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 04:00:00 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), Journal Name: Inorganic Chemistry; (United States) Vol. 31:12; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

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