Formation of bimetallic, trimetallic, and pentametallic yttrium methoxide and methoxide oxide complexes from reactions of alkali-metal methoxides with bis(cyclopentadienyl)yttrium chloride

Journal Article · Wed Jun 10 00:00:00 EDT 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00038a035· OSTI ID:7180882

Evans, W J; Sollberger, M S; Shreeve, J L; Olofson, J M; Hain, Jr, J H; Ziller, J W ^[1]

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1. Univ. of California, Irvine (United States)

The superficially simple metathetical reaction of (C5H5)[sub 2]YCl(THF) [where C5H5=C[sub 5]H[sub 5]] with alkali-metal methoxides has been found to form a variety of products and product mixtures depending on reaction conditions. (C5H5)[sub 2]YCl(THF) reacts with NaOMe to form [(C5H5)[sub 2]Y([mu]-OMe)][sub 2] (1) in 80-95% yield depending on the method of isolation of the product. 1 can be generated analogously from KOMe in up to 75% yield depending on reaction conditions and the source of KOMe. The primary byproduct in KOMe reactions, which can be isolated in up to 20% yield, was identified as the trimetallic anion ([(C5H5)[sub 2]Y([mu]-OMe)][sub 2][(C5H5)[sub 2]Y]([mu][sub 3]-O))[sup [minus]] (2). The yield of 2 can be increased to as high as 70% by varying the reaction conditions and the (C5H5)[sub 2]YCl(THF) to KOMe stoichiometry. Me[sub 2]O has been isolated as a byproduct in this oxide-forming reaction. The previously characterized pentametallic complex (C5H5)[sub 5]Y[sub 5]([mu]-OMe)[sub 4]([mu][sub 3]-OMe)[sub 4]([mu][sub 5]-O) (3) is also formed in this reaction system. 3 can be obtained in high yield from the reaction of (C5H5)YCl[sub 2](THF)[sub 3], generated in situ, with 2 equiv of NaOMe in THF at reflux or from the reaction of (C5H5)[sub 2]YCl(THF) and MeOH-solvated KOMe. Crystallographic data have been obtained on 1-3 as well as the (trimethylsilyl)cyclopentadienyl analogue of 1 [(C[sub 5]H[sub 4]SiMe[sub 3])[sub 2]Y([mu]-OMe)][sub 2] (4) and its chloride precursor [(C[sub 5]H[sub 4]SiMe[sub 3])[sub 2]Y([mu]-Cl)][sub 2] (5). Complexes 1,4, and 5 are comprised of (C[sub 5]H[sub 4]R)[sub 2]Y (R = H, SiMe[sub 3]) bent metallocene units bridged by methoxide or chloride ligands.

• OSTI ID: 7180882
• Journal Information: Inorganic Chemistry; (United States), Vol. 31:12; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
YTTRIUM COMPLEXES
CHEMICAL PREPARATION
BOND ANGLE
BOND LENGTHS
CHEMICAL REACTION YIELD
DIMERS
LIGANDS
MOLECULAR STRUCTURE
NMR SPECTRA
ORGANOMETALLIC COMPOUNDS
X-RAY DIFFRACTION
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
DIMENSIONS
LENGTH
ORGANIC COMPOUNDS
SCATTERING
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
YIELDS
400201* - Chemical & Physicochemical Properties