Reaction between a carbazole-based mesoionic carbene ligand and manganese(II) iodide results in the formation of a rare air stable manganese(IV) complex after aerobic workup. Cyclic voltammetry reveals the complex to...
We report the synthesis of 17 molybdenum and tungsten
complexes
supported by the ubiquitous BDI ligand framework (BDI = β-diketiminate).
The focal entry point is the synthesis of four molybdenum and tungsten(V)
BDI complexes of the general formula [MO(BDIR)Cl2] [M = Mo, R = Dipp (1); M = W, R = Dipp (2); M = Mo, R = Mes (3); M = W, R = Mes (4)] synthesized by the reaction between MoOCl3(THF)2 or WOCl3(THF)2 and LiBDIR. Reactivity studies show that the BDIDipp complexes are
excellent precursors toward adduct formation, reacting smoothly with
dimethylaminopyridine (DMAP) and triethylphosphine oxide (OPEt3). No reaction with small phosphines has been observed, strongly
contrasting the chemistry of previously reported rhenium(V) complexes.
Additionally, the complexes 1 and 2 are
good precursors for salt metathesis reactions. While 1 can be chemically reduced to the first stable example of a Mo(IV)
BDI complex 15, reduction of 2 resulted
in degradation of the BDI ligand via a nitrene transfer reaction,
leading to MAD (4-((2,6-diisopropylphenyl)imino)pent-2-enide) supported
tungsten(V) and tungsten(VI) complexes 16 and 17. All reported complexes have been thoroughly studied by VT-NMR and
(heteronuclear) NMR spectroscopy, as well as UV–vis and EPR
spectroscopy, IR spectroscopy, and X-ray diffraction analysis.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.