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  • 1
    Electronic Resource
    Electronic Resource
    Interaction of dodecacarbonyltetra-.mu.-hydridotetraruthenium with diphosphines in the presence of trimethylamine N-oxide. X-ray crystal structure analyses of (.mu.-H)4Ru4(CO)10(.mu.-{Ph2P(CH2)nPPh2}) (n = 1, 3, 4), (.mu.-H)4Ru4(CO)10(.mu.-{Ph2PCH2CH(CH3)PPh2}), and (.mu.-H)4Ru4(CO)10({Ph2PCH2CH(CH3)PPh2}) (1987)
    s.l. : American Chemical Society
    Inorganic chemistry 26 (1987), S. 867-874 
    Details
    ISSN: 1520-510X
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/ic00253a019
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  • 2
    Electronic Resource
    Electronic Resource
    A reversible metal framework rearrangement assisted by coordinated iodide. X-ray structure analysis of [(Ph3P)2N][H2Os4(CO)12(I)] (1985)
    s.l. : American Chemical Society
    Organometallics 4 (1985), S. 2064-2066 
    Details
    ISSN: 1520-6041
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/om00130a027
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  • 3
    Electronic Resource
    Electronic Resource
    Gas-phase thermolysis of N-substituted diallyl- and allylpropargylamines (1997)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 49-54 
    Details
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---Various diallyl- and allylpropargylamines were pyrolyzed in a stirred-flow reactor at temperatures in the range of 330-500°C, pressures of 8-16 Torr and residence times of 0·4-2·4 s using toluene as carrier gas. The reaction products were propene, allene and aldimines. The allene to propene ratio changed considerably with the third substituent on the N atom. At conversions in the range 13-55%, the consumption of the amines showed first-order kinetics. The following Arrhenius parameters [A (s-1) and Ea (kJ mol-1)] were obtained from the rate coefficients: diallyl-tert-butylamine, log  A = 10·32 ± 0·12, Ea = 139 ± 2; diallylneopentylamine, log A = 12·87 ± 0·26, Ea = 168 ± 3; allylpropargyl-tert-butylamine, log A = 10·23 ± 0·18, Ea = 126 ± 2; allylpropargyltosylamine, log A = 13·05 ± 0.36, Ea = 197 ± 5; and allylpropargylphenylamine, log A = 12·10 ± 0·35, Ea = 162 ± 4. Polar, six-center cyclic transition states are suggested for the elimination of propene and allene, via non-concerted bond breaking-bond forming mechanisms. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Gas-phase thermolysis of N-methyl-N-phenyl-tert-butylsulfenamide and morpholinyl-tert-butylsulfenamide (1998)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 407-410 
    Details
    ISSN: 0894-3230
    Keywords: gas-phase thermolysis ; N-methyl-N-phenyl-tert-butylsulfenamide ; morpholinyl-tert-butylsulfenamide ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: N-Methyl-N-phenyl-tert-butylsulfenamide (MPSA) and morpholinyl-tert-butylsulfenamide (MOSA) were thermolyzed in a stirred-flow reactor at temperatures of 340-390 °C and pressures of 7-13 Torr, using toluene as carrier gas, at residence times of 0.3-1.3 s. Isobutene was formed in 99% yield through first-order reactions having the following Arrhenius parameters (A,s-1, Ea, kJ mol-1): MPSA, log A  =  12.41 ± 0.02, Ea  =  158.8 ± 0.2; MOSA, log A  =  12.91 ± 0.22, Ea  =  159 ± 3. It is proposed that the elimination of isobutene takes place by unimolecular reaction mechanisms involving polar, four-center cyclic transition states, forming S-unsubstituted thiohydroxylamines as co-products. Thermochemical parameters, estimated by semiempirical AM1 calculations, are reported for the latter and for the parent molecules. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Gas-phase thermolysis of aryl tert-butyl disulphides (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 579-585 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pyrolysis kinetics of RC6H4SS—t—C4H9 (R=H, p-NO2, p-Cl, p-F) were determined at 390-450°C and 7-15 Torr in a stirred-flow reactor using toluene as carrier gas. The reaction products were 95% isobutene, 5% isobutane and the corresponding RC6H4SSH disulphanes. The first-order rate constants, k (s-1), based on isobutene production, followed the Arrhenius equations: phenyl tert-butyl disulphide, k = 1013.49±0.31 exp (- 182 ± 4 kJ mol-1)(RT)-1; pnitrophenyl tert-butyl disulphide, k = 1013.46 ± 0.32 [exp(- 185 ± 5 kJ mol-1)(RT)-1]; p-chlorophenyl tert-butyl disulphide, k = 1014.44 ± 0.66 [exp(- 196 ± 9 kJ mol-1)(RT)-1; p-fluorophenyl tert-butyl disulphide, k = 1010.80 ± 0.16 exp(- 144.5 ± 2 kJ mol -1)(RT)-1]; The observed reactivities, within the above temperature range, follow the order p—F 〉 H 〉 p—Cl 〉 p—NO2. A four-centre, cuadrupolar cyclic transition state mechanism is proposed for the formation of the isobutene and aryldisulphane products. The optimized ground-state molecular geometries of the reactants were calculated by using the MINDO/3 procedure.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040909
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  • 6
    Electronic Resource
    Electronic Resource
    Gas phase thermolysis of N-(tert-butylthio)allylamine and N-(tert-butylthio)diethylamine (1994)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 7 (1994), S. 585-590 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The title sulphenamides were pyrolysed in a stirred-flow reactor at temperatures of 310-410°C, pressures of 8-15 Torr and residence times of 0·4-2 s using toluene as the carrier gas. N-(tert-Butylthio)allylamine formed 73 ± 4% isobutene, 23 ± 3% propene and N-allylthiohydroxylamine. The first-order rate coefficients for the formation of isobutene and propene, respectively, followed the Arrhenius equations kC4(s-1) = 1012·52 ± 0·36 exp(-163 ± 5 kJ mol-1 RT) and kC3(s-1) = 1010·99 ± 0·29 exp(-151 ± 4 kJ mol-1 RT) N-(tert-Butylthio)diethylamine gave 97 ± 1% isobutene, 1·9 ± 0·4% isobutane and N,N-diethylthiohydroxylamine. The first-order rate coefficients for isobutene elimination followed the Arrhenius equation k(s-1) = 1013·45 ± 0·24 exp(-164 ± 3 kJ mol-1 RT). The formation of the products is interpreted in terms of an elimination reaction with a unimolecular, four-centered, cyclic transition state. The reactivity of these sulphenamides was found to be much higher than that of previously studied alkyl or aryl tert-butyl sulphides and disulphides.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610071102
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  • 7
    Electronic Resource
    Electronic Resource
    Gas phase thermolysis of benzyl t-butyl sulfide, phenyl t-butyl sulfide, and phenyl t-butyl ether (1989)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 193-206 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis kinetics of the title compounds has been studied in a stirred-flow reactor over the temperature range 440-530°C and pressures between 5 and 14 torr. Benzyl t-butyl sulfide and phenyl t-butyl ether formed isobutene as product in over 98% yield, together with the corresponding benzyl thiol and phenol. The benzyl thiol decomposes to a large extent into hydrogen sulfide and bibenzyl. In the pyrolysis of phenyl t-butyl sulfide, the hydrocarbon products consisted of 80 ±5% isobutene plus 20% isobutane, while the sulfur containing products were thiophenol and diphenyl disulfide. Order one kinetics was observed for the consumption of the reactants. The first order rate coefficients, based on isobutene production, followed the Arrhenius equations: Benzyl t-butyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$k(s^{ - 1}) = 10^{13.82 \pm 0.41} \exp ( - 214 \pm 6{\rm kJ/mol }RT)$$\end{document} Phenyl t-butyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$k(s^{ - 1}) = 10^{12.03 \pm 0.39} \exp ( - 188 \pm 6{\rm kJ/mol }RT)$$\end{document} Phenyl t-butyl ether: \documentclass{article}\pagestyle{empty}\begin{document}$$k(s^{ - 1}) = 10^{14.30 \pm 0.21} \exp ( - 211 \pm 3{\rm kJ/mol }RT)$$\end{document}For benzyl t-butyl sulfide and phenyl t-butyl ether, the results suggest a unimolecular mechanism involving polar four center cyclic transition states. For phenyl t-butyl sulfide, the t-butyl-sulfur single bond fission mechanism is a parallel, less important process than the complex fission one.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550210305
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  • 8
    Electronic Resource
    Electronic Resource
    Substituent effects in the gas-phase thermolysis of aryl tert-butyl ethers and sulfides (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 1127-1136 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolyses of p-nitrophenyl t-butyl ether, p-methoxyphenyl t-butyl ether, p-aminophenyl t-butyl ether, p-nitrophenyl t-butyl sulfide, and propargyl t-butyl sulfide have been studied in a stirred-flow reactor over the temperature range 430-530°C and pressures in the range 7-14 torr, using toluene as carrier gas. The reactions yielded between 90 and 99% isobutene plus the corresponding phenol, thiophenol, or thiol as products. The first order rate coefficients for reactant consumption, based on isobutene production, followed the Arrhenius equationsp-nitrophenyl t-butyl ether\documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - 1}) = 10^{12.79 \pm 0.24} {\rm exp}(- 179 \pm 3{\rm kJ/mol}RT) $$\end{document} p-methoxyphenyl t-butyl ether \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - 1}) = 10^{14.50 \pm 0.30} {\rm exp}(- 210 \pm 4{\rm kJ/mol}RT) $$\end{document} p-aminophenyl t-butyl ether: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - 1}) = 10^{14.59 \pm 0.28} {\rm exp}(- 208 \pm 4{\rm kJ/mol}RT) $$\end{document} p-nitrophenyl t-butyl sulfide \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - 1}) = 10^{12.12 \pm 0.27} {\rm exp}(- 185 \pm 4{\rm kJ/mol}RT) $$\end{document} propargyl t--butyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - 1}) = 10^{13.79 \pm 0.24} {\rm exp}(- 204 \pm 3{\rm kJ/mol}RT) $$\end{document}The results support a unimolecular elimination of the isobutene involving polar, four-center cyclic transition states.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550221103
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  • 9
    Electronic Resource
    Electronic Resource
    Erratum (1994)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 593-594 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550260513
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  • 10
    Electronic Resource
    Electronic Resource
    Gas-phase thermolysis of t-butylsulfenamides: N, N-dimethyl t-butylsulfenamide, 2,6-dimethylpiperidinyl t-butylsulfenamide, and N-t-butyl t-butylsulfenamide (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 353-359 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The amide derivatives of t-butylsulfenic acid mentioned in the title have been thermolyzed in a stirred-flow reactor at temperatures of 273-390°C and pressures of 7-15 torr, using toluene as carrier gas, at residence times of 0.4-2 s. Isobutene formed in 95-99% yields, through order one reactions, following the Arrhenius equations: N, N-dimethyl t-butylsulfenamide: $$k(s^{-1})=10^{14.45\pm 0.46}\exp(-175\pm 5 {\rm kJ/mol}\,{\bf RT})$$ 2,6-dimethylpiperidyl t-butylsulfenamide: $$k(s^{-1})=10^{14.38\pm 0.26}\exp(-161\pm 3 {\rm kJ/mol}\,{\bf RT})$$ N-t-butyl t-butylsulfenamide: $$k(s^{-1})=10^{14.75\pm 0.37}\exp(-184\pm 7 {\rm kJ/mol}\,{\bf RT})$$These thermolyses are considered to take place through unimolecular, four-center cyclic transition-state reaction mechanisms, giving rise to isobutene plus the corresponding S-unsubstituted thiohydroxylamines. The latter decompose outside the reactor at temperatures above -78°C forming free sulfur and dimethylamine, 2,6-dimethylpiperidine, and t-butylamine, respectively. © 1996 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.4
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