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), Vol. 30:26; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CERIUM COMPLEXES
CRYSTAL STRUCTURE
LANTHANUM COMPLEXES
ALKOXIDES
CHEMICAL PREPARATION
EXPERIMENTAL DATA
ORGANIC SILICON COMPOUNDS
X-RAY DIFFRACTION
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
RARE EARTH COMPLEXES
SCATTERING
SYNTHESIS
400201* - Chemical & Physicochemical Properties