Thulium halides

Holmium is obtained from monazite, bastnasite and other rare-earth minerals as a by-product during recovery of dysprosium, thulium and other rare-earth metals. The recovery steps in production of all lanthanide elements are very similar. These involve breaking up ores by treatment with hot concentrated sulfuric acid or by caustic fusion separation of rare-earths by ion-exchange processes conversion to halide salts and reduction of the hahde(s) to metal (See Dysprosium, Gadolinium and Erbium). 

Compounds of divalent samarium, europium, and ytterbium are well-known. In recent years, lower halides of other lanthanides, such as neodymium 48), praseodymium 45, 49, 90), and thulium 4) have been obtained by reducing the trihalide with the metal. The corresponding reaction of thorium tetraiodide with thorium metal has led to the identification of two crystalline forms of Thl2 41, 91) it is unlikely that the Th ", or even Th ", ion is present in Thl2, but like Prl2, which is formulated as Pr " (r)2( ) (2), the compound is probably of the type Th " (r)2(2 ) 41). Certainly one crystal form is diamagnetic 41), suggesting the latter formulation. 

Since no accurate vapor pressure data are available for the erbium and thulium hahdes, the molar absorptivities were determined directly from a weighed amount of the respective rare-earth halides. Good results could be obtained from this method if the respective halogen, bromine, or iodine were added to the cell such that its pressure at 1000°C. was 1 atm. This procedure greatly reduced the reaction of the rare-earth... 

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). 

The MCI2 (M = Ca, Sr, and Ba) crystals are ideal candidates for studies of the spectroscopic properties of Tm " ions. First, no charge-compensation defects are required after thulium ions are introduced into these hosts. Second, there is reliable experimental information about the absorption/emission spectra of these materials [2-8]. Moreover, the earth-alkaline halides are also important from an application point of view because the laser action has been achieved in CaF2 Tm [9]. The spectra of Tm " were modeled in our earlier publication [10]. 

Halides of the lanthanides in the oxidation state -1-2 have been known since the early decades of the twentieth century. EuCl2, SmCl2, and YbCb were the first to be reported. For these 3 elements, ah 12 possible halides are known. This is not the case for the elements thulium, dysprosium, and neodymium for which only the halides of the fiiad chlorine, bromine, and iodine have been synthesized and crystallographically characterized. They structmaUy bear close resemblance to the respective alkahne-earth metal halides. The electronic configmations of the M + ions of these six elements are 6s 5d 4f with n = 4 (Nd), 6 (Sm), 7 (Eu), 10 (Dy), 13 (Tm), and 14 (Yb). 

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