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Title: A triangular heterometallic siloxide containing barium

Reaction of KOSiPh[sub 3] with Ba[sub 3](OSiPh[sub 3])[sub 6](THF) in THF displaces barium from the triangular reagent to yield a colorless solid. Recrystallization in the presence of MeOC[sub 2]H[sub 4]OMe(DME) yields KBa[sub 2](OSiPh[sub 3])[sub 5](DME)[sub 2], characterized by [sup 1]H and [sup 29]Si NMR spectroscopy and X-ray diffraction. The molecule contains a triangular KBa[sub 2]([mu][sub 3]-OSiPh[sub 3])[sub 2]([mu][sub 2]-OSiPh[sub 3])[sub 3] core with [eta][sup 1] and [eta][sup 2]-DME ligation on each barium. The benzene-soluble molecule is fluxional in solution at both the OSiPh[sub 3] and the DME groups. At -70C in CH[sub 2]Cl[sub 2]/C[sub 6]D[sub 6], both [eta][sup 1]-DME/[eta][sup 2]-DME site exchange and intramolecular siloxide migration have been slowed, and the spectra are in agreement with retention of the solid-state structure in solution. Crystallographic data for KBa[sub 2](OSiPh[sub 3])[sub 5](DME)[sub 2] (-159C): a = 15.474 (3) [angstrom], b = 26.466 (6) [angstrom], c = 23.783 (5) [angstrom], [beta] = 99.80 (1)[degree] with Z = 4 in space group P2[sub 1]/n.
Authors:
; ;  [1]
  1. (Indiana Univ., Bloomington (United States))
Publication Date:
OSTI Identifier:
6770350
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; (United States); Journal Volume: 30:26
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BARIUM COMPOUNDS; CRYSTAL STRUCTURE; ORGANIC SILICON COMPOUNDS; OXYGEN COMPOUNDS; POTASSIUM COMPOUNDS; CHEMICAL PREPARATION; DME; EXPERIMENTAL DATA; LATTICE PARAMETERS; NUCLEAR MAGNETIC RESONANCE; SILICON 29; X-RAY DIFFRACTION; ALKALI METAL COMPOUNDS; ALKALINE EARTH METAL COMPOUNDS; COHERENT SCATTERING; DATA; DIFFRACTION; ETHERS; EVEN-ODD NUCLEI; INFORMATION; ISOTOPES; LIGHT NUCLEI; MAGNETIC RESONANCE; NUCLEI; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC OXYGEN COMPOUNDS; RESONANCE; SCATTERING; SILICON ISOTOPES; STABLE ISOTOPES; SYNTHESIS 400201* -- Chemical & Physicochemical Properties