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The preparation of beta-diketiminato...
~
Buffone, Gerald Philip, Jr.
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The preparation of beta-diketiminato organochromium complexes for homogeneous olefin polymerization catalysis.
紀錄類型:
書目-電子資源 : Monograph/item
正題名/作者:
The preparation of beta-diketiminato organochromium complexes for homogeneous olefin polymerization catalysis./
作者:
Buffone, Gerald Philip, Jr.
面頁冊數:
237 p.
附註:
Source: Dissertation Abstracts International, Volume: 66-12, Section: B, page: 6619.
Contained By:
Dissertation Abstracts International66-12B.
標題:
Chemistry, Organic. -
電子資源:
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3200541
ISBN:
9780542458064
The preparation of beta-diketiminato organochromium complexes for homogeneous olefin polymerization catalysis.
Buffone, Gerald Philip, Jr.
The preparation of beta-diketiminato organochromium complexes for homogeneous olefin polymerization catalysis.
- 237 p.
Source: Dissertation Abstracts International, Volume: 66-12, Section: B, page: 6619.
Thesis (Ph.D.)--University of Delaware, 2006.
This dissertation describes research on paramagnetic beta-diketiminato chromium complexes, and in particular, the synthesis and olefin polymerization reactivity of cationic CrIII alkyl complexes as homogeneous models for the Phillips catalyst, i.e. CrO3/SiO2.
ISBN: 9780542458064Subjects--Topical Terms:
516206
Chemistry, Organic.
The preparation of beta-diketiminato organochromium complexes for homogeneous olefin polymerization catalysis.
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237 p.
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Source: Dissertation Abstracts International, Volume: 66-12, Section: B, page: 6619.
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Adviser: Klaus H. Theopold.
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Thesis (Ph.D.)--University of Delaware, 2006.
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This dissertation describes research on paramagnetic beta-diketiminato chromium complexes, and in particular, the synthesis and olefin polymerization reactivity of cationic CrIII alkyl complexes as homogeneous models for the Phillips catalyst, i.e. CrO3/SiO2.
520
$a
Chapter 1 discusses the synthesis and reactivity of the cationic chromium alkyl complex [(2,6-Me2Ph)2nacnacCr(OEt2)CH 2SiMe3]+ BARF- (39). Catalyst 39 is a homogeneous model for the Phillips olefin polymerization catalyst.
520
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In Chapter 2, we have investigated the synthesis of CrII alkyl complexes as precursors to three coordinate chromium alkyl polymerization catalysts. The attempted alkylation of [(2,6-iPr2Ph) 2nacnacCr(mu-Cl)]2 (36) with allyl magnesium chloride gave an allyl complex, i.e. (2,6-iPr2Ph) 2nacnacCr(eta3-Allyl) (57). The pyridine derivative [(2,6-iPr2Ph)2nacnacCr(py)Cl] (59) was synthesized in an effort to discover an efficient route to the proposed three-coordinate "base free" polymerization catalyst [(2,6- iPr2Ph)2nacnacCr (CH2Si(CH3 )3)]+ BARF- (54). The transformation to 59 was achieved via treatment of 36 with two equivalents of pyridine.
520
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Chapter 3 reports the synthesis of a novel class of nacnac chromium "internal base alkyl" (IBA) complexes. Lithium-hydrogen exchange reactions between tert-butyl lithium and the corresponding alkoxytrimethylsilane provided the IBA precursors (EtO)(CH3)2SiCH2Li (75) and (tBuO)(CH3)2SiCH2Li ( 77). The reaction of 37 with two equivalents of IBA anion 77 yielded the IBA complex (2,6-Me2Ph)2nacnacCr(CH 2Si(OtBu)(CH3)2) 2 (86). Attempted protolysis of 86 with one equivalent of H(Et2O)2BARF did not yield a stable cationic chromium IBA complex, i.e. [(2,6-Me2Ph)2nacnacCr(CH 2Si(OtBu)(CH3)2)]+ BARF (87). (Abstract shortened by UMI.)
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