPh 2 Me)(OAr)Cl complexes were evaluated as cross-metathesis catalysts between cyclooctene and Z -1,2-dichloroethylene. The efficiencies of the test reaction for complexes in which OAr = OTPP, OHMT, OHIPT, or OHTBT (where OTPP is 2,3,5,6-tetraphenylphenoxide, OHMT is hexamethylterphenoxide, OHIPT is hexaisopropylterphenoxide, and OHTBT is hexa- t- butylterphenoxide) maximize when OAr is OHMT or OHIPT. Mo(N- t -Bu)(CH- t -Bu)(PPh 2 Me)Cl 2 is essentially inactive for the reaction between cyclooctene and Z -1,2-dichloroethylene. X-ray structural studies were carried out on Mo(NAd)(CHCMe 2 Ph)(PPh 2 Me)Cl 2 , Mo(N- t -Bu)(CH- t -Bu)(PPh 2 Me)(OHMT)Cl, Mo(NAd)(CHCMe 2 Ph)(Cl)(OHTBT)(PMe 3 ), and [Mo(NAd)(CHCMe 2 Ph)(PMe 3 )(Cl)] 2 ( μ -O), the product of the reaction between Mo(NAd)(CHCMe 2 Ph)(Cl)(OHTBT)(PMe 3 ) and 0.5 equiv of water.

Syntheses of Molybdenum Adamantylimido and t-Butylimido Alkylidene Chloride Complexes Using HCl and Diphenylmethylphosphine