Thulium diiodide

It would be interesting to examine thulium diiodide in one-electron reduction reactions. On the basis of the work by Evans and Allen (2000), Tml2 has the potential to be an effective replacement for Sml2, when the latter is too weak as a reductant, when subambient reaction temperatures are desirable, etc. Perhaps, Tml2 activity in THF can be controlled by the addition of hexamethylphosphotri-amide in the same manner as it regulates power and reactivity of SmBr2 (Knettle and Flowers 2001). 

Treatment of thulium diiodide with substituted phospholide and arsolide salts afforded stable bis(phospholyl)- and bis(arsolyl)thulium(ll) complexes (Scheme 201) as green solids, that were characterized by multinuclear NMR and X-ray crystal structures. The latter clearly revealed the beneficial effects of the steric and electronic properties of crowded phospholyl and arsolyl ligands for the stabilization of divalent thulium.727 Several other homoleptic samarium(ll) and thulium(n) phospholyl sandwich complexes containing the 2,5-di-/-butyl-3,4-dimethylphospholide (=dtp) or 2,5-bis(trimethylsilyl)-3,4-dimethylphospholide (=dsp) ligand have been synthesized and structurally characterized. X-ray studies revealed that [Sm(dtp)2]2 and [Sm(dsp)2]2 are both dimeric in the solid state due to... 

Molecular chemistry of neodymium, dysprosium and thulium diiodides... 

The well-known Sm ry -arene complexes are generally prepared by the reaction of arenes with rare-earth trihalides in the presence of aluminium halides. This reaction was also effective with samarium diiodide and was extended to thulium diiodide however, an attempt to react Tml2 with naphthalene in toluene in the presence of aluminium trichloride was not successful but resulted in the isolation of an ry -toluene complex of Tm [77 -(CH3C6H5)Tm(AlCl4)3] (Figure 6) (Fagin et al., 2005). 

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