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Synthesis and Characterization of Atomically Precise Copper Nanoclusters.

Record Type:	Language materials, manuscript : Monograph/item
Title/Author:	Synthesis and Characterization of Atomically Precise Copper Nanoclusters./
Author:	Nguyen, Thuy-Ai Dang.
Description:	1 online resource (370 pages)
Notes:	Source: Dissertation Abstracts International, Volume: 79-02(E), Section: B.
Subject:	Nanoscience. -
Online resource:	click for full text (PQDT)
ISBN:	9780355430097

Synthesis and Characterization of Atomically Precise Copper Nanoclusters.
Nguyen, Thuy-Ai Dang.

Synthesis and Characterization of Atomically Precise Copper Nanoclusters. - 1 online resource (370 pages)

Source: Dissertation Abstracts International, Volume: 79-02(E), Section: B.

Thesis (Ph.D.)--University of California, Santa Barbara, 2017.

Includes bibliographical references

The reactivity of MCl3(eta1-TEMPO) (M = Fe, Al; TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) with a variety of lignin models, including 3,4-dimethoxybenzyl alcohol, 1-phenyl-2-phenoxyethanol and 1,2-diphenyl-2-methoxyethanol is investigated. FeCl3(TEMPO) is effective in cleanly converting these substrates to the corresponding aldehyde or ketone. AlCl3(eta1-TEMPO) is also able to oxidize these substrates, however in a few instances the products of over-oxidation are also observed. In contrast, 2-phenoxyethanol is not oxidized by MCl 3(eta1-TEMPO); instead it likely coordinates to the metal center, forming a 2-phenoxyethoxide complex. Oxidation of activated alkanes by MCl3(eta1-TEMPO) suggests that the reactions proceed via an initial 1-electron concerted proton-electron transfer (CPET) event. Finally, reaction of TEMPO with FeBr3 in Et 2O results in oxidation of the solvent.

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2018

Mode of access: World Wide Web

ISBN: 9780355430097Subjects--Topical Terms:

632473
Nanoscience.
Index Terms--Genre/Form:

554714
Electronic books.

Synthesis and Characterization of Atomically Precise Copper Nanoclusters.
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100 1 $a Nguyen, Thuy-Ai Dang. $3 1187044
245 1 0 $a Synthesis and Characterization of Atomically Precise Copper Nanoclusters.
264 0 $c 2017
300 $a 1 online resource (370 pages)
336 $a text $b txt $2 rdacontent
337 $a computer $b c $2 rdamedia
338 $a online resource $b cr $2 rdacarrier
500 $a Source: Dissertation Abstracts International, Volume: 79-02(E), Section: B.
500 $a Adviser: Trevor W. Hayton.
502 $a Thesis (Ph.D.)--University of California, Santa Barbara, 2017.
504 $a Includes bibliographical references
520 $a The reactivity of MCl3(eta1-TEMPO) (M = Fe, Al; TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) with a variety of lignin models, including 3,4-dimethoxybenzyl alcohol, 1-phenyl-2-phenoxyethanol and 1,2-diphenyl-2-methoxyethanol is investigated. FeCl3(TEMPO) is effective in cleanly converting these substrates to the corresponding aldehyde or ketone. AlCl3(eta1-TEMPO) is also able to oxidize these substrates, however in a few instances the products of over-oxidation are also observed. In contrast, 2-phenoxyethanol is not oxidized by MCl 3(eta1-TEMPO); instead it likely coordinates to the metal center, forming a 2-phenoxyethoxide complex. Oxidation of activated alkanes by MCl3(eta1-TEMPO) suggests that the reactions proceed via an initial 1-electron concerted proton-electron transfer (CPET) event. Finally, reaction of TEMPO with FeBr3 in Et 2O results in oxidation of the solvent.
520 $a The copper hydride clusters [Cu14H12(phen) 6(PPh3)4][X]2 (X = Cl, OTf) are obtained in good yields by reaction of [(Ph3P)CuH]6 with 1,10-phenanthroline, in the presence of a halide or pseudohalide source. [Cu14H 12(phen)6(PPh3)4][Cl]2 reacts with CO2 in CH2Cl2, in the presence of excess Ph3P, to form the formate complex, [(Ph3P)2Cu(kappa 2-O2CH)], along with [(phen)(Ph3P)CuCl].
520 $a [Cu25H22(PPh3)12]Cl and [Cu 18H17(PPh3)10]Cl, are isolated from the reaction of Cu(OAc) and CuCl with Ph2SiH2, in the presence of PPh3. [Cu25H22(PPh3) 12]Cl formally features partial Cu(0) character. Subsequent reaction with Ph2phen resulted in the isolation of [Cu29Cl 4H22(Ph2phen)12]Cl (Ph2phen = 4,7-diphenyl-1,10-phenanthroline), in good yields. A time-resolved kinetic evaluation of the formation of [Cu29Cl4H22(Ph 2phen)12]Cl reveals that the mechanism of cluster growth is initiated by rapid ligand exchange, followed by slower extrusion of CuCl monomer, transport, and subsequent capture by intact clusters.
520 $a Two Cu26 nanoclusters, tentatively formulated as [Cu 26H17(PPh3)9(OAc)3] and [Cu26H22(PPh3)10(OAc)2], are isolated from the reaction of Cu(OAc) with Ph2SiH2, in the presence of PPh3. As formulated, [Cu26H 17(PPh3)9(OAc)3] features a magic number N* = 6, which is unprecedented for a copper nanocluster. XANES supports an assignment of more Cu(0) character than [Cu25H 22(PPh3)12]Cl (N* = 2) for this complex.
520 $a A critical reevaluation of the synthesis and characterization of Cu 8(MPP)4 is reported. This product was reportedly formed by reaction of Cu(NO3)2 with 2-mercapto-5-n-propylpyrimidine (HMPP) and NaBH4, in ethanol, in the presence of [N(C8H 17)4][Br]. However, upon reevaluation, no experimental evidence to support the existence of Cu8(MPP)4 was found. Instead, the material isolated from this reaction is a complex mixture containing [N(C8H17)4]+, Br -, NO3-, 2-mercapto-5-n-propyl-1,6-dihydropyrimidine (H2MPP*), along with the Cu(I) coordination polymer, [Cu(MPP)]n. H2MPP* and [Cu(MPP)]n, as well as the related Cu(I) coordination complexes, [Cu(HMPP*)]n and [Cu2(MPP*)]n are independently synthesized to support these conclusions.
533 $a Electronic reproduction. $b Ann Arbor, Mich. : $c ProQuest, $d 2018
538 $a Mode of access: World Wide Web
650 4 $a Nanoscience. $3 632473
650 4 $a Inorganic chemistry. $3 1182077
655 7 $a Electronic books. $2 local $3 554714
690 $a 0565
690 $a 0488
710 2 $a ProQuest Information and Learning Co. $3 1178819
710 2 $a University of California, Santa Barbara. $b Chemistry. $3 1186922
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=10635086 $z click for full text (PQDT)