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Chemistry of dithiolene complexes re...

Wang, Jun-Jieh.

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Chemistry of dithiolene complexes related to mononuclear molybdenum and tungsten enzyme sites.

Record Type:	Language materials, printed : Monograph/item
Title/Author:	Chemistry of dithiolene complexes related to mononuclear molybdenum and tungsten enzyme sites./
Author:	Wang, Jun-Jieh.
Description:	208 p.
Notes:	Adviser: Richard H. Holm.
Contained By:	Dissertation Abstracts International68-05B.
Subject:	Chemistry, Biochemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3265121
ISBN:	9780549038245

Chemistry of dithiolene complexes related to mononuclear molybdenum and tungsten enzyme sites.
Wang, Jun-Jieh.

Chemistry of dithiolene complexes related to mononuclear molybdenum and tungsten enzyme sites. - 208 p.

Adviser: Richard H. Holm.

Thesis (Ph.D.)--Harvard University, 2007.

To date, enzymes containing mononuclear molybdenum or tungsten active sites are all found to be chelated with one or two pyranopterindithiolate (S2pd) cofactors. Chapter 1 provides an introductory background of these molybdo- and tungstoenzymes as well as the S2pd ligand. In research related to these enzymes, the ene-1,2-dithiolate ligands, Me 2C2S22- and C6H 4S22- (bdt), were selected as representations of S2pd in synthetic analogues of protein sites. Investigation of these dithiolene-containing Mo and W complexes provides both structural and functional approaches to the enzyme sites.

ISBN: 9780549038245Subjects--Topical Terms:

1017722
Chemistry, Biochemistry.

Chemistry of dithiolene complexes related to mononuclear molybdenum and tungsten enzyme sites.
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020 $a 9780549038245
035 $a (UMI)AAI3265121
035 $a AAI3265121
040 $a UMI $c UMI
100 1 $a Wang, Jun-Jieh. $3 1285763
245 1 0 $a Chemistry of dithiolene complexes related to mononuclear molybdenum and tungsten enzyme sites.
300 $a 208 p.
500 $a Adviser: Richard H. Holm.
500 $a Source: Dissertation Abstracts International, Volume: 68-05, Section: B, page: 3047.
502 $a Thesis (Ph.D.)--Harvard University, 2007.
520 $a To date, enzymes containing mononuclear molybdenum or tungsten active sites are all found to be chelated with one or two pyranopterindithiolate (S2pd) cofactors. Chapter 1 provides an introductory background of these molybdo- and tungstoenzymes as well as the S2pd ligand. In research related to these enzymes, the ene-1,2-dithiolate ligands, Me 2C2S22- and C6H 4S22- (bdt), were selected as representations of S2pd in synthetic analogues of protein sites. Investigation of these dithiolene-containing Mo and W complexes provides both structural and functional approaches to the enzyme sites.
520 $a Structural. In Chapters 2 and 3, it is shown that ligand substitution of the bis(dithiolene) complexes [M(CO)2(S2C 2Me2)2] eliminates both carbonyl ligands, leading to square pyramidal [MIV(QR)(S2C2Me 2)2]1-, trigonal prismatic [M IV(O2CR) (S2C2Me2) 2]1-, and distorted trigonal prismatic [W VIO(QR)(S2C2Me2)2] 1- (M = Mo, W; Q = O, S) complexes were synthesized to represent the active sites of arsenite oxidase/arsenate reductase; selenate reductase, nitrate reductase, and (likely) perchlorate reductase. In Chapter 4, the synthesis and structures of the mono(dithiolene) complexes [WVIOS(OSiR 2R')(bdt)]1- and [WVIO2S(bdt)] 2- are described. These are the first and only synthetic molecules that contain a cis-WVIOS structure and a dithiolene ligand. These five-coordinate square pyramidal complexes are synthetic analogues of active sites in the xanthine oxidase family.
520 $a Functional. In Chapter 3, five-coordinate [M IV(QR)(S2C2Me2)2] 1- complexes are shown to be biomimetic models of oxotransferases, accepting an oxygen atom from SeO42- or other substrates XO = N-oxides and S-oxides to form six-coordinate [MVIO(QR)(S2C2Me 2)2]1- complexes in acetonitrile and to complete second-order oxo transfer reactions whose negative entropies of activation implicate associative transition states. Furthermore in Chapter 2, in addition to classic oxo transfer in the reaction [MIV(OC 6H4-p-X')(S2C2Me 2)2]1- + Ph3AsQ → [M VIQ(OC6H4-p-X')(S2C 2Me2)2]1- + Ph3As, Ph3AsS was introduced to complete the first quantitative examination of metal-mediated sulfido transfer reactions. Kinetics comparisons with oxo transfer reactions for M = Mo and W are presented. Results of oxo transfer reactions of [MoVIO2(SR)(bdt)]1- to substrates are also discussed in Chapter 4.
590 $a School code: 0084.
650 4 $a Chemistry, Biochemistry. $3 1017722
650 4 $a Chemistry, Inorganic. $3 517253
690 $a 0487
690 $a 0488
710 2 $a Harvard University. $3 528741
773 0 $t Dissertation Abstracts International $g 68-05B.
790 $a 0084
790 1 0 $a Holm, Richard H., $e advisor
791 $a Ph.D.
792 $a 2007
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3265121