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Dioxygen reactivity of multinuclear ...

Lum, June S.

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Dioxygen reactivity of multinuclear fluorinated copper(I) alkoxides facilitated by secondary ligand interactions and synthesis and characterization of monomeric oxygen-donor complexes of divalent copper and zinc.

Record Type:	Language materials, printed : Monograph/item
Title/Author:	Dioxygen reactivity of multinuclear fluorinated copper(I) alkoxides facilitated by secondary ligand interactions and synthesis and characterization of monomeric oxygen-donor complexes of divalent copper and zinc./
Author:	Lum, June S.
Description:	228 p.
Notes:	Source: Dissertation Abstracts International, Volume: 74-03(E), Section: B.
Contained By:	Dissertation Abstracts International74-03B(E).
Subject:	Chemistry, Inorganic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3532989
ISBN:	9781267765581

Dioxygen reactivity of multinuclear fluorinated copper(I) alkoxides facilitated by secondary ligand interactions and synthesis and characterization of monomeric oxygen-donor complexes of divalent copper and zinc.
Lum, June S.

Dioxygen reactivity of multinuclear fluorinated copper(I) alkoxides facilitated by secondary ligand interactions and synthesis and characterization of monomeric oxygen-donor complexes of divalent copper and zinc. - 228 p.

Source: Dissertation Abstracts International, Volume: 74-03(E), Section: B.

Thesis (Ph.D.)--Boston University, 2013.

Copper(I) complexes with fluorinated alkoxide ligands with the form K[Cu(OCRMe F2)2], in which R = MeF ( 4), Ph (5), or Me (6), were synthesized and characterized. The dioxygen (O2) reactivity of the series of complexes was investigated at -78°C and two stoichiometries of {CunO 2}species were observed. Manometric O2 uptake studies showed dinuclear {Cu2O2} and triuclear {Cu3O 2} species and their chromophores were measured with UV-vis spectroscopy. Warming these species to room temperature resulted in irreversible spectroscopic changes, and ligand hydroxylation was observed for complexes 5 and 6. ESI-MS study of reactions with 18O 2 confirmed O2 as the source of the ligand hydroxyl O atom. A tetrameric Cu(II) carbonate complex, {{K2(DME)1.5}[Cu(OCMeMe F2)2CO3]}4 (14), was obtained from CO2 addition to the {Cu2O3} moiety derived from 6..

ISBN: 9781267765581Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Dioxygen reactivity of multinuclear fluorinated copper(I) alkoxides facilitated by secondary ligand interactions and synthesis and characterization of monomeric oxygen-donor complexes of divalent copper and zinc.
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020 $a 9781267765581
035 $a (MiAaPQ)AAI3532989
035 $a AAI3532989
040 $a MiAaPQ $c MiAaPQ
100 1 $a Lum, June S. $3 2096702
245 1 0 $a Dioxygen reactivity of multinuclear fluorinated copper(I) alkoxides facilitated by secondary ligand interactions and synthesis and characterization of monomeric oxygen-donor complexes of divalent copper and zinc.
300 $a 228 p.
500 $a Source: Dissertation Abstracts International, Volume: 74-03(E), Section: B.
500 $a Adviser: Linda H. Doerrer.
502 $a Thesis (Ph.D.)--Boston University, 2013.
520 $a Copper(I) complexes with fluorinated alkoxide ligands with the form K[Cu(OCRMe F2)2], in which R = MeF ( 4), Ph (5), or Me (6), were synthesized and characterized. The dioxygen (O2) reactivity of the series of complexes was investigated at -78°C and two stoichiometries of {CunO 2}species were observed. Manometric O2 uptake studies showed dinuclear {Cu2O2} and triuclear {Cu3O 2} species and their chromophores were measured with UV-vis spectroscopy. Warming these species to room temperature resulted in irreversible spectroscopic changes, and ligand hydroxylation was observed for complexes 5 and 6. ESI-MS study of reactions with 18O 2 confirmed O2 as the source of the ligand hydroxyl O atom. A tetrameric Cu(II) carbonate complex, {{K2(DME)1.5}[Cu(OCMeMe F2)2CO3]}4 (14), was obtained from CO2 addition to the {Cu2O3} moiety derived from 6..
520 $a Irreversible reduction of O2 required secondary potassium-ligand (K···F and K-O) interactions which bridge multiple [Cu(OCRMe F2)2]- anions in solid-state structures of 4, 5, and 6, and were quantified by K+ cation bond valence analysis. Solution conductivity studies confirmed that neutral aggregates of K[Cu(OCRMeF2) 2] complexes are retained in solution. Ionic copper(I) complexes of the form {K(18C6)}[Cu(OCRMeF2)2] in which R = MeF (7), Ph (8), or Me ( 9) and (Ph4P)[Cu(OCRMeF2) 2], with R = MeF (10) were prepared, none of which react with O2 at -78°C.
520 $a The Cu(II) alkoxide compounds {K(18C6)}[Cu(OCRMeF 2)3], in which R= MeF (15) and Me (16) were prepared and spectroscopically and magnetically characterized. Compound 16 was demonstrated to be trigonal-planar by X-ray crystallography and all other data for 15 are consistent with trigonal-planar coordination. Two four-coordinate Cu(II) compounds with dodecafluoropinacolate (ddfp) ligands were also synthesized and characterized spectroscopically. The structurally characterized square-planar ddfp compounds have the form {K(solvent)2}2[Cu(ddfp)2], in which solvent = H2O (17) or DME (18). Diamagnetic Zn(II) derivatives with aryloxide ligands of the form {K(18C6)} 2[Zn(OAr)4], in which Ar = ArF (19) or Ar' (20) and {K(18C6)}[Zn(OCRMeF2) 3], with R = Ph (21) were also prepared and characterized by X-ray crystallography and multinuclear NMR.
590 $a School code: 0017.
650 4 $a Chemistry, Inorganic. $3 517253
690 $a 0488
710 2 $a Boston University. $3 1017454
773 0 $t Dissertation Abstracts International $g 74-03B(E).
790 $a 0017
791 $a Ph.D.
792 $a 2013
793 $a English
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3532989