Synthesis, reactivity, and stability of Di- and trivalent samarium amides
- Univ. of Ottawa, Ontario (Canada)
SmCl{sub 3}(THF){sub 3} (THF = tetrahydrofuran) reacts with anionic dialkylamides R{sub 2}N{sup {minus}} [R = Cy (cyclohexyl), i-Pr (isopropyl), Ph (phenyl)] to give different products, depending on the nature of the R substituents. Reaction with Cy{sub 2}NLi in a 1:2 molar ratio formed [(Cy{sub 2}N){sub 2}Sm({mu}-Cl)(THF)]{sub 2} (1) in 80% yield, whereas reaction with (i-Pr){sub 2}NLi under similar conditions have [(i-Pr{sub 2}N){sub 2}SmCl{sub 3}(Li(TMEDA)){sub 2}] (2) Partial loss of THF from complex 1 reorganized the molecule into the tetranuclear (Cy{sub 2}N){sub 6}Sm{sub 4}Cl{sub 6}(THF){sub 2} (3) Attempts to reduce complex 1 with a number of reagents gave [(Cy{sub 2}N){sub 3}SmTHF]{center_dot}toluene (5), while [(Cy{sub 2}N){sub 4}SmLi(THF)](4) was isolated upon alkylation reactions carried out with either NpLi or NfLi [Np = CH{sub 2}C(CH{sub 3}){sub 3}; Nf = CH{sub 2}C(CH{sub 3}){sub 2}Ph]. Direct synthesis of Sm(II) amides from SmI{sub 2}(THF){sub 2} starting material was successful only in the case of diphenylamide anion (Ph{sub 2}N{sup {minus}}). Depending on the stoichiometry, -ate (Ph{sub 2}N){sub 4}Sm[Na(TMEDA)]{sub 2} (6) or neutral [(Ph{sub 2}N){sub 2}Sm(THF){sub 4}]{center_dot}THF (7) was obtained.
- OSTI ID:
- 263749
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 7 Vol. 35; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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