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Theoretical studies of nitrilotriacetic acid and nitrilotripropionic acid geometries for estimation of the stability of metal complexes by Density Functional Theory
Dissertation (MSc)--University of Pretoria, 2010.
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University of Pretoria
2013
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| _version_ | 1867613631872499712 |
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| access_status_str | Open Access |
| author2 | Cukrowski, Ignacy |
| author_browse | Cukrowski, Ignacy |
| author_facet | Cukrowski, Ignacy |
| collection | Thesis |
| dc_rights_str_mv | © 2009, University of Pretoria. All rights reserved. The copyright in this work vests in the University of Pretoria. No part of this work may be reproduced or transmitted in any form or by any means, without the prior written permission of the University of Pretoria. |
| description | Dissertation (MSc)--University of Pretoria, 2010. |
| format | Thesis |
| id | oai:repository.up.ac.za:2263/27811 |
| institution | University of Pretoria (South Africa) |
| last_indexed | 2026-06-10T12:39:13.632Z |
| license_str | Other — see source repository |
| provenance_str_mv | Harvested via OAI-PMH from UPSpace — University of Pretoria Institutional Repository |
| publishDate | 2013 |
| publishDateRange | 2013 |
| publishDateSort | 2013 |
| publisher | University of Pretoria |
| publisherStr | University of Pretoria |
| record_format | dspace |
| source_str | UPSpace — University of Pretoria Institutional Repository |
| spelling | oai:repository.up.ac.za:2263/27811 Theoretical studies of nitrilotriacetic acid and nitrilotripropionic acid geometries for estimation of the stability of metal complexes by Density Functional Theory Cukrowski, Ignacy Marques, Helder M. kk.govender@gmail.com Govender, Krishna Kuben Nta Complex stability. Protonation constants Ntpa Computational chemistry UCTD Dissertation (MSc)--University of Pretoria, 2010. Nitrilotriacetic Acid (NTA) is an organic ligand which has been extensively studied due to its biological significance and excellent chelating properties. Nitrilotripropionic Acid (NTPA) is a ligand that is believed to possess similar properties to NTA, but has not been as extensively studied. It has been experimentally determined that metal complexes of NTA are orders of magnitude stronger than those formed with NTPA. This is surprising, especially considering that the ligands do not differ that much from each other. NTPA contains an additional –CH2– group in each of the acid containing arms as compared to NTA. The aim of these studies were to explain, theoretically, why this is the case. Analyses were conducted with a number of software programs including, Gaussian 03, Schrödinger Maestro and AIM 2000. All Density Functional Theory (DFT) studies were conducted in solvent at the RB3LYP/6-311+G(d,p) level of theory in conjunction with a number of different solvation models. En route to explaining why the complexes differ in stability a new methodology was utilized (isodesmic reactions) in which the four stepwise protonation constants of both NTA and NTPA were successfully predicted; in fact these were the most accurate values predicted to date by DFT methods. The final step of these studies focused on predicting stability constants of metal (Zn2+ and Ni2+) complexes of NTA and NTPA. These predictions were not as accurate as those achieved for the prediction of protonation constants; however, success was achieved in predicting the trend – complexes with NTA are orders of magnitude stronger than complexes formed with NTPA. The most important observation revealed that H–clashes and C–H∙∙∙O hydrogen bonds present in M(NTPA) complexes, which are not present in M(NTA) complexes, result in the formation of additional rings which contributes to the formation of a cage. It was discovered that the H-clashes present in the M(NTPA) complexes were contributing to the overall stability of the molecule. This is completely contradictory to a previous explanation in which H-clashes, being a result of steric crowding, resulted in destabilization of a complex. If the H-clashes were not present in the M(NTPA) complexes there would not be enough stabilizing factors present in the molecule which will inevitably result in the non-existence of M(NTPA) complexes. Copyright Chemistry unrestricted 2013-09-07T12:25:37Z 2010-05-26 2013-09-07T12:25:37Z 2009-09-07 2009 2009-09-07 Dissertation Govender, KK 2009, Theoretical studies of nitrilotriacetic acid and nitrilotripropionic acid geometries for estimation of the stability of metal complexes by Density Functional Theory, MSc dissertation, University of Pretoria, Pretoria, viewed yymmdd < http://hdl.handle.net/2263/27811 > C10/111/gm http://hdl.handle.net/2263/27811 http://upetd.up.ac.za/thesis/available/etd-09072009-110815/ © 2009, University of Pretoria. All rights reserved. The copyright in this work vests in the University of Pretoria. No part of this work may be reproduced or transmitted in any form or by any means, without the prior written permission of the University of Pretoria. application/pdf University of Pretoria |
| spellingShingle | Nta Complex stability. Protonation constants Ntpa Computational chemistry UCTD Theoretical studies of nitrilotriacetic acid and nitrilotripropionic acid geometries for estimation of the stability of metal complexes by Density Functional Theory |
| title | Theoretical studies of nitrilotriacetic acid and nitrilotripropionic acid geometries for estimation of the stability of metal complexes by Density Functional Theory |
| title_full | Theoretical studies of nitrilotriacetic acid and nitrilotripropionic acid geometries for estimation of the stability of metal complexes by Density Functional Theory |
| title_fullStr | Theoretical studies of nitrilotriacetic acid and nitrilotripropionic acid geometries for estimation of the stability of metal complexes by Density Functional Theory |
| title_full_unstemmed | Theoretical studies of nitrilotriacetic acid and nitrilotripropionic acid geometries for estimation of the stability of metal complexes by Density Functional Theory |
| title_short | Theoretical studies of nitrilotriacetic acid and nitrilotripropionic acid geometries for estimation of the stability of metal complexes by Density Functional Theory |
| title_sort | theoretical studies of nitrilotriacetic acid and nitrilotripropionic acid geometries for estimation of the stability of metal complexes by density functional theory |
| topic | Nta Complex stability. Protonation constants Ntpa Computational chemistry UCTD |
| url | http://hdl.handle.net/2263/27811 http://upetd.up.ac.za/thesis/available/etd-09072009-110815/ |