Trapping an Unexpected/Unprecedented Hexanuclear Ce(III) Hydrolysis Product with Neutral 4‐Amino‐1,2,4‐triazole
[1];
[2];
[3];
[4];
[5];
[6];
[2];
[7]
- Department of Chemistry &, Biochemistry The University of Alabama Tuscaloosa AL 35487 USA, Present Address: Department of Chemistry and Nuclear Science and Engineering Center Colorado School of Mines, 1500 Illinois St. Golden CO 80401 USA
- Department of Materials and Environmental Chemistry Stockholm University Svante Arrhenius väg 16 C Stockholm 10691 Sweden, Department of Biological and Chemical Engineering and iNANO Aarhus University 8000 Aarhus C Denmark
- Department of Chemistry &, Biochemistry The University of Alabama Tuscaloosa AL 35487 USA
- Laboratory of Organic Electronics Department of Science and Technology Linköping University 60174 Norrköping Sweden
- Department of Chemistry &, Biochemistry The University of Alabama Tuscaloosa AL 35487 USA, Present Address: Department of Chemistry University of Michigan, 4307 Chemistry 930 North University Ave Ann Arbor MI 48109 USA
- Department of Physics and Astronomy Uppsala University Box 516 75120 Uppsala Sweden
- Department of Chemistry &, Biochemistry The University of Alabama Tuscaloosa AL 35487 USA, Department of Materials and Environmental Chemistry Stockholm University Svante Arrhenius väg 16 C Stockholm 10691 Sweden
Abstract Using Ce(III) as both a representative lanthanide and actinide analog, the ability of mixtures of acidic and basic azoles to allow direct access to homoleptic N‐donor f‐element complexes in one pot reactions from hydrated salts as starting materials was examined by reacting mixtures of 4‐amino‐1,2,4‐triazole (4‐NH 2 ‐1,2,4‐Triaz), 5‐amino‐tetrazole (5‐NH 2 ‐HTetaz), and 1,2,3‐triazole (1,2,3‐HTriaz) in 1 : 1 and 1 : 3 ratios with CeCl 3 ⋅ 7H 2 O, [C 2 mim] 3 [CeCl 6 ] ([C 2 mim] + =1‐ethyl‐2‐methylimidazolium), and Ce(NO 3 ) 3 ⋅ 6H 2 O. Although unsuccessful in our goal, structural analysis revealed that neutral 4‐NH 2 ‐1,2,4‐Triaz is structure directing via η 2 μ 2 κ 2 bridging, with the formation of the dinuclear complexes [Ce 2 Cl 2 (μ 2 ‐4‐NH 2 ‐1,2,4‐Triaz) 4 (H 2 O) 8 ]Cl 4 ⋅ 4H 2 O, [Ce 2 (μ 2 ‐4‐NH 2 ‐1,2,4‐Triaz) 4 (4‐NH 2 ‐1,2,4‐Triaz) 2 (Cl) 6 ], and [4‐NH 2 ‐1,2,4‐HTriaz][Ce 2 (μ 2 ‐4‐NH 2 ‐1,2,4‐Triaz) 2 (μ 2 ‐NO 3 )(NO 3 ) 6 (H 2 O) 2 ]. When the synthetic conditions favored hydrolysis, the hexanuclear Ce(III) complex [Ce 6 (μ 3 ‐O) 4 (μ 3 ‐OH) 2 (μ 3 ‐Cl) 2 (Cl) 6 (μ 2 ‐4‐NH 2 ‐1,2,4‐Triaz) 12 ] ⋅ 7H 2 O was isolated. This unexpected hydrolysis product represents the first example of a high nuclearity lanthanide complex where all Ln atoms are pairwise connected through 12 N‐donor ligands or 12 neutral bridging ligands of any type, a rare example of incorporation of non‐oxo coordinating anions in the M 6 X 8 core, and the first reported Ce(III) hexanuclear complex of this type.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 1999279
- Alternate ID(s):
- OSTI ID: 1999280
- Journal Information:
- European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry Vol. 26 Journal Issue: 31; ISSN 1434-1948
- Publisher:
- Wiley Blackwell (John Wiley & Sons)Copyright Statement
- Country of Publication:
- Germany
- Language:
- English
Similar Records
Primary to secondary sphere coordination of 15-crown-5 to lanthanide(III) chlorides: Structural analysis of [MCl{sub 3}(15-crown-5)] (M = La, Ce) and [Er(OH{sub 2}){sub 8}]Cl{sub 3} {center_dot} 15-crown-5
Acidic 1,3-propanediaminetetraacetato lanthanides with luminescent and catalytic ester hydrolysis properties