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Synthesis and reactivity of terminal...

Wicht, Denyce Kramer.

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Synthesis and reactivity of terminal platinum(II) phosphido complexes: Application to the platinum-catalyzed asymmetric hydrophosphination of acrylonitrile.

紀錄類型:	書目-語言資料,印刷品 : Monograph/item
正題名/作者:	Synthesis and reactivity of terminal platinum(II) phosphido complexes: Application to the platinum-catalyzed asymmetric hydrophosphination of acrylonitrile./
作者:	Wicht, Denyce Kramer.
面頁冊數:	352 p.
附註:	Chair: David S. Glueck.
Contained By:	Dissertation Abstracts International60-09B.
標題:	Chemistry, Inorganic. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9943906
ISBN:	9780599455474

Synthesis and reactivity of terminal platinum(II) phosphido complexes: Application to the platinum-catalyzed asymmetric hydrophosphination of acrylonitrile.
Wicht, Denyce Kramer.

Synthesis and reactivity of terminal platinum(II) phosphido complexes: Application to the platinum-catalyzed asymmetric hydrophosphination of acrylonitrile. - 352 p.

Chair: David S. Glueck.

Thesis (Ph.D.)--Dartmouth College, 1999.

The proposed mechanism of platinum-catalyzed hydrophosphination of acrylonitrile, which involves insertion into a Pt-phosphido bond, is described. Diastereoselectivity in acrylonitrile insertion was observed and we investigated an asymmetric version of the catalysis for the synthesis of P-chiral tertiary phosphines of the type PRR'(CH2CH2CN) from racemic secondary phosphines PHRR'. A series of chiral platinum(0) trans-stilbene complexes which could serve as convenient catalyst precursors in the desired transformation were prepared and enantioselective binding of the alkene is described. The syntheses of chiral platinum(II) phosphido complexes are reported; the results of protonation and insertion reactions are consistent with rapid inversion at the phosphido phosphorus. In addition, the dynamic behavior of a series of perfluoroacyl platinum(II) phosphido complexes also provides evidence for low barriers to pyramidal inversion.

ISBN: 9780599455474Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Synthesis and reactivity of terminal platinum(II) phosphido complexes: Application to the platinum-catalyzed asymmetric hydrophosphination of acrylonitrile.
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245 1 0 $a Synthesis and reactivity of terminal platinum(II) phosphido complexes: Application to the platinum-catalyzed asymmetric hydrophosphination of acrylonitrile.
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500 $a Chair: David S. Glueck.
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502 $a Thesis (Ph.D.)--Dartmouth College, 1999.
520 $a The proposed mechanism of platinum-catalyzed hydrophosphination of acrylonitrile, which involves insertion into a Pt-phosphido bond, is described. Diastereoselectivity in acrylonitrile insertion was observed and we investigated an asymmetric version of the catalysis for the synthesis of P-chiral tertiary phosphines of the type PRR'(CH2CH2CN) from racemic secondary phosphines PHRR'. A series of chiral platinum(0) trans-stilbene complexes which could serve as convenient catalyst precursors in the desired transformation were prepared and enantioselective binding of the alkene is described. The syntheses of chiral platinum(II) phosphido complexes are reported; the results of protonation and insertion reactions are consistent with rapid inversion at the phosphido phosphorus. In addition, the dynamic behavior of a series of perfluoroacyl platinum(II) phosphido complexes also provides evidence for low barriers to pyramidal inversion.
590 $a School code: 0059.
650 4 $a Chemistry, Inorganic. $3 517253
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