Neodymium trichloride

In 1906, Matignon reported an enthalpy of solution of -21.54 kcal mol-1 (-90 kj mol ) for neodymium trichloride in ethanol (178). His ethanol may have been less than perfectly anhydrous, and the value for pure ethanol somewhat less negative than this, perhaps —80 or — 70 kJ mol 1. Certainly a value in this region is considerably less negative than his value for the enthalpy of solution of neodymium trichloride in water, —148 kj mol-1. The difference may reasonably be attributed to less favorable solvation qf the constituent ions in ethanol than in water. Ion solvation would be expected to be even less favorable in isopropanol, so it is not surprising to find an enthalpy of solution of about + 40 kJ mol-1 for neodymium trichloride in this alcohol. This estimate must be considered as only approximate, as it is derived from... 

Intercomparison op Reported Solubilities for Neodymium Trichloride in Methanol and in Ethanol0 (at 25°C)... 

Lanthanum and neodymium trichlorides are readily soluble in ethylene glycol and in glycerol [Table XXVI (228,288)]. 

The most studied solvent here is pyridine (Table XXIX (178, 298). The reported solubilities parallel the affinities suggested by known solvates—e.g., YCl3-3py, SmCl3-3py, but PrCl3-2py (cf. Section III,C,2). Qualitative information on related solvents is that neodymium trichloride is very sparingly soluble in aniline, but insoluble in toluidine, pyrrole, piperidine, and quinoline. Praseodymium trichloride is also insoluble in quinoline, but yttrium trichloride is slightly soluble in this solvent (178). 

An interesting selectivity in the transfer of alkyl groups (n-Alk>Me) is observed in these addition reactions. The regioselectivity of the reaction of crotylmagnesium chloride (213) with benzaldehyde strongly depends on the presence of various rare-earth metal chlorides. The a- to y ratio of products can be switched to the opposite by using only another metal salt. Yttrium trichloride gives exclusively y-product, while neodymium trichloride leads to 89% of the a-attack (with 92% of ( )-isomer) (equation 142) °. 

In an early paper Wayda and Evans reported that LiC5Me5 reacts with anhydrous neodymium trichloride in refluxing THF to give exclusively the disubstituted complex 29f [62] ... 

An entirely analogous reaction occurs when anhydrous neodymium trichloride is reacted under similar conditions with two equivalents of Li[(CF3)3C6H2C(NSiMe3)2]. In this reaction (Eq. 13) the very bulky benzamidi-nate ligand behaves like a steric equivalent of C5Me5 [63] ... 

Neodymium(IIl), tris(T)- -cyclopentadienyl) (tetrahydrofuran)-, 26 20 Neodymium trichloride—tetrahydro-furan(2 3), 27 140... 

NdCls 3/2C4HgO, Neodymium trichloride-tetrahydrofuran(2 3), 27 140,28 290 NdOC gH27, Neodymium, tert-butylbis-(i -cyclopentadienylKtetrahydrofuran)-, 27 158... 

Kudin, L.S., Smirnov, A.A., 2003a. Molecular and ionic composition of vapor over neodymium trichloride. In Proceedings of the II International Symposium on High Temperature Mass Spectrometry (Plyos, 2003), Ivanovo, pp. 118-123. 

---