Mechanism of acid-induced decomposition of 2-hydroxyethyl- and 2-alkoxyethyl-cobaloximes
The decomposition of hydroxyethyl-, ethoxyethyl- and phenoxyethyl(aquo)cobaloximes in sulfuric acid/water mixtures to produce ethylene has been studied spectrophotometrically and manometrically. Definitive kinetic evidence for formation of an intermediate which is common to all three starting comple...
Ausführliche Beschreibung
Gespeichert in:
| Autor*in: |
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| Format: |
E-Artikel |
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| Sprache: |
Englisch |
| Erschienen: |
1985 |
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| Reproduktion: |
Elsevier Journal Backfiles on ScienceDirect 1907 - 2002 |
|---|---|
| Übergeordnetes Werk: |
in: Journal of Organometallic Chemistry - Amsterdam : Elsevier, 287(1985), 3, Seite 377-394 |
| Übergeordnetes Werk: |
volume:287 ; year:1985 ; number:3 ; pages:377-394 |
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| 245 | 1 | 0 | |a Mechanism of acid-induced decomposition of 2-hydroxyethyl- and 2-alkoxyethyl-cobaloximes |
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| 520 | |a The decomposition of hydroxyethyl-, ethoxyethyl- and phenoxyethyl(aquo)cobaloximes in sulfuric acid/water mixtures to produce ethylene has been studied spectrophotometrically and manometrically. Definitive kinetic evidence for formation of an intermediate which is common to all three starting complexes and accumulates at acidities greater than 7.3 M H"2SO"4 has been obtained. A complete rate law which accounts for all of the ionizations of starting materials and intermediate has been derived and fit to the rate data. The rate-determining step for product formation is decomposition of the intermediate at all acidities: the intermediate accumulates in strong acid because of a shift in the equilibrium for its formation due to the reduced activity of water in strongly acidic media. Activation parameters for the decomposition of the intermediate, which may be formulated as an ethylene-cobaloxime(III) π-complex or as a σ-bonded ethyl carbonium ion, have been obtained. ^1H and ^1^3C NMR observations of the intermediate and its deuterated analog (from 1,1,2,2-tetradeuterio-2-hydroxyethyl(aquo)cobaloxime) have led to the conclusion that it is probably a σ-bonded ethyl carbonium ion which may be stabilized by σ-π hyperconjugation. | ||
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(DE-627)NLEJ175022704 (DE-599)GBVNLZ175022704 DE-627 ger DE-627 rakwb eng Mechanism of acid-induced decomposition of 2-hydroxyethyl- and 2-alkoxyethyl-cobaloximes 1985 nicht spezifiziert zzz rdacontent nicht spezifiziert z rdamedia nicht spezifiziert zu rdacarrier The decomposition of hydroxyethyl-, ethoxyethyl- and phenoxyethyl(aquo)cobaloximes in sulfuric acid/water mixtures to produce ethylene has been studied spectrophotometrically and manometrically. Definitive kinetic evidence for formation of an intermediate which is common to all three starting complexes and accumulates at acidities greater than 7.3 M H"2SO"4 has been obtained. A complete rate law which accounts for all of the ionizations of starting materials and intermediate has been derived and fit to the rate data. The rate-determining step for product formation is decomposition of the intermediate at all acidities: the intermediate accumulates in strong acid because of a shift in the equilibrium for its formation due to the reduced activity of water in strongly acidic media. Activation parameters for the decomposition of the intermediate, which may be formulated as an ethylene-cobaloxime(III) π-complex or as a σ-bonded ethyl carbonium ion, have been obtained. ^1H and ^1^3C NMR observations of the intermediate and its deuterated analog (from 1,1,2,2-tetradeuterio-2-hydroxyethyl(aquo)cobaloxime) have led to the conclusion that it is probably a σ-bonded ethyl carbonium ion which may be stabilized by σ-π hyperconjugation. Elsevier Journal Backfiles on ScienceDirect 1907 - 2002 Brown, K.L. oth Ramamurthy, S. oth Marynick, D.S. oth in Journal of Organometallic Chemistry Amsterdam : Elsevier 287(1985), 3, Seite 377-394 (DE-627)NLEJ174930496 (DE-600)1491530-3 0022-328X nnns volume:287 year:1985 number:3 pages:377-394 http://linkinghub.elsevier.com/retrieve/pii/0022-328X(85)80092-9 GBV_USEFLAG_H ZDB-1-SDJ GBV_NL_ARTICLE AR 287 1985 3 377-394 |
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(DE-627)NLEJ175022704 (DE-599)GBVNLZ175022704 DE-627 ger DE-627 rakwb eng Mechanism of acid-induced decomposition of 2-hydroxyethyl- and 2-alkoxyethyl-cobaloximes 1985 nicht spezifiziert zzz rdacontent nicht spezifiziert z rdamedia nicht spezifiziert zu rdacarrier The decomposition of hydroxyethyl-, ethoxyethyl- and phenoxyethyl(aquo)cobaloximes in sulfuric acid/water mixtures to produce ethylene has been studied spectrophotometrically and manometrically. Definitive kinetic evidence for formation of an intermediate which is common to all three starting complexes and accumulates at acidities greater than 7.3 M H"2SO"4 has been obtained. A complete rate law which accounts for all of the ionizations of starting materials and intermediate has been derived and fit to the rate data. The rate-determining step for product formation is decomposition of the intermediate at all acidities: the intermediate accumulates in strong acid because of a shift in the equilibrium for its formation due to the reduced activity of water in strongly acidic media. Activation parameters for the decomposition of the intermediate, which may be formulated as an ethylene-cobaloxime(III) π-complex or as a σ-bonded ethyl carbonium ion, have been obtained. ^1H and ^1^3C NMR observations of the intermediate and its deuterated analog (from 1,1,2,2-tetradeuterio-2-hydroxyethyl(aquo)cobaloxime) have led to the conclusion that it is probably a σ-bonded ethyl carbonium ion which may be stabilized by σ-π hyperconjugation. Elsevier Journal Backfiles on ScienceDirect 1907 - 2002 Brown, K.L. oth Ramamurthy, S. oth Marynick, D.S. oth in Journal of Organometallic Chemistry Amsterdam : Elsevier 287(1985), 3, Seite 377-394 (DE-627)NLEJ174930496 (DE-600)1491530-3 0022-328X nnns volume:287 year:1985 number:3 pages:377-394 http://linkinghub.elsevier.com/retrieve/pii/0022-328X(85)80092-9 GBV_USEFLAG_H ZDB-1-SDJ GBV_NL_ARTICLE AR 287 1985 3 377-394 |
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(DE-627)NLEJ175022704 (DE-599)GBVNLZ175022704 DE-627 ger DE-627 rakwb eng Mechanism of acid-induced decomposition of 2-hydroxyethyl- and 2-alkoxyethyl-cobaloximes 1985 nicht spezifiziert zzz rdacontent nicht spezifiziert z rdamedia nicht spezifiziert zu rdacarrier The decomposition of hydroxyethyl-, ethoxyethyl- and phenoxyethyl(aquo)cobaloximes in sulfuric acid/water mixtures to produce ethylene has been studied spectrophotometrically and manometrically. Definitive kinetic evidence for formation of an intermediate which is common to all three starting complexes and accumulates at acidities greater than 7.3 M H"2SO"4 has been obtained. A complete rate law which accounts for all of the ionizations of starting materials and intermediate has been derived and fit to the rate data. The rate-determining step for product formation is decomposition of the intermediate at all acidities: the intermediate accumulates in strong acid because of a shift in the equilibrium for its formation due to the reduced activity of water in strongly acidic media. Activation parameters for the decomposition of the intermediate, which may be formulated as an ethylene-cobaloxime(III) π-complex or as a σ-bonded ethyl carbonium ion, have been obtained. ^1H and ^1^3C NMR observations of the intermediate and its deuterated analog (from 1,1,2,2-tetradeuterio-2-hydroxyethyl(aquo)cobaloxime) have led to the conclusion that it is probably a σ-bonded ethyl carbonium ion which may be stabilized by σ-π hyperconjugation. Elsevier Journal Backfiles on ScienceDirect 1907 - 2002 Brown, K.L. oth Ramamurthy, S. oth Marynick, D.S. oth in Journal of Organometallic Chemistry Amsterdam : Elsevier 287(1985), 3, Seite 377-394 (DE-627)NLEJ174930496 (DE-600)1491530-3 0022-328X nnns volume:287 year:1985 number:3 pages:377-394 http://linkinghub.elsevier.com/retrieve/pii/0022-328X(85)80092-9 GBV_USEFLAG_H ZDB-1-SDJ GBV_NL_ARTICLE AR 287 1985 3 377-394 |
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(DE-627)NLEJ175022704 (DE-599)GBVNLZ175022704 DE-627 ger DE-627 rakwb eng Mechanism of acid-induced decomposition of 2-hydroxyethyl- and 2-alkoxyethyl-cobaloximes 1985 nicht spezifiziert zzz rdacontent nicht spezifiziert z rdamedia nicht spezifiziert zu rdacarrier The decomposition of hydroxyethyl-, ethoxyethyl- and phenoxyethyl(aquo)cobaloximes in sulfuric acid/water mixtures to produce ethylene has been studied spectrophotometrically and manometrically. Definitive kinetic evidence for formation of an intermediate which is common to all three starting complexes and accumulates at acidities greater than 7.3 M H"2SO"4 has been obtained. A complete rate law which accounts for all of the ionizations of starting materials and intermediate has been derived and fit to the rate data. The rate-determining step for product formation is decomposition of the intermediate at all acidities: the intermediate accumulates in strong acid because of a shift in the equilibrium for its formation due to the reduced activity of water in strongly acidic media. Activation parameters for the decomposition of the intermediate, which may be formulated as an ethylene-cobaloxime(III) π-complex or as a σ-bonded ethyl carbonium ion, have been obtained. ^1H and ^1^3C NMR observations of the intermediate and its deuterated analog (from 1,1,2,2-tetradeuterio-2-hydroxyethyl(aquo)cobaloxime) have led to the conclusion that it is probably a σ-bonded ethyl carbonium ion which may be stabilized by σ-π hyperconjugation. Elsevier Journal Backfiles on ScienceDirect 1907 - 2002 Brown, K.L. oth Ramamurthy, S. oth Marynick, D.S. oth in Journal of Organometallic Chemistry Amsterdam : Elsevier 287(1985), 3, Seite 377-394 (DE-627)NLEJ174930496 (DE-600)1491530-3 0022-328X nnns volume:287 year:1985 number:3 pages:377-394 http://linkinghub.elsevier.com/retrieve/pii/0022-328X(85)80092-9 GBV_USEFLAG_H ZDB-1-SDJ GBV_NL_ARTICLE AR 287 1985 3 377-394 |
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(DE-627)NLEJ175022704 (DE-599)GBVNLZ175022704 DE-627 ger DE-627 rakwb eng Mechanism of acid-induced decomposition of 2-hydroxyethyl- and 2-alkoxyethyl-cobaloximes 1985 nicht spezifiziert zzz rdacontent nicht spezifiziert z rdamedia nicht spezifiziert zu rdacarrier The decomposition of hydroxyethyl-, ethoxyethyl- and phenoxyethyl(aquo)cobaloximes in sulfuric acid/water mixtures to produce ethylene has been studied spectrophotometrically and manometrically. Definitive kinetic evidence for formation of an intermediate which is common to all three starting complexes and accumulates at acidities greater than 7.3 M H"2SO"4 has been obtained. A complete rate law which accounts for all of the ionizations of starting materials and intermediate has been derived and fit to the rate data. The rate-determining step for product formation is decomposition of the intermediate at all acidities: the intermediate accumulates in strong acid because of a shift in the equilibrium for its formation due to the reduced activity of water in strongly acidic media. Activation parameters for the decomposition of the intermediate, which may be formulated as an ethylene-cobaloxime(III) π-complex or as a σ-bonded ethyl carbonium ion, have been obtained. ^1H and ^1^3C NMR observations of the intermediate and its deuterated analog (from 1,1,2,2-tetradeuterio-2-hydroxyethyl(aquo)cobaloxime) have led to the conclusion that it is probably a σ-bonded ethyl carbonium ion which may be stabilized by σ-π hyperconjugation. Elsevier Journal Backfiles on ScienceDirect 1907 - 2002 Brown, K.L. oth Ramamurthy, S. oth Marynick, D.S. oth in Journal of Organometallic Chemistry Amsterdam : Elsevier 287(1985), 3, Seite 377-394 (DE-627)NLEJ174930496 (DE-600)1491530-3 0022-328X nnns volume:287 year:1985 number:3 pages:377-394 http://linkinghub.elsevier.com/retrieve/pii/0022-328X(85)80092-9 GBV_USEFLAG_H ZDB-1-SDJ GBV_NL_ARTICLE AR 287 1985 3 377-394 |
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mechanism of acid-induced decomposition of 2-hydroxyethyl- and 2-alkoxyethyl-cobaloximes |
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Mechanism of acid-induced decomposition of 2-hydroxyethyl- and 2-alkoxyethyl-cobaloximes |
| abstract |
The decomposition of hydroxyethyl-, ethoxyethyl- and phenoxyethyl(aquo)cobaloximes in sulfuric acid/water mixtures to produce ethylene has been studied spectrophotometrically and manometrically. Definitive kinetic evidence for formation of an intermediate which is common to all three starting complexes and accumulates at acidities greater than 7.3 M H"2SO"4 has been obtained. A complete rate law which accounts for all of the ionizations of starting materials and intermediate has been derived and fit to the rate data. The rate-determining step for product formation is decomposition of the intermediate at all acidities: the intermediate accumulates in strong acid because of a shift in the equilibrium for its formation due to the reduced activity of water in strongly acidic media. Activation parameters for the decomposition of the intermediate, which may be formulated as an ethylene-cobaloxime(III) π-complex or as a σ-bonded ethyl carbonium ion, have been obtained. ^1H and ^1^3C NMR observations of the intermediate and its deuterated analog (from 1,1,2,2-tetradeuterio-2-hydroxyethyl(aquo)cobaloxime) have led to the conclusion that it is probably a σ-bonded ethyl carbonium ion which may be stabilized by σ-π hyperconjugation. |
| abstractGer |
The decomposition of hydroxyethyl-, ethoxyethyl- and phenoxyethyl(aquo)cobaloximes in sulfuric acid/water mixtures to produce ethylene has been studied spectrophotometrically and manometrically. Definitive kinetic evidence for formation of an intermediate which is common to all three starting complexes and accumulates at acidities greater than 7.3 M H"2SO"4 has been obtained. A complete rate law which accounts for all of the ionizations of starting materials and intermediate has been derived and fit to the rate data. The rate-determining step for product formation is decomposition of the intermediate at all acidities: the intermediate accumulates in strong acid because of a shift in the equilibrium for its formation due to the reduced activity of water in strongly acidic media. Activation parameters for the decomposition of the intermediate, which may be formulated as an ethylene-cobaloxime(III) π-complex or as a σ-bonded ethyl carbonium ion, have been obtained. ^1H and ^1^3C NMR observations of the intermediate and its deuterated analog (from 1,1,2,2-tetradeuterio-2-hydroxyethyl(aquo)cobaloxime) have led to the conclusion that it is probably a σ-bonded ethyl carbonium ion which may be stabilized by σ-π hyperconjugation. |
| abstract_unstemmed |
The decomposition of hydroxyethyl-, ethoxyethyl- and phenoxyethyl(aquo)cobaloximes in sulfuric acid/water mixtures to produce ethylene has been studied spectrophotometrically and manometrically. Definitive kinetic evidence for formation of an intermediate which is common to all three starting complexes and accumulates at acidities greater than 7.3 M H"2SO"4 has been obtained. A complete rate law which accounts for all of the ionizations of starting materials and intermediate has been derived and fit to the rate data. The rate-determining step for product formation is decomposition of the intermediate at all acidities: the intermediate accumulates in strong acid because of a shift in the equilibrium for its formation due to the reduced activity of water in strongly acidic media. Activation parameters for the decomposition of the intermediate, which may be formulated as an ethylene-cobaloxime(III) π-complex or as a σ-bonded ethyl carbonium ion, have been obtained. ^1H and ^1^3C NMR observations of the intermediate and its deuterated analog (from 1,1,2,2-tetradeuterio-2-hydroxyethyl(aquo)cobaloxime) have led to the conclusion that it is probably a σ-bonded ethyl carbonium ion which may be stabilized by σ-π hyperconjugation. |
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<?xml version="1.0" encoding="UTF-8"?><collection xmlns="http://www.loc.gov/MARC21/slim"><record><leader>01000caa a22002652 4500</leader><controlfield tag="001">NLEJ175022704</controlfield><controlfield tag="003">DE-627</controlfield><controlfield tag="005">20230506081818.0</controlfield><controlfield tag="007">cr uuu---uuuuu</controlfield><controlfield tag="008">070505s1985 xx |||||o 00| ||eng c</controlfield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(DE-627)NLEJ175022704</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(DE-599)GBVNLZ175022704</subfield></datafield><datafield tag="040" ind1=" " ind2=" "><subfield code="a">DE-627</subfield><subfield code="b">ger</subfield><subfield code="c">DE-627</subfield><subfield code="e">rakwb</subfield></datafield><datafield tag="041" ind1=" " ind2=" "><subfield code="a">eng</subfield></datafield><datafield tag="245" ind1="1" ind2="0"><subfield code="a">Mechanism of acid-induced decomposition of 2-hydroxyethyl- and 2-alkoxyethyl-cobaloximes</subfield></datafield><datafield tag="264" ind1=" " ind2="1"><subfield code="c">1985</subfield></datafield><datafield tag="336" ind1=" " ind2=" "><subfield code="a">nicht spezifiziert</subfield><subfield code="b">zzz</subfield><subfield code="2">rdacontent</subfield></datafield><datafield tag="337" ind1=" " ind2=" "><subfield code="a">nicht spezifiziert</subfield><subfield code="b">z</subfield><subfield code="2">rdamedia</subfield></datafield><datafield tag="338" ind1=" " ind2=" "><subfield code="a">nicht spezifiziert</subfield><subfield code="b">zu</subfield><subfield code="2">rdacarrier</subfield></datafield><datafield tag="520" ind1=" " ind2=" "><subfield code="a">The decomposition of hydroxyethyl-, ethoxyethyl- and phenoxyethyl(aquo)cobaloximes in sulfuric acid/water mixtures to produce ethylene has been studied spectrophotometrically and manometrically. Definitive kinetic evidence for formation of an intermediate which is common to all three starting complexes and accumulates at acidities greater than 7.3 M H"2SO"4 has been obtained. A complete rate law which accounts for all of the ionizations of starting materials and intermediate has been derived and fit to the rate data. The rate-determining step for product formation is decomposition of the intermediate at all acidities: the intermediate accumulates in strong acid because of a shift in the equilibrium for its formation due to the reduced activity of water in strongly acidic media. Activation parameters for the decomposition of the intermediate, which may be formulated as an ethylene-cobaloxime(III) π-complex or as a σ-bonded ethyl carbonium ion, have been obtained. ^1H and ^1^3C NMR observations of the intermediate and its deuterated analog (from 1,1,2,2-tetradeuterio-2-hydroxyethyl(aquo)cobaloxime) have led to the conclusion that it is probably a σ-bonded ethyl carbonium ion which may be stabilized by σ-π hyperconjugation.</subfield></datafield><datafield tag="533" ind1=" " ind2=" "><subfield code="f">Elsevier Journal Backfiles on ScienceDirect 1907 - 2002</subfield></datafield><datafield tag="700" ind1="1" ind2=" "><subfield code="a">Brown, K.L.</subfield><subfield code="4">oth</subfield></datafield><datafield tag="700" ind1="1" ind2=" "><subfield code="a">Ramamurthy, S.</subfield><subfield code="4">oth</subfield></datafield><datafield tag="700" ind1="1" ind2=" "><subfield code="a">Marynick, D.S.</subfield><subfield code="4">oth</subfield></datafield><datafield tag="773" ind1="0" ind2="8"><subfield code="i">in</subfield><subfield code="t">Journal of Organometallic Chemistry</subfield><subfield code="d">Amsterdam : Elsevier</subfield><subfield code="g">287(1985), 3, Seite 377-394</subfield><subfield code="w">(DE-627)NLEJ174930496</subfield><subfield code="w">(DE-600)1491530-3</subfield><subfield code="x">0022-328X</subfield><subfield code="7">nnns</subfield></datafield><datafield tag="773" ind1="1" ind2="8"><subfield code="g">volume:287</subfield><subfield code="g">year:1985</subfield><subfield code="g">number:3</subfield><subfield code="g">pages:377-394</subfield></datafield><datafield tag="856" ind1="4" ind2="0"><subfield code="u">http://linkinghub.elsevier.com/retrieve/pii/0022-328X(85)80092-9</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_USEFLAG_H</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">ZDB-1-SDJ</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_NL_ARTICLE</subfield></datafield><datafield tag="951" ind1=" " ind2=" "><subfield code="a">AR</subfield></datafield><datafield tag="952" ind1=" " ind2=" "><subfield code="d">287</subfield><subfield code="j">1985</subfield><subfield code="e">3</subfield><subfield code="h">377-394</subfield></datafield></record></collection>
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7.399535 |