
TY  - JOUR
A1  - Deacon, Glen B. 
A1  - Feng, Tiecheng 
A1  - Junk, Peter C. 
A1  - Skelton, Brian W. 
A1  - Sobolev, Alexander N. 
A1  - White, Allan H. 
T1  - Preparation and X-Ray Crystal Structures of Tetrahydrofuran-Complexed Rare Earth Chlorides &#8212;  a Structurally Rich Series
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1998
VL  - 51
IS  - 1
SP  - 75
EP  - 89
KW  - 
UR  - https://doi.org/10.1071/C97174 
N2  - Anhydrous lanthanoid metal chlorides LnCl3(thf)n (Ln = La, Ce, Nd, Sm, n = 2; Ln = Tb, Ho, n = 2&#183;5; Ln = Dy, Tm, n= 2&#183;7; Ln = Gd, Yb, Lu, n = 3; Ln = Er, n = 3&#183;5) have been prepared in excellent yield by the direct reaction of the lanthanoid metal powders with hexachloroethane in tetrahydrofuran (thf), and (Ln = Eu, n = 0&#183;8; Ln = La, n = 1&#183;7; Ln = Pr, n = 2; Ln = Gd, n = 2&#183;5; Ln = Er, n = 3) in good yield except for EuCl3(thf)0&#183;8 from bulk metal. &#91;YbCl3(thf)2&#93;2 was prepared by prolonged treatment of solid YbCl3(thf)3 with pentane. The X-ray crystal structures of &#91;LnC3(thf)2&#93; (Ln = La, Ce or Pr), &#91;LnCl3(thf)3.5&#93; (Ln = Gd or Er), &#91;YbCl3(thf)3&#93; and &#91;LaCl3(thf)(H2O)&#93; have been determined. For &#91;LaCl3(thf)2&#93;, a square antiprismatic single-stranded polymer, ... La(-Cl)3(thf)3La(-Cl)3(thf)2 ..., is the first eight-coordinate LnCl3(thf)n complex. The metal is surrounded by two sets of three bridging chlorines and cis thf oxygens. &#91;LnCl3(thf)2&#93; (Ln = Ce, Pr) have seven-coordinate structures with doubly chloride-bridged linear chains, ... LnCl(&#181;-Cl)3(thf)2LnCl(&#181;-Cl)2(thf)2 ... where the lanthanoid atom exists in a pentagonal bipyramidal environment, the pentagonal bipyramidal plane being defined by four chloride atoms and one oxygen atom of the thf ligand, and the axial positions being occupied by a chloride and a thf oxygen atom. &#91;LnCl3(thf)3.5&#93; (Ln = Gd, Er) crystallize as discrete ion pairs, &#91;LnCl2(thf)5&#93;+ &#91;LnCl4(thf)2&#93;&#175;. The lanthanoid atom in the cation displays pentagonal bipyramidal geometry with two apical chloride atoms and five equatorial thf ligands while the anion has quasi-regular octahedral stereochemistry with trans thf ligands. &#91;LaCl3(thf)(H2O)&#93; displays an eight-coordinate two-dimensional polymeric array with six bridging chlorides per lanthanum atom. Far-infrared spectra have been recorded for a number of products and used as a basis for structural proposals, particularly for products with fractional thf. 
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