Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations [electronic resource]
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| Format: | Government Document Electronic eBook |
| Language: | English |
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Washington, D.C. : Oak Ridge, Tenn. :
United States. Department of Energy. Office of Basic Energy Sciences ; distributed by the Office of Scientific and Technical Information, U.S. Department of Energy,
2015.
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| Abstract: | Here, a new class of cyclopentadiene-bis(oxazoline) compounds and their piano-stool-type organometallic complexes have been prepared as catalysts for hydroamination of aminoalkenes. The two compounds MeC(Ox<sup>Me2</sup>)<sub>2</sub>C<sub>5</sub>H<sub>5</sub> (Bo<sup>M</sup>CpH; Ox<sup>Me2</sup> = 4,4-dimethyl-2-oxazoline) and MeC(Ox<sup>Me2</sup>)<sub>2</sub>C<sub>5</sub>Me<sub>4</sub>H (Bo<sup>M</sup>Cp<sup>tet</sup>H) are synthesized from C<sub>5</sub>R<sub>4</sub>HI (R = H, Me) and MeC(Ox<sup>Me2</sup>)<sub>2</sub>Li. These cyclopentadiene-bis(oxazolines) are converted into ligands that support a variety of metal centers in piano-stool-type geometries, and here we report the preparation of Mg, Tl, Ti, and Zr compounds. Bo<sup>M</sup>CpH and Bo<sup>M</sup>Cp<sup>tet</sup>H react with MgMe<sub>2</sub>(O<sub>2</sub>C<sub>4</sub>H<sub>8</sub>)<sub>2</sub> to give the magnesium methyl complexes {Bo<sup>M</sup>Cp}MgMe and {Bo<sup>M</sup>Cp<sup>tet</sup>}MgMe. Bo<sup>M</sup>CpH and Bo<sup>M</sup>Cp<sup>tet</sup>H are converted to Bo<sup>M</sup>CpTl and Bo<sup>M</sup>Cp<sup>tet</sup>Tl by reaction with TlOEt. The thallium derivatives react with TiCl<sub>3</sub>(THF)<sub>3</sub> to provide [{Bo<sup>M</sup>Cp}TiCl(μ-Cl)]<sub>2</sub> and [{Bo<sup>M</sup>Cptet}TiCl(μ-Cl)]<sub>2</sub>, the former of which is crystallographically characterized as a dimeric species. Bo<sup>M</sup>CpH and Zr(NMe<sub>2</sub>)<sub>4</sub> react to eliminate dimethylamine and afford {Bo<sup>M</sup>Cp}Zr(NMe<sub>2</sub>)<sub>3</sub>, which is crystallographically characterized as a monomeric four-legged piano-stool compound. {Bo<sup>M</sup>Cp}Zr(NMe<sub>2</sub>)<sub>3</sub>, {Bo<sup>M</sup>Cp}MgMe, and {Bo<sup>M</sup>Cp<sup>tet</sup>}MgMe are efficient catalysts for the hydroamination/cyclization of aminoalkenes under mild conditions. |
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| Item Description: | Published through SciTech Connect. 11/25/2015. "is-j--8905" Organometallics 34 23 ISSN 0276-7333 AM. Naresh Eedugurala; Megan Hovey; Hung -An Ho; Barun Jana; Nicole L. Lampland; Arkady Ellern; Aaron D. Sadow. |
| Physical Description: | p. 5566-5575 : digital, PDF file. |