478158-40-6Relevant articles and documents
The effect of substituents on the phenyl portion of the imido ligand on the structure and properties of molybdenum(VI) imido complexes
Minelli, Martin,Hoang, My Le,Kraus, Michael,Kucera, Gena,Loertscher, Jennifer,Reynolds, Mark,Timm, Nathan,Chiang, Michael Y.,Powell, Douglas
, p. 5954 - 5960 (2008/10/08)
Anilines with alkyl substituents on the phenyl ring (ArNH2 = 2,4,6-trimethylaniline; 2,3-, 2,4-, 2,6-, and 3,4-dimethylaniline; and 2,6-diisopropylaniline) react with MoO(X)2(dtc)2 (X = Cl or Br; dtc = diethyldithiocarbamate) in methanol in the presence of 2 equiv of triethylamine to form ionic imido complexes of the type [MoNAr(dtc)3]2- [Mo6O19] or MoNAr(dtc)3]4[Mo8O26]. The same reaction in THF with butyllithium as base yields imido complexes of the type MoNAr(X)2(dtc)2. The structures of three ionic, five chloro, and two bromo complexes have been determined by X-ray crystallography. In all complexes, the molybenum center is a distorted pentagonal bipyramid. While the structures are similar, the angles of the imido linkages differ. The effect of the substituents on the phenyl ring of the imido ligand on the 95Mo NMR chemical shifts was determined. The Mo nucleus becomes more deshielded with the substituents in the following order: 3,4-Me2 2 2 2 3 95Mo centers tend to have angles of the imido linkage that are closer to 180°.
