Bis[hydrazido(2-)] and related complexes of molybdenum(VI): towards alkene-metathesis catalysts based on hydrazido(2-) ligation

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Jonathan R. Dilworth, Vernon C. Gibson, Canzhong Lu, John R. Miller, Carl Redshaw and Yifan Zheng


Abstract

The complex [Mo(NBut)2Cl2(dme)] (dme = 1,2-dimethoxyethane) underwent an imide-ligand exchange reaction with an excess of 1,1-diphenylhydrazine hydrochloride in refluxing dme to give the bis[hydrazido(2-)] complex [MoCl2(NNPh2)2(dme)] 1. Reaction of 1 with an excess of PMe3 in CH2Cl2 gave [MoCl2(NNPh2)2(PMe3)2 ] 2. Treatment of Na2[MoO4] with 2 molar equivalents of Ph2NNH2·HCl in the presence of NEt3 and SiMe3Cl in refluxing dme afforded the salt [NHEt3][MoCl4(NNPh2)(NHNPh2)] 3. The crystal structures of 1–3 have been determined; all possess octahedral geometries with unidentate hydrazido groups. The hydrazido(2-) Mo–N bond distances vary from 1.749(2) and 1.771(2) Å in 1, to 1.793(3) in 2 and 1.748(2) Å in 3, with no simple correlation with the Mo–Nα–Nβ angle. The anionic component of 3 contains a bent hydrazide(1-) ligand (Mo–N–N 136.0°) and a linear hydrazido(2-) group (Mo–N–N 174.4°).


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