Synthesis of molybdenum nitrido complexes for triple-bond metathesis of alkynes and nitriles

Complexes of the type N≡Mo(OR)(3) (R = tertiary alkyl, tertiary silyl, bulky aryl) have been synthesized in the search for molybdenum-based nitrile-alkyne cross-metathesis (NACM) catalysts. Protonolysis of known N≡Mo(NMe(2))(3) led to the formation of N≡Mo(O-2,6-(i)Pr(2)C(6)H(3))(3)(NHMe(2)) (12), N≡Mo(OSiPh(3))(3)(NHMe(2)) (5-NHMe(2)), and N≡Mo(OCPh(2)Me)(3)(NHMe(2)) (17-NHMe(2)). The X-ray structure of 12 revealed an NHMe(2) ligand bound cis to the nitrido ligand, while 5-NHMe(2) possessed an NHMe(2) bound trans to the nitride ligand. Consequently, 17-NHMe(2) readily lost its amine ligand to form N≡Mo(OCPh(2)Me)(3) (17), while 12 and 5-NHMe(2) retained their amine ligands in solution. Starting from bulkier tris-anilide complexes, N≡Mo(N[R]Ar)(3) (R = isopropyl, tert-butyl; Ar = 3,5-dimethylphenyl) allowed for the formation of base-free complexes N≡Mo(OSiPh(3))(3) (5) and N≡Mo(OSiPh(2)(t)Bu)(3) (16). Achievement of a NACM cycle requires the nitride complex to react with alkynes to form alkylidyne complexes; therefore the alkyne cross-metathesis (ACM) activity of the complexes was tested. Complex 5 was found to be an efficient catalyst for the ACM of 1-phenyl-1-butyne at room temperature. Complexes 12 and 5-NHMe(2) were also active for ACM at 75 °C, while 17-NHMe(2) and 16 did not show ACM activity. Only 5 proved to be active for the NACM of anisonitrile, which is a reactive substrate in NACM catalyzed by tungsten. NACM with 5 required a reaction temperature of 180 °C in order to initiate the requisite alkylidyne-to-nitride conversion, with slightly more than two turnovers achieved prior to catalyst deactivation. Known molybdenum nitrido complexes were screened for NACM activity under similar conditions, and only N≡Mo(OSiPh(3))(3)(py) (5-py) displayed any trace of NACM activity.