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| Item type: | Article | ||||
|---|---|---|---|---|---|
| Journal or Publication Title: | Monatshefte für Chemie | ||||
| Publisher: | Springer | ||||
| Volume: | 128 | ||||
| Number of Issue or Book Chapter: | 5 | ||||
| Page Range: | pp. 443-474 | ||||
| Date: | 1997 | ||||
| Additional Information (public): | 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) | ||||
| Institutions: | Chemistry and Pharmacy > Institute of Pharmacy > Alumni or Retired Professors > Prof. Schönenberger | ||||
| Projects (Historical): | SFB 234 | ||||
| Identification Number: |
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| 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 Decimal Classification: | 500 Science > 540 Chemistry & allied sciences | ||||
| Status: | Published | ||||
| Refereed: | Yes, this version has been refereed | ||||
| Created at the University of Regensburg: | Yes | ||||
| Item ID: | 17717 |
Abstract
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) ...
Abstract
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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