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New chiral C(1)-symmetric metallocen...
~
Giardello, Michael Albert.
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New chiral C(1)-symmetric metallocenes designed for asymmetric catalysis.
紀錄類型:
書目-電子資源 : Monograph/item
正題名/作者:
New chiral C(1)-symmetric metallocenes designed for asymmetric catalysis./
作者:
Giardello, Michael Albert.
面頁冊數:
336 p.
附註:
Source: Dissertation Abstracts International, Volume: 55-01, Section: B, page: 0110.
Contained By:
Dissertation Abstracts International55-01B.
標題:
Chemistry, Inorganic. -
電子資源:
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9415730
New chiral C(1)-symmetric metallocenes designed for asymmetric catalysis.
Giardello, Michael Albert.
New chiral C(1)-symmetric metallocenes designed for asymmetric catalysis.
- 336 p.
Source: Dissertation Abstracts International, Volume: 55-01, Section: B, page: 0110.
Thesis (Ph.D.)--Northwestern University, 1993.
New organolanthanide complexes of the chelating cyclopentadienyl-based ligand Subjects--Topical Terms:
517253
Chemistry, Inorganic.
New chiral C(1)-symmetric metallocenes designed for asymmetric catalysis.
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Giardello, Michael Albert.
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New chiral C(1)-symmetric metallocenes designed for asymmetric catalysis.
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336 p.
500
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Source: Dissertation Abstracts International, Volume: 55-01, Section: B, page: 0110.
500
$a
Adviser: Tobin J. Marks.
502
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Thesis (Ph.D.)--Northwestern University, 1993.
520
$a
New organolanthanide complexes of the chelating cyclopentadienyl-based ligand
$\
rm Me\sb2SiCp\sp{\prime\prime}\lbrack R\sp*Cp\rbrack
$
preferentially adopt a single planar chiral configuration of the asymmetric metal-ligand template. The chloro complexes
$\
rm Me\sb2SiCp\sp{\prime\prime}\lbrack R\sp*Cp\rbrack Ln(\mu
$-
Cl)
$\
sb2
$\
sb2)\sb2
$
were isolated diastereomerically pure, although the epimers are in equilibrium in donor solvents. Both antipodes of these complexes are isolable through selective epimerization. The optical purity of the derived hydrocarbyl and amide complexes
$\
rm Me\sb2SiCp\sp{\prime\prime}\lbrack R\sp*Cp\rbrack LnE(SiMe\sb3)\sb2
$
(E = CH or N) depends on the planar chiral configuration of the chloro precursors, particularly with respect to the steric interactions between the chiral auxiliary and the incoming nucleophile during the substitution reaction.
520
$a
The complexes
$\
rm Me\sb2SiCp\sp{\prime\prime}\lbrack R\sp*Cp\rbrack LnE(TMS)\sb2
$
rapidly and efficiently catalyze the stereoselective hydroamination/cyclization of amino-olefins and the asymmetric hydrogenation of 2-phenyl-1-butene under mild conditions with moderate to very high enantioselectivities. Both antipodes of the target products can be prepared by choice of precatalyst. For a given chiral auxiliary, one antipode of the organolanthanide precatalyst is significantly more reactive/selective. The absolute configuration of the catalyst precursors have been assigned from CD spectroscopy and X-ray diffraction studies. Consequently, the stereochemistry of the catalytic products were rationalized on the basis of presumed catalyst-substrate steric interactions which develop in the transition state of the enantioselective step (operationally irreversible olefin insertion into the Ln-N or Ln-H bond).
520
$a
The Zr and Hf complexes of the ancillary ligand
$\
rm Me\sb2SiCp\sp{\prime\prime}\lbrack R\sp*Cp\rbrack
$
have been synthesized. Optically pure metallocenes of the (
$-
$)
-menthyl derivative can be isolated from a single recrystallization of the complexation and alkylation reaction products. The (+)-neomenthyl derivative, however, is isolated as a pseudo-racemate. The metallocenes are configurationally stable in donor solvents indefinitely. Propylene polymerization catalysts are prepared from reaction of the various metallocenes with a variety of co-catalysts. Polymer isotacticities and molecular weights depend on the amount and nature of the co-catalyst. These co-catalyst effects are reasonably a consequence of the demonstrated tight, sterically demanding, and differing ion pairing between the various anions and the chiral cationic reaction centers.
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$a
School code: 0163.
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$a
Chemistry, Inorganic.
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Northwestern University.
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Marks, Tobin J.,
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1993
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http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9415730
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