{"title":"re(v)和tc(v)的反水氧四氰配合物中水取代的动力学和高压机理研究:对核医学的一些启示。","authors":"J Mattheus Botha, Andreas Roodt","doi":"10.1155/2008/745989","DOIUrl":null,"url":null,"abstract":"<p><p>A kinetic study of the aqua substitution in the [TcO(OH(2))(CN)(4)](-) complex by different thiourea ligands (TU = thiourea, NMTU = N-methyl thiourea, NNDMTU = N, N'-dimethylthiourea) yielded second-order formation rate constants (25 degrees C) as follows [NNDMTU, NMTU, TU, respectively]: k(f) = 11.5 +/- 0.1, 11.38 +/- 0.04, and 7.4 +/- 0.1 M(-1)s(-1), with activation parameters: Delta H(#) (k(f) ) : 55 +/- 2, 42 +/- 3, 35 +/- 5 kJ mol(-1); DeltaS(#) (k(f) ) : - 40 +/- 8, - 84 +/- 11, - 110 +/- 17 J K(-1)mol(-1). A subsequent high-pressure investigation of the aqua substitution in the [ReO(OH(2))(CN)(4)](-) and [TcO(OH(2))(CN)(4)](-) complexes by selected entering ligands yielded DeltaV(#) (k(f) ) values as follows: Re(V): -1.7 +/- 0.3(NCS(-)), -22.1 +/- 0.9 (TU) and for Tc(V): -3.5 +/- 0.3(NCS(-)), -14 +/- 1 (NNDMTU), and -6.0 +/- 0.5 (TU) cm(3)mol (-1), respectively. These results point to an interchange associative mechanism for the negative NCS(-) as entering group but even a pure associative mechanism for the neutral thiourea ligands.</p>","PeriodicalId":18452,"journal":{"name":"Metal-Based Drugs","volume":"2008 ","pages":"745989"},"PeriodicalIF":0.0000,"publicationDate":"2008-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1155/2008/745989","citationCount":"6","resultStr":"{\"title\":\"Kinetic and high-pressure mechanistic investigation of the aqua substitution in the trans-aquaoxotetracyano complexes of re(v) and tc(v): some implications for nuclear medicine.\",\"authors\":\"J Mattheus Botha, Andreas Roodt\",\"doi\":\"10.1155/2008/745989\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>A kinetic study of the aqua substitution in the [TcO(OH(2))(CN)(4)](-) complex by different thiourea ligands (TU = thiourea, NMTU = N-methyl thiourea, NNDMTU = N, N'-dimethylthiourea) yielded second-order formation rate constants (25 degrees C) as follows [NNDMTU, NMTU, TU, respectively]: k(f) = 11.5 +/- 0.1, 11.38 +/- 0.04, and 7.4 +/- 0.1 M(-1)s(-1), with activation parameters: Delta H(#) (k(f) ) : 55 +/- 2, 42 +/- 3, 35 +/- 5 kJ mol(-1); DeltaS(#) (k(f) ) : - 40 +/- 8, - 84 +/- 11, - 110 +/- 17 J K(-1)mol(-1). A subsequent high-pressure investigation of the aqua substitution in the [ReO(OH(2))(CN)(4)](-) and [TcO(OH(2))(CN)(4)](-) complexes by selected entering ligands yielded DeltaV(#) (k(f) ) values as follows: Re(V): -1.7 +/- 0.3(NCS(-)), -22.1 +/- 0.9 (TU) and for Tc(V): -3.5 +/- 0.3(NCS(-)), -14 +/- 1 (NNDMTU), and -6.0 +/- 0.5 (TU) cm(3)mol (-1), respectively. These results point to an interchange associative mechanism for the negative NCS(-) as entering group but even a pure associative mechanism for the neutral thiourea ligands.</p>\",\"PeriodicalId\":18452,\"journal\":{\"name\":\"Metal-Based Drugs\",\"volume\":\"2008 \",\"pages\":\"745989\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2008-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1155/2008/745989\",\"citationCount\":\"6\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Metal-Based Drugs\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1155/2008/745989\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Metal-Based Drugs","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1155/2008/745989","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Kinetic and high-pressure mechanistic investigation of the aqua substitution in the trans-aquaoxotetracyano complexes of re(v) and tc(v): some implications for nuclear medicine.
A kinetic study of the aqua substitution in the [TcO(OH(2))(CN)(4)](-) complex by different thiourea ligands (TU = thiourea, NMTU = N-methyl thiourea, NNDMTU = N, N'-dimethylthiourea) yielded second-order formation rate constants (25 degrees C) as follows [NNDMTU, NMTU, TU, respectively]: k(f) = 11.5 +/- 0.1, 11.38 +/- 0.04, and 7.4 +/- 0.1 M(-1)s(-1), with activation parameters: Delta H(#) (k(f) ) : 55 +/- 2, 42 +/- 3, 35 +/- 5 kJ mol(-1); DeltaS(#) (k(f) ) : - 40 +/- 8, - 84 +/- 11, - 110 +/- 17 J K(-1)mol(-1). A subsequent high-pressure investigation of the aqua substitution in the [ReO(OH(2))(CN)(4)](-) and [TcO(OH(2))(CN)(4)](-) complexes by selected entering ligands yielded DeltaV(#) (k(f) ) values as follows: Re(V): -1.7 +/- 0.3(NCS(-)), -22.1 +/- 0.9 (TU) and for Tc(V): -3.5 +/- 0.3(NCS(-)), -14 +/- 1 (NNDMTU), and -6.0 +/- 0.5 (TU) cm(3)mol (-1), respectively. These results point to an interchange associative mechanism for the negative NCS(-) as entering group but even a pure associative mechanism for the neutral thiourea ligands.
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