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| Dokumentenart: | Artikel | ||||
|---|---|---|---|---|---|
| Titel eines Journals oder einer Zeitschrift: | Monatshefte für Chemie | ||||
| Verlag: | Springer | ||||
| Band: | 128 | ||||
| Nummer des Zeitschriftenheftes oder des Kapitels: | 5 | ||||
| Seitenbereich: | S. 443-474 | ||||
| Datum: | 1997 | ||||
| Zusätzliche Informationen (Öffentlich): | CAN 127:322968 65-5 General Physical Chemistry 14096-51-6; 15663-27-1 (Cisplatin); 81520-29-8; 90130-44-2; 91265-66-6; 91326-61-3; 93856-31-6; 93983-45-0; 138230-33-8; 138258-84-1 Role: PEP (Physical, engineering or chemical process), PRP (Properties), PROC (Process) (mol.-mech. and quantum chem. study of species involved in hydrolysis of cis-diamminedichloroplatinum(II) and substituted bis(ethylenediamine)-dichloroplatinum(II) complexes) | ||||
| Institutionen: | Chemie und Pharmazie > Institut für Pharmazie > Entpflichtete oder im Ruhestand befindliche Professoren > Prof. Schönenberger | ||||
| Sonstige Projekte: | SFB 234 | ||||
| Identifikationsnummer: |
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| Stichwörter / Keywords: | Conformers EHMO Hydrolysis Isomerization Molecular mechanics Molecular structure Total energy Transition state structure (mol.-mech. and quantum chem. study of species involved in hydrolysis of cis-diamminedichloroplatinum(II) and substituted bis(ethylenediamine)-dichloroplatinum(II) complexes) Amines Role: PEP (Physical, engineering or chemical process), PRP (Properties), PROC (Process) (platinum complexes mol.-mech. and quantum chem. study of species involved in hydrolysis of cis-diamminedichloroplatinum(II) and substituted bis(ethylenediamine)-dichloroplatinum(II) complexes) amminechloroplatinum complex hydrolysis transition state simulation ethylenediaminechloro platinum complex hydrolysis mol mechanic EHMO amminechloroplatinum complex hydrolysis transition state | ||||
| Dewey-Dezimal-Klassifikation: | 500 Naturwissenschaften und Mathematik > 540 Chemie | ||||
| Status: | Veröffentlicht | ||||
| Begutachtet: | Ja, diese Version wurde begutachtet | ||||
| An der Universität Regensburg entstanden: | Ja | ||||
| Dokumenten-ID: | 17717 |
Zusammenfassung
Cis-diamminedichloroplatinum(II) (cisplatin) and its substituted ethylenediamine derivs. cis-PtCl2(R2en) (en = ethylenediamine, R = H, Ph, 2-, 3-, and 4-PhOH) were investigated with respect to the possible structures of the hypothetical transition state complexes (TSC) of the hydrolytic SN2 reaction in which 1 Cl is replaced by H2O. TSCs with trigonal bipyramid (TBP) and square pyramid (SP) ...
Zusammenfassung
Cis-diamminedichloroplatinum(II) (cisplatin) and its substituted ethylenediamine derivs. cis-PtCl2(R2en) (en = ethylenediamine, R = H, Ph, 2-, 3-, and 4-PhOH) were investigated with respect to the possible structures of the hypothetical transition state complexes (TSC) of the hydrolytic SN2 reaction in which 1 Cl is replaced by H2O. TSCs with trigonal bipyramid (TBP) and square pyramid (SP) geometry (coordination no. 5), were studied by mol. mechanics (MM) and extended Huckel (EH) methods. The EH and MM energies as well as the no. of occurrence (entropy factor) for the cisplatinum compd. point to a preferred TBP TSC geometry with NH3 and Cl in axial positions. However, for en and substituted en compds., TSCs with SP geometries (CI in apical position) are preferred. The calcd. EH and MM energies of the TBP and SP structures do not differ significantly and TBP .tautm. SP interconversions may play an essential role in TSC formation. To improve the discrimination, the MM-optimized geometries were treated in terms of displacement coordinates for D3h (TBP) and C4v (SP) by calcg. the total distortion vectors (DV). DV identified once again the TBP with NH3 and Cl in axial position as the least-distorted conformer, but it also revealed the combinations of displacement coordinates which shape the TSC geometry.
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