Modellrechnungen zur ionischen Polymerisation von Olefinen; Das aktive Kettenende bei kationischen Systemen

Hallpap, Peter; Heublein, G.

doi:10.1002/zfch.19750151015

Cited by 3 publications

References 6 publications

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Zur stabilität der komplexen anionen bei der kationischen polymerisation

1979

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The counterions appearing in the mechanism of the cationic polymerization are able to decay according toand so give rise to termination reactions. For the model systems (C,H,),C"MtXf + , (Mt = B, Al, Sn, P, As, Sb,In, Ti, Fe; X = F, C1, Br) the decay has been investigated by spectroscopic and conductometric methods. The overall decay rate constant k, is hardly influenced by traces of water (cH2,, < mol. 1-I ) and by structure variations of the cation. On the other hand, k, increases by decreasing the concentration of the salt. When the structure is vaned k, increases with decreasing donor strength of the ligands X, the sensitivity of the anion to changes in the ligand sphere increases corresponding to the ionization potential of the central atom Mt. Addition of tetracyanoethylene raises the stability of the anions. The results can be. explained by the HSAB principle and fit well in a scheme of stabilization of anions by acceptors.

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Zur stabilität der komplexen anionen bei der kationischen polymerisation

1979

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Modellrechnungen zum Gegenioneneinfluß auf die kationische Polymerisation; Geometrieoptimierung und Verhalten gemischter Halogenoantimonate SbCl_nBr

et al. 1979

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Model Calculations on the Counterion Effect in the Cationic Polymerization; Geometry Optimization and Behaviour of the Mixed Halogenoantimonates SbClnBr −n−6. The CNDO/2 method including geometry optimization with respect to the energy has been applied to calculate the structure and the electronic properties of the complex anions SbClnBr −6−n. Independently on the composition of the anions the bond lengths Sb‐X (X = Cl, Br) remain those of the pure antimonates. The HOMOs are delocalized over the ligand sphere. They mainly contain components of Br and are lifted by increasing Br amount. The LUMOs have central atom character and are lowered by Br. Charge distribution and Wiberg bond indices indicate extra easy cleavage of the Sb‐Br bond if Cl holds a trans position to Br. The computed data agree with spectral properties, the acceptor behaviour and the decay trend of the antimonates SbClnBr −6−n.

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Elucidation of cationic polymerization mechanisms by means of quantum chemical methods

Hallpap¹,

Bölke²,

Heublein

Polysiloxane Copolymers/Anionic Polymerization

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Modellrechnungen zur ionischen Polymerisation von Olefinen; Das aktive Kettenende bei kationischen Systemen

Cited by 3 publications

References 6 publications

Zur stabilität der komplexen anionen bei der kationischen polymerisation

Zur stabilität der komplexen anionen bei der kationischen polymerisation

Modellrechnungen zum Gegenioneneinfluß auf die kationische Polymerisation; Geometrieoptimierung und Verhalten gemischter Halogenoantimonate SbCl_nBr

Elucidation of cationic polymerization mechanisms by means of quantum chemical methods

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Modellrechnungen zur ionischen Polymerisation von Olefinen; Das aktive Kettenende bei kationischen Systemen

Cited by 3 publications

References 6 publications

Zur stabilität der komplexen anionen bei der kationischen polymerisation

Zur stabilität der komplexen anionen bei der kationischen polymerisation

Modellrechnungen zum Gegenioneneinfluß auf die kationische Polymerisation; Geometrieoptimierung und Verhalten gemischter Halogenoantimonate SbClnBr

Elucidation of cationic polymerization mechanisms by means of quantum chemical methods

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Modellrechnungen zum Gegenioneneinfluß auf die kationische Polymerisation; Geometrieoptimierung und Verhalten gemischter Halogenoantimonate SbCl_nBr