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I. SYNTHESES OF 1,2-BIS(PHOSPHINO)BE...

LIU, SHIUH-TZUNG.

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I. SYNTHESES OF 1,2-BIS(PHOSPHINO)BENZENES AND A POLYPHOSPHINO MACROCYCLE. II. TRANSITION METAL COMPLEXATION AND HYDROGENATION STUDIES (ORGANOPHOSPHINES, PHENYLENEBISPHOSPHINES, CATALYST, NICKEL COMPLEXES, RHODIUM).

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	I. SYNTHESES OF 1,2-BIS(PHOSPHINO)BENZENES AND A POLYPHOSPHINO MACROCYCLE. II. TRANSITION METAL COMPLEXATION AND HYDROGENATION STUDIES (ORGANOPHOSPHINES, PHENYLENEBISPHOSPHINES, CATALYST, NICKEL COMPLEXES, RHODIUM)./
作者:	LIU, SHIUH-TZUNG.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, : 1985,
面頁冊數:	205 p.
附註:	Source: Dissertations Abstracts International, Volume: 46-07, Section: B.
Contained By:	Dissertations Abstracts International46-07B.
標題:	Organic chemistry. -
電子資源:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=8527605

I. SYNTHESES OF 1,2-BIS(PHOSPHINO)BENZENES AND A POLYPHOSPHINO MACROCYCLE. II. TRANSITION METAL COMPLEXATION AND HYDROGENATION STUDIES (ORGANOPHOSPHINES, PHENYLENEBISPHOSPHINES, CATALYST, NICKEL COMPLEXES, RHODIUM).
LIU, SHIUH-TZUNG.

I. SYNTHESES OF 1,2-BIS(PHOSPHINO)BENZENES AND A POLYPHOSPHINO MACROCYCLE. II. TRANSITION METAL COMPLEXATION AND HYDROGENATION STUDIES (ORGANOPHOSPHINES, PHENYLENEBISPHOSPHINES, CATALYST, NICKEL COMPLEXES, RHODIUM). - Ann Arbor : ProQuest Dissertations & Theses, 1985 - 205 p.

Source: Dissertations Abstracts International, Volume: 46-07, Section: B.

Thesis (Ph.D.)--The University of Texas at Austin, 1985.

This item must not be sold to any third party vendors.

I. The reduction of 1,2-bis(dimethoxyphosphoryl)benzene to give 1,2-bis(phosphino)benzene in 83% yield was accomplished by a new reducing agent LiAlClH(,3), which was derived from trimethylsilyl chloride and lithium aluminum hydride in tetrahydrofuran. The bisphosphine may then be transformed into 1,2-bis(alkylphosphino)benzenes (alkyl = methyl, ethyl and 2-propyl) and 1,2-bis(dialkylphosphino)benzenes (alkyl = 1(DEGREES), 2(DEGREES) and 3(DEGREES) alkyl substituents). A protecting group for a P-H group in a secondary phosphine has been developed, which is a 1-naphthylmethyl and a phosphine sulfide. This has been used to elaborate (1-naphthylmethyl)phosphine into bis(3-chloropropyl)-1-naphthylmethylphosphine sulfide, which upon reaction with dilithium bis(phenylphosphino)benzene, was transformed into the 11-P(,3) macrocycle, cis-2,10-diphenyl-7-(1'-naphthylmethyl)-7-thio-2,7,10-triphosphabicyclo 9.4.0 pentadeca-1(11),12,14-triene. The 1-naphthylmethyl moiety was removed quantitively with potassium naphthalenide to give the 11-P(,3) molecule with a secondary phosphine sulfide at 7-position. This was reduced with LiAlClH(,3) to give the 11-P(,3)H macrocycle containing a secondary phosphine, cis-2,10,diphenyl-2,7,10-triphosphabicyclo 9.4.0 pentadeca-1(11),12,14-triene. This macrocycle forms complexes with Rh(I) and Mo(0) in which all three ligating sites are involved in the metal coordination. II. The complexation of NiCl(,2) and (NBD)(,2)RhPF(,6) (NBD = norbornadiene) toward a series of ditertiary o-phenylene-bisphosphines (bidentate) has been examined. The exclusive formation of 1:1 complexes (bidentate : metal) was forced by having at least one of the alkyl substituents on each phosphorus atom greater than ethyl group. The hydrogenation of cyclooctene, (alpha)-acetamidocinnamic acid and other olefinic substrates by using (bidentate)Rh(NBD)PF(,6), (11-P(,3)H)Rh(NBD)PF(,6), and (triphos)Rh(NBD)PF(,6) has been studied. The complex, (11-P(,3)H)Rh(NBD)('+), exhibits unusual catalytic reactivity towards simple olefin substrates, which is attributed to the fac-coordination arrangement and the secondary phosphine site of macrocycle bonded to the rhodium complex.Subjects--Topical Terms:

523952
Organic chemistry.

I. SYNTHESES OF 1,2-BIS(PHOSPHINO)BENZENES AND A POLYPHOSPHINO MACROCYCLE. II. TRANSITION METAL COMPLEXATION AND HYDROGENATION STUDIES (ORGANOPHOSPHINES, PHENYLENEBISPHOSPHINES, CATALYST, NICKEL COMPLEXES, RHODIUM).
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100 1 $a LIU, SHIUH-TZUNG. $3 3558651
245 1 0 $a I. SYNTHESES OF 1,2-BIS(PHOSPHINO)BENZENES AND A POLYPHOSPHINO MACROCYCLE. II. TRANSITION METAL COMPLEXATION AND HYDROGENATION STUDIES (ORGANOPHOSPHINES, PHENYLENEBISPHOSPHINES, CATALYST, NICKEL COMPLEXES, RHODIUM).
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 1985
300 $a 205 p.
500 $a Source: Dissertations Abstracts International, Volume: 46-07, Section: B.
500 $a Publisher info.: Dissertation/Thesis.
502 $a Thesis (Ph.D.)--The University of Texas at Austin, 1985.
506 $a This item must not be sold to any third party vendors.
506 $a This item must not be added to any third party search indexes.
520 $a I. The reduction of 1,2-bis(dimethoxyphosphoryl)benzene to give 1,2-bis(phosphino)benzene in 83% yield was accomplished by a new reducing agent LiAlClH(,3), which was derived from trimethylsilyl chloride and lithium aluminum hydride in tetrahydrofuran. The bisphosphine may then be transformed into 1,2-bis(alkylphosphino)benzenes (alkyl = methyl, ethyl and 2-propyl) and 1,2-bis(dialkylphosphino)benzenes (alkyl = 1(DEGREES), 2(DEGREES) and 3(DEGREES) alkyl substituents). A protecting group for a P-H group in a secondary phosphine has been developed, which is a 1-naphthylmethyl and a phosphine sulfide. This has been used to elaborate (1-naphthylmethyl)phosphine into bis(3-chloropropyl)-1-naphthylmethylphosphine sulfide, which upon reaction with dilithium bis(phenylphosphino)benzene, was transformed into the 11-P(,3) macrocycle, cis-2,10-diphenyl-7-(1'-naphthylmethyl)-7-thio-2,7,10-triphosphabicyclo 9.4.0 pentadeca-1(11),12,14-triene. The 1-naphthylmethyl moiety was removed quantitively with potassium naphthalenide to give the 11-P(,3) molecule with a secondary phosphine sulfide at 7-position. This was reduced with LiAlClH(,3) to give the 11-P(,3)H macrocycle containing a secondary phosphine, cis-2,10,diphenyl-2,7,10-triphosphabicyclo 9.4.0 pentadeca-1(11),12,14-triene. This macrocycle forms complexes with Rh(I) and Mo(0) in which all three ligating sites are involved in the metal coordination. II. The complexation of NiCl(,2) and (NBD)(,2)RhPF(,6) (NBD = norbornadiene) toward a series of ditertiary o-phenylene-bisphosphines (bidentate) has been examined. The exclusive formation of 1:1 complexes (bidentate : metal) was forced by having at least one of the alkyl substituents on each phosphorus atom greater than ethyl group. The hydrogenation of cyclooctene, (alpha)-acetamidocinnamic acid and other olefinic substrates by using (bidentate)Rh(NBD)PF(,6), (11-P(,3)H)Rh(NBD)PF(,6), and (triphos)Rh(NBD)PF(,6) has been studied. The complex, (11-P(,3)H)Rh(NBD)('+), exhibits unusual catalytic reactivity towards simple olefin substrates, which is attributed to the fac-coordination arrangement and the secondary phosphine site of macrocycle bonded to the rhodium complex.
590 $a School code: 0227.
650 4 $a Organic chemistry. $3 523952
690 $a 0490
710 2 $a The University of Texas at Austin. $3 718984
773 0 $t Dissertations Abstracts International $g 46-07B.
790 $a 0227
791 $a Ph.D.
792 $a 1985
793 $a English
856 4 0 $u https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=8527605