Synthesis and solution properties of lanthanum(III), europium(III), and lutetium(III) THP complexes and an X-ray diffraction study of a crystal containing four stereoisomers of a europium(III) THP complex (THP = 1,4,7,10-tetrakis(2-hydroxypropryl)-1,4,7,10-tetraazacyclododecane). Methyl groups impart rigidity to S,S,S,S-THP macrocyclic complexes
- State Univ. of New York, Buffalo, NY (United States)
The macrocycle 1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane (THP) prepared from racemic propylene oxide and cyclen (1,4,7,10-tetraazacyclododecane) consists of a mixture of stereoisomers that arise from the chiral {alpha}-carbons of the hydroxypropyl groups. {sup 13}C NMR studies suggest that five different diastereomers are formed. Lanthanum(III), europium(III), and lutetium(III) THP complexes are synthesized from the mixture of THP stereoisomers. Europium(III) THP complexes containing R,R,R,S and S,S,S,R configurations at the {alpha}-carbons of the hydroxypropyl groups cocrystallize from solution. The complex [Eu(THP)(H{sub 2}O)]{sub 2}(CF{sub 3}SO{sub 3}){sub 6}{center_dot}2EtOH{center_dot}H{sub 2}O crystallizes in the centrosymetric monoclinic space group P2{sub 1}/c (No. 14). Four stereoisomers (two enantiomeric pairs) of the complex appear in the crystal. Each asymmetric unit consists of two different diastereomers of the europium(III) cation, six triflate anions, two ethanol molecules, and one water molecule of solvation. The structure was solved and refined to R = 5.54% and R{sub w} = 5.72% for those 3351 reflections with {vert_bar}F{sub o}{vert_bar} > 6{sigma}{vert_bar}F{sub o}{vert_bar}. In addition, synthesis of the THP stereoisomer with all hydroxypropyl groups containing the S-configuration (S-THP) is accomplished by use of S-propylene oxide. The synthesis of lanthanum(III), europium(III), and lutetium(III) complexes of S-THP is reported; {sup 1}H and {sup 13}C NMR spectra of the lanthanum and lutetium complexes indicate that only one diastereomer is present in solution.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 75741
- Journal Information:
- Inorganic Chemistry, Vol. 33, Issue 4; Other Information: PBD: 16 Feb 1994
- Country of Publication:
- United States
- Language:
- English
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