Oligomerization of dialkylazidogallium compounds: a structural and solution-phase studyElectronic supplementary information (ESI) available: Fig. S1: Mass spectrum of 1 with M+ peak at 225 and higher oligomers present in the vapor phase. See http://www.rsc.org/suppdata/dt/b3/b307813b/

2003 ◽  
pp. 3675 ◽  
Author(s):  
Sean D. Dingman ◽  
Nigam P. Rath ◽  
William E. Buhro
Keyword(s):  
Mass Spectrum ◽  
Vapor Phase ◽  
Solution Phase ◽  
Supplementary Information

The relative rates of bromination of cyclohexane and cyclopentane with molecular bromine. Comparison of the reactions in solution and in vapor phase

1981 ◽  
Vol 59 (9) ◽  
pp. 1368-1374 ◽  
Author(s):  
Dennis D. Tanner ◽  
Tomoki C-S. Ruo ◽  
Hideki Takiguchi ◽  
Andre Guillaume
Keyword(s):  
Vapor Phase ◽  
Hydrogen Bromide ◽  
Bromine Atom ◽  
Relative Rate ◽  
Solution Phase ◽  
Molecular Bromine ◽  
Transfer Rates ◽  
Relative Rate Constants ◽  
Halogenated Alkanes ◽  
Relative Transfer

The relative rates of transfer of the cyclopentyl radical with molecular bromine and hydrogen bromide (k2′/k−1′) and with hydrogen tribromide and hydrogen bromide (k3′/k−1′) have been determined. The relative transfer rates are compared with the analogous values previously reported for the reactions of cyclohexyl radicals (k2/k−1 and k3/k−1). Utilizing the values of k2′/k−1 and k2/k−1 the competitive vapor phase rates of bromine atom abstraction of hydrogen from the two substrates could be obtained. An expression using a combination of the five sets of relative rate constants was used to determine the effect of competitive cage reversal which occurs in the solution phase bromination of the two substrate radicals with caged hydrogen bromide. For two structurally similar radicals, cage reversal (internal return) was found to affect the relative rates of bromination by 30%, while the relative transfer rates, although differing each by a factor of two, fortuitously nearly cancel each other's effect.The effect of both internal and external reversal reactions on the relative rates of bromination of structurally dissimilar substrates, halogenated alkanes and their parent hydrocarbons, is discussed.

Vapor-phase and solution-phase UV spectroscopic studies of η5-pentadienyl derivatives of iron and ruthenium

1998 ◽  
Vol 563 (1-2) ◽  
pp. 209-217 ◽  
Author(s):  
Sergey Yu Ketkov ◽  
Richard D Ernst ◽  
Lothar Stahl ◽  
Wimonrat Trakarnpruk
Keyword(s):  
Vapor Phase ◽  
Spectroscopic Studies ◽  
Solution Phase ◽  
Derivatives Of

A reinvestigation of the vapor phase bromination of 2-bromobutane

1984 ◽  
Vol 62 (11) ◽  
pp. 2310-2316 ◽  
Author(s):  
Dennis D. Tanner ◽  
Tomoki C. S. Ruo ◽  
Yoshio Kosugi ◽  
Alan Potter
Keyword(s):  
Vapor Phase ◽  
Thermal Instability ◽  
Addition Reaction ◽  
Bromine Atom ◽  
Solution Phase ◽  
Reaction Schemes

The solution phase photobromination of 2-bromobutane yields 2,2-dibromobutane, meso-2,3-dibromobutane, dl-2,3-dibromobutane, small amounts of 1,2-dibromobutane, and 2,2,3-tribromobutane. However, in the corresponding vapor phase bromination these products appear along with other polybrominated products. The yield of these polybromides increases with temperature. The increase in yield of the polyhalogenated materials is rationalized by considering the thermal instability of the β-bromoalkyl radical, which eliminates a bromine atom to form the corresponding alkene. It is demonstrated that in the vapor phase allylic bromination competes successfully with bromine addition. Reaction schemes are suggested to explain the formation of polybromides. An explanation is also offered for the discrepancy between these results and those of previously reported vapor phase work.

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