Cis-trans isomerization of dimeric [Me(2)Al(mu-NH(t)Bu)](2)

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The trans (2a)-cis (2b) isomerization of [Me(2)Al(mu-NH'Bu)](2) (2) has been studied by 1(H) NMR spectroscopy The equilibrium has been observed to follow reversible first order kinetics with Delta H degrees = 2.22 +/- 0.07 KJmol(-1) and Delta S degrees = 2.85 +/- 0.07 JK(-1)mol(-1). The activation parameters for the conversion 2a-->2b are Delta H-1 = 49.7 +/- 2.3 kJmol(-1) and Delta S-1 = -126.3 +/- 0.2 JK(-1)mol(-1) and for the reverse reaction 2b-->2a are Delta H--1 = 47.5 +/- 2.3 kJmol(-1) and Delta S--1 = -129.1 +/- 0.5 JK(-1)mol(-1). The isomerization is markedly accelerated in the presence of Lewis bases. A crossover experiment indicates that the isomer interconversion is a unimolecular process. The large negative entropies of activation suggest either the existence of a sterically congested intermediate or theparticipation of solvent in the isomerization process.
Publisher
KOREAN CHEMICAL SOC
Issue Date
1996-12
Language
English
Article Type
Article
Keywords

CRYSTAL

Citation

BULLETIN OF THE KOREAN CHEMICAL SOCIETY, v.17, no.12, pp.1147 - 1149

ISSN
0253-2964
URI
http://hdl.handle.net/10203/75274
Appears in Collection
CH-Journal Papers(저널논문)
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