A comparative synthetic and structural study of triphenylmethoxide and triphenylsiloxide complexes of the early lanthanides, including X-ray crystal structures of La[sub 2](OCPh[sub 3])[sub 6] and Ce[sub 2](OSiPh[sub 3])[sub 6]
- Univ. of California, Irvine (United States)
La[N(SiMe[sub 3])[sub 2]][sub 3] reacts with 3 equiv of triphenylmethanol in toluene to form the dimer [La(OCPh[sub 3])[sub 2]([mu]-OCPh[sub 3])][sub 2] (1) in 90% yield. 1 crystallizes in the triclinic space group P[bar 1] with a = 12.019 (3) [angstrom], b = 14.287 (2) [angstrom], c = 16.375 (3) [angstrom], [alpha] = 73.99 (1)[degree], [beta] = 85.39 (2)[degree], [gamma] = 76.07 (2)[degree], V = 2622.8 (8) [angstrom][sup 3], and D[sub calcd] = 1.34 Mg/m[sup 3] for Z = 1. Each lanthanum atom in 1 is surrounded by two terminal and two unsymmetrically bridging alkoxide ligands such that for the four oxygen donor atoms nearly describe a tetrahedron. The cerium analogue [Ce(OCPh[sub 3])[sub 2]([mu]-OCPh[sub 3])][sub 2] (2) can be prepared similarly, and a single-crystal analysis shows it to be isomorphous with 1. Triphenylsilanol reacts with Ln[N(SiMe[sub 3])[sub 2]][sub 3] (Ln = La, Ce) in toluene to form the analogous Ph[sub 3]SiO complexes [Ln(OSiPh[sub 3])[sub 2]([mu]-OSiPh[sub 3])][sub 2] (Ln = La (3), Ce (4)). Complex 4 crystallizes from toluene in the triclinic space group P[bar 1] with a = 13.766 (2) [angstrom], b = 14.376 [angstrom], c = 14.603 (2) [angstrom], [alpha] = 73.34 (1)[degree], [beta] = 70.45 (1)[degree], [gamma] = 75.87 (1)[degree], V = 2573.4 (5) [angstrom][sup 3], and D[sub calcd] = 1.37 Mg/m[sup 3] for Z = 1. The structure of 4 is similar to that of 1 except that the four oxygen atoms surrounding each metal center approximate a square-pyramidal geometry which has a carbon atom of one of the arene rings in one basal position. By single-crystal analysis, complex 3 is isomorphous with 4. Complexes 3 and 4 dissolve the THF to form the previously characterized Ln(OSiPh[sub 3])[sub 3](THF)[sub 3] complexes. Compounds 1 and 2 are less soluble than 3 and 4 but dissolve in hot THF to form the more soluble THF adducts, Ln(OCPh[sub 3])[sub 3](THF)[sub x].
- OSTI ID:
- 7073856
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:26; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ALKOXIDES
CERIUM COMPLEXES
CHEMICAL PREPARATION
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
EXPERIMENTAL DATA
INFORMATION
LANTHANUM COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SILICON COMPOUNDS
RARE EARTH COMPLEXES
SCATTERING
SYNTHESIS
X-RAY DIFFRACTION