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Abstract: Synthetic pathways to several salts of the anion [Cp*2ZrH3]- have been developed. Reaction of Cp*2ZrH2 (3) prepared from [Cp*2Zr(N2)]2(-N2) (2), with KH in THF, afforded [Cp*2ZrH3]K (1) in a 74% yield. In a similar manner, addition of LiH gave [Cp*2ZrH3]Li (4). While this synthetic pathway...
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Abstract: 1,2-disubstituted cyclopentadienyl diimine anions are examples of extended -systems that bind metals through the nitrogen atoms. Reaction of Cp2Mg with benzonitrile gives the product (1,2-C5H3(C(Ph)NH)2)CpMg(NCPh) (1) in 98% yield. In an analogous manner, the related complexes (1,2-C5H3(C(...
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Catalytic dehydrocoupling of phosphines was investigated using the anionic zirconocene trihydride salts [Cp*Zr-2(mu-H)(3)Li](3) (1a) or [Cp*Zr-2(mu-H)(3)K(thf)(4)] (1b), and the metallocycles [CpTi(NPtBu3)(CH2)(4)] (6) and [Cp*M(NPtBu3)(CH2)(4)] (M = Ti 20, Zr 21) as catalyst precursors. Dehydrocoup...
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Abstract: The reactions of Cp2MH3 (M = Nb, Ta) or Cp'2NbH3 (Cp' = Me3SiC5H4) with excess primary phosphines yield the complexes Cp2NbH[(PPh)2] (1), Cp'2NbH[(PPh)2] (2), and Cp2TaH[(PR)2] (R = Ph, 3; R = Cy, 4). Crystallographic studies of each of these compounds confirmed the transoid disposition of...
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alpha-Methoxy acrylonitriles, available from aldehydes and ketones, react with sodium azide in the presence of eerie ammonium nitrate to give azido nitrates; from these compounds, alpha-amino acids are obtained by sequential treatment with sodium acetate in acetic acid and then methanolic potassium ...
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Abstract: The complexes [CpTi(SCHCH2CH2S)]2 (Cp = Cp (3), MeCp (4)) are readily prepared from reaction of CpTi(SCH2CH2CH2S)Cl (Cp = Cp (1), MeCp (2)) with MeLi, AlMe3, or t-BuLi. Both compounds are centrosymmetric dimers in the solid state containing strained thiatitanacyclopropane rings. PMe3 cleav...
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Abstract: The reaction of (Me3SiC5H4)2ZrCl2 with excess LiAlH4 affords the product 5. The structural characterization of 5 reveals two types of aggregation of the (Me3SiC5H4)2ZrH2 and AlH3 fragments formulated as [(Me3SiC5H4)2ZrH(-H)2]3Al and [(Me3SiC5H4)2ZrH(-H)2]2AlH. In this Zr3Al aggregate, thre...
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Oxidation of Cr[N(SiMe3)(2)](2)(THF)(2) with iodine and dicumyl peroxide results in tetrahedral Cr(IV)Cr[N(SiMe3)(2)](2)I-2 and trigonal planar Cr(III) Cr[N(SiMe3)(2)](OCMe2Ph)(2), respectively; both complexes have been characterised by single-crystal X-ray diffraction, and both are active for ethyl...
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This thesis describes the synthetic strategies for the incorporation of a number of metal species into a series of polynorbornenes, as well as their characterization and thermal analysis. This was accomplished through the synthesis of new monometallic norbornene compounds containing chromium and iro...
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Multifunctional macromolecules continue to attract attention. Here, three generations of a new family of bifunctional organoiron dendrimers are reported, which are synthesized from a redox-active organoiron complex, η6-dichlorobenzene-η5-cyclopentadienyl-iron(II). The facile chemistry of the compl...