schliessen

Filtern

 

Bibliotheken

Biomimetic oxidation reactions of a naked manganese(V)-oxo porphyrin complex.

The intrinsic reactivity of a manganese(V)‐oxo porphyrin complex, a typically fleeting intermediate in catalytic oxidation reactions in solution, has been elucidated in a study focused on its gas‐phase ion‐chemistry. The naked high‐valent Mn‐oxo porphyrin intermediate ([(tpfpp)MnO]; tpfpp=‐tetrakis(... Full description

Journal Title: Chemistry (Weinheim an der Bergstrasse Germany), October 17, 2011, Vol.17(43), pp.12092-12100
Main Author: Lanucara, Francesco
Other Authors: Crestoni, Maria Elisa
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: E-ISSN: 1521-3765 ; DOI: 10.1002/chem.201101432
Link: http://search.proquest.com/docview/898171034/?pq-origsite=primo
Zum Text:
SendSend as email Add to Book BagAdd to Book Bag
Staff View
recordid: proquest898171034
title: Biomimetic oxidation reactions of a naked manganese(V)-oxo porphyrin complex.
format: Article
creator:
  • Lanucara, Francesco
  • Crestoni, Maria Elisa
subjects:
  • Biomimetics–Chemistry
  • Catalysis–Chemistry
  • Electrons–Chemistry
  • Gases–Chemistry
  • Kinetics–Chemistry
  • Ligands–Chemistry
  • Manganese–Chemistry
  • Metalloporphyrins–Chemistry
  • Molecular Structure–Chemistry
  • Oxidation-Reduction–Chemistry
  • Porphyrins–Chemistry
  • Gases
  • Ligands
  • Metalloporphyrins
  • Porphyrins
  • Manganese
ispartof: Chemistry (Weinheim an der Bergstrasse, Germany), October 17, 2011, Vol.17(43), pp.12092-12100
description: The intrinsic reactivity of a manganese(V)‐oxo porphyrin complex, a typically fleeting intermediate in catalytic oxidation reactions in solution, has been elucidated in a study focused on its gas‐phase ion‐chemistry. The naked high‐valent Mn‐oxo porphyrin intermediate ([(tpfpp)MnO]; tpfpp=‐tetrakis(pentafluorophenyl)porphinato dianion), has been obtained by controlled treatment of [(tpfpp)Mn]Cl (‐Cl) with iodosylbenzene in methanol, delivered in the gas phase by electrospray ionization and assayed by FT‐ICR mass spectrometry. A direct kinetic study of the reaction with selected substrates, each containing a heteroatom X (X=S, N, P) including amines, sulfides, and phosphites, was thus performed. Ionic products arising from electron transfer (ET), hydride transfer (HT), oxygen‐atom transfer (OAT), and formal addition (Add) may be observed, with a predominance of two‐electron processes, whereas the product of hydrogen‐atom transfer (HAT), [(tpfpp)MnOH], is never detected. A thermochemical threshold for the formation of the product radical cation allows an evaluation of the electron‐transfer ability of a Mn‐oxo complex, yielding a lower limit of 7.85 eV for the ionization energy of gaseous [(tpfpp)MnO]. Linear free‐energy analyses of the reactions of ‐substituted ,‐dimethylanilines and thioanisoles indicate that a considerable amount of positive charge is developed on the heteroatom in the oxidation transition state. Substrates endowed with different heteroatoms, but similar ionization energy display a comparable reaction efficiency, consistent with a mechanism initiated by ET. For the first time, the kinetic acidity of putative hydroxo intermediates playing a role in catalytic oxidations, [(tpfpp)FeOH] and [(tpfpp)MnOH], has been investigated with selected reference bases, revealing a comparatively higher basicity for the ferryl, [(tpfpp)FeO], with respect to the manganyl, [(tpfpp)MnO], unit. Finally, the neat association reaction of has been studied with various ligands showing that harder ligands are more strongly bound. : New insight into the reactivity of bare [(tpfpp)MnO] ions (tpfpp=‐tetrakis(pentafluorophenyl)porphinato dianion) with substrates (L) containing a heteroatom (e.g., amines, sulfides, phosphites) is obtained by ESI‐FT‐ICR mass spectrometry. The reaction pathways are initiated by electron transfer and yield products involving O‐atom coupling and transfer, besides hydride transfer (see scheme).
language: eng
source:
identifier: E-ISSN: 1521-3765 ; DOI: 10.1002/chem.201101432
fulltext: fulltext
issn:
  • 15213765
  • 1521-3765
url: Link


@attributes
ID1684396233
RANK0.07
NO1
SEARCH_ENGINEprimo_central_multiple_fe
SEARCH_ENGINE_TYPEPrimo Central Search Engine
LOCALfalse
PrimoNMBib
record
control
sourcerecordid898171034
sourceidproquest
recordidTN_proquest898171034
sourcesystemPC
pqid898171034
display
typearticle
titleBiomimetic oxidation reactions of a naked manganese(V)-oxo porphyrin complex.
creatorLanucara, Francesco ; Crestoni, Maria Elisa
contributorLanucara, Francesco (correspondence author) ; Lanucara, Francesco (record owner)
ispartofChemistry (Weinheim an der Bergstrasse, Germany), October 17, 2011, Vol.17(43), pp.12092-12100
identifierE-ISSN: 1521-3765 ; DOI: 10.1002/chem.201101432
subjectBiomimetics–Chemistry ; Catalysis–Chemistry ; Electrons–Chemistry ; Gases–Chemistry ; Kinetics–Chemistry ; Ligands–Chemistry ; Manganese–Chemistry ; Metalloporphyrins–Chemistry ; Molecular Structure–Chemistry ; Oxidation-Reduction–Chemistry ; Porphyrins–Chemistry ; Gases ; Ligands ; Metalloporphyrins ; Porphyrins ; Manganese
languageeng
source
descriptionThe intrinsic reactivity of a manganese(V)‐oxo porphyrin complex, a typically fleeting intermediate in catalytic oxidation reactions in solution, has been elucidated in a study focused on its gas‐phase ion‐chemistry. The naked high‐valent Mn‐oxo porphyrin intermediate ([(tpfpp)MnO]; tpfpp=‐tetrakis(pentafluorophenyl)porphinato dianion), has been obtained by controlled treatment of [(tpfpp)Mn]Cl (‐Cl) with iodosylbenzene in methanol, delivered in the gas phase by electrospray ionization and assayed by FT‐ICR mass spectrometry. A direct kinetic study of the reaction with selected substrates, each containing a heteroatom X (X=S, N, P) including amines, sulfides, and phosphites, was thus performed. Ionic products arising from electron transfer (ET), hydride transfer (HT), oxygen‐atom transfer (OAT), and formal addition (Add) may be observed, with a predominance of two‐electron processes, whereas the product of hydrogen‐atom transfer (HAT), [(tpfpp)MnOH], is never detected. A thermochemical threshold for the formation of the product radical cation allows an evaluation of the electron‐transfer ability of a Mn‐oxo complex, yielding a lower limit of 7.85 eV for the ionization energy of gaseous [(tpfpp)MnO]. Linear free‐energy analyses of the reactions of ‐substituted ,‐dimethylanilines and thioanisoles indicate that a considerable amount of positive charge is developed on the heteroatom in the oxidation transition state. Substrates endowed with different heteroatoms, but similar ionization energy display a comparable reaction efficiency, consistent with a mechanism initiated by ET. For the first time, the kinetic acidity of putative hydroxo intermediates playing a role in catalytic oxidations, [(tpfpp)FeOH] and [(tpfpp)MnOH], has been investigated with selected reference bases, revealing a comparatively higher basicity for the ferryl, [(tpfpp)FeO], with respect to the manganyl, [(tpfpp)MnO], unit. Finally, the neat association reaction of has been studied with various ligands showing that harder ligands are more strongly bound. : New insight into the reactivity of bare [(tpfpp)MnO] ions (tpfpp=‐tetrakis(pentafluorophenyl)porphinato dianion) with substrates (L) containing a heteroatom (e.g., amines, sulfides, phosphites) is obtained by ESI‐FT‐ICR mass spectrometry. The reaction pathways are initiated by electron transfer and yield products involving O‐atom coupling and transfer, besides hydride transfer (see scheme).
version5
lds50peer_reviewed
links
openurl$$Topenurl_article
openurlfulltext$$Topenurlfull_article
backlink$$Uhttp://search.proquest.com/docview/898171034/?pq-origsite=primo$$EView_record_in_ProQuest_(subscribers_only)
search
creatorcontrib
0Lanucara, Francesco
1Crestoni, Maria Elisa
titleBiomimetic oxidation reactions of a naked manganese(V)-oxo porphyrin complex.
subject
0Biomimetics–Chemistry
1Catalysis–Chemistry
2Electrons–Chemistry
3Gases–Chemistry
4Kinetics–Chemistry
5Ligands–Chemistry
6Manganese–Chemistry
7Metalloporphyrins–Chemistry
8Molecular Structure–Chemistry
9Oxidation-Reduction–Chemistry
10Porphyrins–Chemistry
11Gases
12Ligands
13Metalloporphyrins...
general
0English
110.1002/chem.201101432
2MEDLINE (ProQuest)
3ProQuest Biological Science Collection
4ProQuest Natural Science Collection
5ProQuest SciTech Collection
6Biological Science Database
7Natural Science Collection
8SciTech Premium Collection
9Health Research Premium Collection
10Health Research Premium Collection (Alumni edition)
11Biological Science Index (ProQuest)
sourceidproquest
recordidproquest898171034
issn
015213765
11521-3765
rsrctypearticle
creationdate2011
addtitleChemistry (Weinheim an der Bergstrasse, Germany)
searchscope
01007527
11007944
21009130
310000004
410000038
510000050
610000120
710000159
810000238
910000253
1010000260
1110000270
1210000271
1310000302
1410000350
15proquest
scope
01007527
11007944
21009130
310000004
410000038
510000050
610000120
710000159
810000238
910000253
1010000260
1110000270
1210000271
1310000302
1410000350
15proquest
lsr43
01007527false
11007944false
21009130false
310000004false
410000038false
510000050false
610000120false
710000159false
810000238false
910000253false
1010000260false
1110000270false
1210000271false
1310000302false
1410000350false
contributorLanucara, Francesco
startdate20111017
enddate20111017
citationpf 12092 pt 12100 vol 17 issue 43
lsr30VSR-Enriched:[description, pqid, issn]
sort
titleBiomimetic oxidation reactions of a naked manganese(V)-oxo porphyrin complex.
authorLanucara, Francesco ; Crestoni, Maria Elisa
creationdate20111017
lso0120111017
facets
frbrgroupid6671765571564277644
frbrtype5
newrecords20181218
languageeng
creationdate2011
topic
0Biomimetics–Chemistry
1Catalysis–Chemistry
2Electrons–Chemistry
3Gases–Chemistry
4Kinetics–Chemistry
5Ligands–Chemistry
6Manganese–Chemistry
7Metalloporphyrins–Chemistry
8Molecular Structure–Chemistry
9Oxidation-Reduction–Chemistry
10Porphyrins–Chemistry
11Gases
12Ligands
13Metalloporphyrins...
collection
0MEDLINE (ProQuest)
1ProQuest Biological Science Collection
2ProQuest Natural Science Collection
3ProQuest SciTech Collection
4Biological Science Database
5Natural Science Collection
6SciTech Premium Collection
7Health Research Premium Collection
8Health Research Premium Collection (Alumni edition)
9Biological Science Index (ProQuest)
prefilterarticles
rsrctypearticles
creatorcontrib
0Lanucara, Francesco
1Crestoni, Maria Elisa
jtitleChemistry (Weinheim an der Bergstrasse, Germany)
toplevelpeer_reviewed
delivery
delcategoryRemote Search Resource
fulltextfulltext
addata
aulast
0Lanucara
1Crestoni
aufirst
0Francesco
1Maria Elisa
au
0Lanucara, Francesco
1Crestoni, Maria Elisa
addauLanucara, Francesco
atitleBiomimetic oxidation reactions of a naked manganese(V)-oxo porphyrin complex.
jtitleChemistry (Weinheim an der Bergstrasse, Germany)
risdate20111017
volume17
issue43
spage12092
epage12100
pages12092-12100
eissn1521-3765
formatjournal
genrearticle
ristypeJOUR
doi10.1002/chem.201101432
urlhttp://search.proquest.com/docview/898171034/
issn09476539
date2011-10-17