Studies in negative ion mass spectrometry: XIVPart XIII, Org. Mass Spectrom. 14, 676 (1979). - Electron attachment reactions of a series of η6-arenetricarbonylchromium(O) complexes
Blake, M. R. ; Garnett, J. L. ; Gregor, I. K. ; Wild, S. B.
Chichester : Wiley-Blackwell
Published 1980
Chichester : Wiley-Blackwell
Published 1980
| ISSN: |
0030-493X
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|---|---|
| Keywords: |
Chemistry ; Analytical Chemistry and Spectroscopy
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| Source: |
Wiley InterScience Backfile Collection 1832-2000
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| Topics: |
Chemistry and Pharmacology
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| Notes: |
Electron attachment reactions of a series of (η6-arene)tricarbonylchromium(O) complexes have been examined in the gas phase. The electron capture process has been shown to be influenced by the structure of the η6-arene ligand and its substituents. Whereas (η6-benzene)- and (η6-mesitylene)tricarbonylchromium(O) undergo dissocative electron capture, or reductive decarbonylation, yielding [M—CO]-· ions of highest abundance in their negative ion mass spectra, [η6-(2,2-dimethylindan-1,3-dione)]tricarbonylchromium(O) forms a molecular negative ion which undergoes sequential CO eliminations and finally a demetallation to give the arene radical ion. A localization of charge on the coordinated arene ligand is proposed for the formation of [M]-· in this case. (η6-Methylbenzoate)tricarbonylchromium(O) also forms a molecular negative ion by secondary electron attachment which decomposes by simultaneous and consecutive eliminations of up to four CO molecules. The elucidation of a mechanism and sequence for these CO eliminations has been achieved by synthesizing and examining the negative ion mass spectrum of [η6-(C6H5·13CO2Me)]Cr(CO)3. The first CO loss in the principal fragmentation pathway occurs solely from the -Cr(CO)3 group of [M]-·. The effect of para substituent groups on the stabilities of molecular negative ions and their fragmentations has been ascertained using a series of para-substituted (η6-methylbenzoate)tricarbonylchromium(O) compounds containing the groups NH2, OH, OCH3, CL and COOMe. The stabilities of the [M]-· ions have been rationalized in terms of the Hammett and Taft parameters σP, σI, σRP, σPO and σRO. The overall electronic substituent effect transmitted to the carbonyl groups of the -Cr(CO)3 unit involves both resonance and inductive components. In this series of compounds the stability of [M]-· decreases as the electron withdrawing capacities of the para substituents increase.
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| Additional Material: |
3 Ill.
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| Type of Medium: |
Electronic Resource
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| URL: |
| _version_ | 1798298027031527426 |
|---|---|
| addmaterial | 3 Ill. |
| autor | Blake, M. R. Garnett, J. L. Gregor, I. K. Wild, S. B. |
| autorsonst | Blake, M. R. Garnett, J. L. Gregor, I. K. Wild, S. B. |
| book_url | http://dx.doi.org/10.1002/oms.1210150711 |
| datenlieferant | nat_lic_papers |
| hauptsatz | hsatz_simple |
| identnr | NLM159265061 |
| issn | 0030-493X |
| journal_name | Biological Mass Spectrometry |
| materialart | 1 |
| notes | Electron attachment reactions of a series of (η6-arene)tricarbonylchromium(O) complexes have been examined in the gas phase. The electron capture process has been shown to be influenced by the structure of the η6-arene ligand and its substituents. Whereas (η6-benzene)- and (η6-mesitylene)tricarbonylchromium(O) undergo dissocative electron capture, or reductive decarbonylation, yielding [M—CO]-· ions of highest abundance in their negative ion mass spectra, [η6-(2,2-dimethylindan-1,3-dione)]tricarbonylchromium(O) forms a molecular negative ion which undergoes sequential CO eliminations and finally a demetallation to give the arene radical ion. A localization of charge on the coordinated arene ligand is proposed for the formation of [M]-· in this case. (η6-Methylbenzoate)tricarbonylchromium(O) also forms a molecular negative ion by secondary electron attachment which decomposes by simultaneous and consecutive eliminations of up to four CO molecules. The elucidation of a mechanism and sequence for these CO eliminations has been achieved by synthesizing and examining the negative ion mass spectrum of [η6-(C6H5·13CO2Me)]Cr(CO)3. The first CO loss in the principal fragmentation pathway occurs solely from the -Cr(CO)3 group of [M]-·. The effect of para substituent groups on the stabilities of molecular negative ions and their fragmentations has been ascertained using a series of para-substituted (η6-methylbenzoate)tricarbonylchromium(O) compounds containing the groups NH2, OH, OCH3, CL and COOMe. The stabilities of the [M]-· ions have been rationalized in terms of the Hammett and Taft parameters σP, σI, σRP, σPO and σRO. The overall electronic substituent effect transmitted to the carbonyl groups of the -Cr(CO)3 unit involves both resonance and inductive components. In this series of compounds the stability of [M]-· decreases as the electron withdrawing capacities of the para substituents increase. |
| package_name | Wiley-Blackwell |
| publikationsjahr_anzeige | 1980 |
| publikationsjahr_facette | 1980 |
| publikationsjahr_intervall | 8019:1980-1984 |
| publikationsjahr_sort | 1980 |
| publikationsort | Chichester |
| publisher | Wiley-Blackwell |
| reference | 15 (1980), S. 369-375 |
| schlagwort | Chemistry Analytical Chemistry and Spectroscopy |
| search_space | articles |
| shingle_author_1 | Blake, M. R. Garnett, J. L. Gregor, I. K. Wild, S. B. |
| shingle_author_2 | Blake, M. R. Garnett, J. L. Gregor, I. K. Wild, S. B. |
| shingle_author_3 | Blake, M. R. Garnett, J. L. Gregor, I. K. Wild, S. B. |
| shingle_author_4 | Blake, M. R. Garnett, J. L. Gregor, I. K. Wild, S. B. |
| shingle_catch_all_1 | Blake, M. R. Garnett, J. L. Gregor, I. K. Wild, S. B. Studies in negative ion mass spectrometry: XIVPart XIII, Org. Mass Spectrom. 14, 676 (1979). - Electron attachment reactions of a series of η6-arenetricarbonylchromium(O) complexes Chemistry Analytical Chemistry and Spectroscopy Chemistry Analytical Chemistry and Spectroscopy Electron attachment reactions of a series of (η6-arene)tricarbonylchromium(O) complexes have been examined in the gas phase. The electron capture process has been shown to be influenced by the structure of the η6-arene ligand and its substituents. Whereas (η6-benzene)- and (η6-mesitylene)tricarbonylchromium(O) undergo dissocative electron capture, or reductive decarbonylation, yielding [M—CO]-· ions of highest abundance in their negative ion mass spectra, [η6-(2,2-dimethylindan-1,3-dione)]tricarbonylchromium(O) forms a molecular negative ion which undergoes sequential CO eliminations and finally a demetallation to give the arene radical ion. A localization of charge on the coordinated arene ligand is proposed for the formation of [M]-· in this case. (η6-Methylbenzoate)tricarbonylchromium(O) also forms a molecular negative ion by secondary electron attachment which decomposes by simultaneous and consecutive eliminations of up to four CO molecules. The elucidation of a mechanism and sequence for these CO eliminations has been achieved by synthesizing and examining the negative ion mass spectrum of [η6-(C6H5·13CO2Me)]Cr(CO)3. The first CO loss in the principal fragmentation pathway occurs solely from the -Cr(CO)3 group of [M]-·. The effect of para substituent groups on the stabilities of molecular negative ions and their fragmentations has been ascertained using a series of para-substituted (η6-methylbenzoate)tricarbonylchromium(O) compounds containing the groups NH2, OH, OCH3, CL and COOMe. The stabilities of the [M]-· ions have been rationalized in terms of the Hammett and Taft parameters σP, σI, σRP, σPO and σRO. The overall electronic substituent effect transmitted to the carbonyl groups of the -Cr(CO)3 unit involves both resonance and inductive components. In this series of compounds the stability of [M]-· decreases as the electron withdrawing capacities of the para substituents increase. 0030-493X 0030493X Wiley-Blackwell |
| shingle_catch_all_2 | Blake, M. R. Garnett, J. L. Gregor, I. K. Wild, S. B. Studies in negative ion mass spectrometry: XIVPart XIII, Org. Mass Spectrom. 14, 676 (1979). - Electron attachment reactions of a series of η6-arenetricarbonylchromium(O) complexes Chemistry Analytical Chemistry and Spectroscopy Chemistry Analytical Chemistry and Spectroscopy Electron attachment reactions of a series of (η6-arene)tricarbonylchromium(O) complexes have been examined in the gas phase. The electron capture process has been shown to be influenced by the structure of the η6-arene ligand and its substituents. Whereas (η6-benzene)- and (η6-mesitylene)tricarbonylchromium(O) undergo dissocative electron capture, or reductive decarbonylation, yielding [M—CO]-· ions of highest abundance in their negative ion mass spectra, [η6-(2,2-dimethylindan-1,3-dione)]tricarbonylchromium(O) forms a molecular negative ion which undergoes sequential CO eliminations and finally a demetallation to give the arene radical ion. A localization of charge on the coordinated arene ligand is proposed for the formation of [M]-· in this case. (η6-Methylbenzoate)tricarbonylchromium(O) also forms a molecular negative ion by secondary electron attachment which decomposes by simultaneous and consecutive eliminations of up to four CO molecules. The elucidation of a mechanism and sequence for these CO eliminations has been achieved by synthesizing and examining the negative ion mass spectrum of [η6-(C6H5·13CO2Me)]Cr(CO)3. The first CO loss in the principal fragmentation pathway occurs solely from the -Cr(CO)3 group of [M]-·. The effect of para substituent groups on the stabilities of molecular negative ions and their fragmentations has been ascertained using a series of para-substituted (η6-methylbenzoate)tricarbonylchromium(O) compounds containing the groups NH2, OH, OCH3, CL and COOMe. The stabilities of the [M]-· ions have been rationalized in terms of the Hammett and Taft parameters σP, σI, σRP, σPO and σRO. The overall electronic substituent effect transmitted to the carbonyl groups of the -Cr(CO)3 unit involves both resonance and inductive components. In this series of compounds the stability of [M]-· decreases as the electron withdrawing capacities of the para substituents increase. 0030-493X 0030493X Wiley-Blackwell |
| shingle_catch_all_3 | Blake, M. R. Garnett, J. L. Gregor, I. K. Wild, S. B. Studies in negative ion mass spectrometry: XIVPart XIII, Org. Mass Spectrom. 14, 676 (1979). - Electron attachment reactions of a series of η6-arenetricarbonylchromium(O) complexes Chemistry Analytical Chemistry and Spectroscopy Chemistry Analytical Chemistry and Spectroscopy Electron attachment reactions of a series of (η6-arene)tricarbonylchromium(O) complexes have been examined in the gas phase. The electron capture process has been shown to be influenced by the structure of the η6-arene ligand and its substituents. Whereas (η6-benzene)- and (η6-mesitylene)tricarbonylchromium(O) undergo dissocative electron capture, or reductive decarbonylation, yielding [M—CO]-· ions of highest abundance in their negative ion mass spectra, [η6-(2,2-dimethylindan-1,3-dione)]tricarbonylchromium(O) forms a molecular negative ion which undergoes sequential CO eliminations and finally a demetallation to give the arene radical ion. A localization of charge on the coordinated arene ligand is proposed for the formation of [M]-· in this case. (η6-Methylbenzoate)tricarbonylchromium(O) also forms a molecular negative ion by secondary electron attachment which decomposes by simultaneous and consecutive eliminations of up to four CO molecules. The elucidation of a mechanism and sequence for these CO eliminations has been achieved by synthesizing and examining the negative ion mass spectrum of [η6-(C6H5·13CO2Me)]Cr(CO)3. The first CO loss in the principal fragmentation pathway occurs solely from the -Cr(CO)3 group of [M]-·. The effect of para substituent groups on the stabilities of molecular negative ions and their fragmentations has been ascertained using a series of para-substituted (η6-methylbenzoate)tricarbonylchromium(O) compounds containing the groups NH2, OH, OCH3, CL and COOMe. The stabilities of the [M]-· ions have been rationalized in terms of the Hammett and Taft parameters σP, σI, σRP, σPO and σRO. The overall electronic substituent effect transmitted to the carbonyl groups of the -Cr(CO)3 unit involves both resonance and inductive components. In this series of compounds the stability of [M]-· decreases as the electron withdrawing capacities of the para substituents increase. 0030-493X 0030493X Wiley-Blackwell |
| shingle_catch_all_4 | Blake, M. R. Garnett, J. L. Gregor, I. K. Wild, S. B. Studies in negative ion mass spectrometry: XIVPart XIII, Org. Mass Spectrom. 14, 676 (1979). - Electron attachment reactions of a series of η6-arenetricarbonylchromium(O) complexes Chemistry Analytical Chemistry and Spectroscopy Chemistry Analytical Chemistry and Spectroscopy Electron attachment reactions of a series of (η6-arene)tricarbonylchromium(O) complexes have been examined in the gas phase. The electron capture process has been shown to be influenced by the structure of the η6-arene ligand and its substituents. Whereas (η6-benzene)- and (η6-mesitylene)tricarbonylchromium(O) undergo dissocative electron capture, or reductive decarbonylation, yielding [M—CO]-· ions of highest abundance in their negative ion mass spectra, [η6-(2,2-dimethylindan-1,3-dione)]tricarbonylchromium(O) forms a molecular negative ion which undergoes sequential CO eliminations and finally a demetallation to give the arene radical ion. A localization of charge on the coordinated arene ligand is proposed for the formation of [M]-· in this case. (η6-Methylbenzoate)tricarbonylchromium(O) also forms a molecular negative ion by secondary electron attachment which decomposes by simultaneous and consecutive eliminations of up to four CO molecules. The elucidation of a mechanism and sequence for these CO eliminations has been achieved by synthesizing and examining the negative ion mass spectrum of [η6-(C6H5·13CO2Me)]Cr(CO)3. The first CO loss in the principal fragmentation pathway occurs solely from the -Cr(CO)3 group of [M]-·. The effect of para substituent groups on the stabilities of molecular negative ions and their fragmentations has been ascertained using a series of para-substituted (η6-methylbenzoate)tricarbonylchromium(O) compounds containing the groups NH2, OH, OCH3, CL and COOMe. The stabilities of the [M]-· ions have been rationalized in terms of the Hammett and Taft parameters σP, σI, σRP, σPO and σRO. The overall electronic substituent effect transmitted to the carbonyl groups of the -Cr(CO)3 unit involves both resonance and inductive components. In this series of compounds the stability of [M]-· decreases as the electron withdrawing capacities of the para substituents increase. 0030-493X 0030493X Wiley-Blackwell |
| shingle_title_1 | Studies in negative ion mass spectrometry: XIVPart XIII, Org. Mass Spectrom. 14, 676 (1979). - Electron attachment reactions of a series of η6-arenetricarbonylchromium(O) complexes |
| shingle_title_2 | Studies in negative ion mass spectrometry: XIVPart XIII, Org. Mass Spectrom. 14, 676 (1979). - Electron attachment reactions of a series of η6-arenetricarbonylchromium(O) complexes |
| shingle_title_3 | Studies in negative ion mass spectrometry: XIVPart XIII, Org. Mass Spectrom. 14, 676 (1979). - Electron attachment reactions of a series of η6-arenetricarbonylchromium(O) complexes |
| shingle_title_4 | Studies in negative ion mass spectrometry: XIVPart XIII, Org. Mass Spectrom. 14, 676 (1979). - Electron attachment reactions of a series of η6-arenetricarbonylchromium(O) complexes |
| sigel_instance_filter | dkfz geomar wilbert ipn albert |
| source_archive | Wiley InterScience Backfile Collection 1832-2000 |
| timestamp | 2024-05-06T10:17:21.467Z |
| titel | Studies in negative ion mass spectrometry: XIVPart XIII, Org. Mass Spectrom. 14, 676 (1979). - Electron attachment reactions of a series of η6-arenetricarbonylchromium(O) complexes |
| titel_suche | Studies in negative ion mass spectrometry: XIVPart XIII, Org. Mass Spectrom. 14, 676 (1979). - Electron attachment reactions of a series of η6-arenetricarbonylchromium(O) complexes |
| topic | V |
| uid | nat_lic_papers_NLM159265061 |