ePrints

Synthesis and structural characterization of Sm(II) and Yb(II) complexes containing sterically demanding, chelating secondary phosphide ligands

Lookup NU author(s): Dr Keith Izod, Paul O'Shaughnessy, Dr Joanne Sheffield, Professor William Clegg, Dr Stephen Liddle

Downloads

Full text for this publication is not currently held within this repository. Alternative links are provided below where available.

Abstract

Metathesis between [{(Me3Si)2CH}(C6H4-2-OMe)P]K and SmI2(THF)2 in THF yields [{([Me3Si]2CH)(C6H4-2-OMe)P}2Sm(DME)(THF)] (1), after recrystallization. A similar reaction between [{(Me3Si)2CH}(C6H3-2-OMe-3-Me)P]K and SmI2(THF)2 yields [{([Me3Si]2CH)(C6H3-2-OMe-3-Me)P}2Sm(DME)]·Et2O (2), while reaction between [{(Me3Si)2CH}(C6H4-2-CH2NMe2)P]K and either SmI2(THF)2 or YbI2 yields the five-coordinate complex [{([Me3Si]2CH)(C6H4-2-CH2NMe2)P}2Sm(THF)] (3) or the solvent-free complex [{([Me3Si]2CH)(C6H4-2-CH2-NMe2)P}2Yb] (4), respectively. X-ray crystallography shows that complex 2 adopts a distorted cis octahedral geometry, while complex 1 adopts a distorted pentagonal bipyramidal geometry (1, triclinic, P1̄, a = 11.0625(9) Å, b = 15.924(6) Å, c = 17.2104(14) Å, α = 72.327(2)°, β = 83.934(2)°, γ = 79.556(2)°, Z = 2; 2, monoclinic, P21, a = 13.176(4) Å, b = 13.080(4) Å, c, = 14.546(4) Å, β = 95.363(6)°, Z = 2). Complex 3 crystallizes as monomers with a square pyramidal geometry at Sm and exhibits short contacts between Sm and the ipso-carbon atoms of the ligands (3, monoclinic, C2/c, a = 14.9880(17) Å, b = 13.0528(15) Å, c = 24.330(3) Å, β = 104.507-(2)°, Z = 4). Whereas preliminary X-ray crystallographic data for 4 indicate a monomeric structure in the solid state, variable-temperature 1H, 13C{1H}, 31P{1H}, and 171Yb NMR spectroscopies suggest that 4 undergoes an unusual dynamic process in solution, which is ascribed to a monomer-dimer equilibrium in which exchange of the bridging and terminal phosphide groups may be frozen out at low temperature.

Publication metadata

Author(s): Izod K, O'Shaughnessy P, Sheffield JM, Clegg W, Liddle ST

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2000

Volume: 39

Issue: 21

Pages: 4741-4748

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/ic0002871

DOI: 10.1021/ic0002871

PubMed id: 11196949

Altmetrics

Share