About: Exploring a Reaction Mechanism for Acetato Ligand Replacement in Paddlewheel Tetrakisacetatodirhodium (II,II) Complex by Ammonia: Computational Density Functional Theory Study

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
Description	This study focuses on the first step of interaction between DNA and the paddle-wheel dirhodium complex. The ammonia molecule was used to model the oligonucleotide sequence. The reaction was considered in neutral and acidic conditions, in gas phase, and in solvent, using the COSMO model. Molecular structures of the complexes were optimized in both models at the B3PW91/6-31G(d) level. The B3LYP functional and aug-cc-pvdz basis set were employed for single-point energy determination and electron distribution analyses. It was shown that in neutral solution the replacement of axial aqua ligand is mildly exoergic. The reaction is characterized by a relatively low activation barrier (10-12 kcal/mol), and, according to Eyring transition state theory, it proceeds very quickly. The breaking of the Rh-O(ac) bond in neutral solution is mildly endoergic (less than 1 kcal/mol) with an activation barrier of about 2,1 kcal/mol. However, this process can occur much more spontaneously (Delta G of -14 kcal/mol) when the dirhodium complex is protonated at the acetyl oxygen in remote position. This study focuses on the first step of interaction between DNA and the paddle-wheel dirhodium complex. The ammonia molecule was used to model the oligonucleotide sequence. The reaction was considered in neutral and acidic conditions, in gas phase, and in solvent, using the COSMO model. Molecular structures of the complexes were optimized in both models at the B3PW91/6-31G(d) level. The B3LYP functional and aug-cc-pvdz basis set were employed for single-point energy determination and electron distribution analyses. It was shown that in neutral solution the replacement of axial aqua ligand is mildly exoergic. The reaction is characterized by a relatively low activation barrier (10-12 kcal/mol), and, according to Eyring transition state theory, it proceeds very quickly. The breaking of the Rh-O(ac) bond in neutral solution is mildly endoergic (less than 1 kcal/mol) with an activation barrier of about 2,1 kcal/mol. However, this process can occur much more spontaneously (Delta G of -14 kcal/mol) when the dirhodium complex is protonated at the acetyl oxygen in remote position. (en)
Title	Exploring a Reaction Mechanism for Acetato Ligand Replacement in Paddlewheel Tetrakisacetatodirhodium (II,II) Complex by Ammonia: Computational Density Functional Theory Study Exploring a Reaction Mechanism for Acetato Ligand Replacement in Paddlewheel Tetrakisacetatodirhodium (II,II) Complex by Ammonia: Computational Density Functional Theory Study (en)
skos:prefLabel	Exploring a Reaction Mechanism for Acetato Ligand Replacement in Paddlewheel Tetrakisacetatodirhodium (II,II) Complex by Ammonia: Computational Density Functional Theory Study Exploring a Reaction Mechanism for Acetato Ligand Replacement in Paddlewheel Tetrakisacetatodirhodium (II,II) Complex by Ammonia: Computational Density Functional Theory Study (en)
skos:notation	RIV/00216208:11320/11:10089866!RIV12-GA0-11320___
http://linked.open...avai/predkladatel	Matematicko-fyzikální fakulta
http://linked.open...avai/riv/aktivita	P Z
http://linked.open...avai/riv/aktivity	P(GAP205/10/0228), P(ME10149), Z(MSM0021620835)
http://linked.open...iv/cisloPeriodika	5
http://linked.open...vai/riv/dodaniDat	2012
http://linked.open...aciTvurceVysledku	Kovaľ, Tomáš Futera, Zdeněk Burda, Jaroslav
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Univerzita Karlova v Praze / Matematicko-fyzikální fakulta
http://linked.open...dnocenehoVysledku	198982
http://linked.open...ai/riv/idVysledku	RIV/00216208:11320/11:10089866
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	ENERGIES; INHIBITION; CANCER; BINDING; NMR; DNA; ANTITUMOR AGENT; ARENE COMPLEXES; RHODIUM(II) COMPLEXES; TITANOCENE DERIVATIVES (en)
http://linked.open.../riv/klicoveSlovo	ANTITUMOR AGENT ARENE COMPLEXES BINDING CANCER INHIBITION RHODIUM(II) COMPLEXES TITANOCENE DERIVATIVES DNA NMR ENERGIES
http://linked.open...odStatuVydavatele	US - Spojené státy americké
http://linked.open...ontrolniKodProRIV	[955BE378030B]
http://linked.open...i/riv/nazevZdroje	The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment & general theory
http://linked.open...in/vavai/riv/obor	BJ
http://linked.open...ichTvurcuVysledku	3 (xsd:int)
http://linked.open...cetTvurcuVysledku	7 (xsd:int)
http://linked.open...vavai/riv/projekt	Structure and Dynaics of Bioinorganic Complexes Theoretical calculations of the interaction and properties of the transition metal complexes with biomolecules.
http://linked.open...UplatneniVysledku	2011
http://linked.open...v/svazekPeriodika	115
http://linked.open...iv/tvurceVysledku	Burda, Jaroslav Futera, Zdeněk Kovaľ, Tomáš Leszczynski, Jerzy Gu, Jiande Mitoraj, Mariusz Srebro, Monika
http://linked.open...ain/vavai/riv/wos	000286797900031
http://linked.open...n/vavai/riv/zamer	Fyzika molekulárních, makromolekulárních a biologických systémů
issn	1089-5639
number of pages	11 (xsd:int)
http://bibframe.org/vocab/doi	10.1021/jp104726s
http://localhost/t...ganizacniJednotka	11320
is http://linked.open...avai/riv/vysledek of	Exploring a Reaction Mechanism for Acetato Ligand Replacement in Paddlewheel Tetrakisacetatodirhodium (II,II) Complex by Ammonia: Computational Density Functional Theory Study Exploring a Reaction Mechanism for Acetato Ligand Replacement in Paddlewheel Tetrakisacetatodirhodium (II,II) Complex by Ammonia: Computational Density Functional Theory Study

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