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| [PMID]: | 22111710 |
| [Au] Autor: | Schutte M; Kemp G; Visser HG; Roodt A |
| [Ad] Endereço: | Department of Chemistry, University of the Free State, P.O. Box 339, Bloemfontein 9300, South Africa. |
| [Ti] Título: | Tuning the reactivity in classic low-spin d6 rhenium(I) tricarbonyl radiopharmaceutical synthon by selective bidentate ligand variation (L,L'-Bid; L,L'= N,N', N,O, and O,O' donor atom sets) in fac-[Re(CO)3(L,L'-Bid)(MeOH)]n complexes. |
| [So] Source: | Inorg Chem;50(24):12486-98, 2011 Dec 19. | | [Is] ISSN: | 1520-510X |
| [Cp] País de publicação: | United States |
| [La] Idioma: | eng |
| [Ab] Resumo: | A range of fac-[Re(CO)(3)(L,L'-Bid)(H(2)O)](n) (L,L'-Bid = neutral or monoanionic bidentate ligands with varied L,L' donor atoms, N,N', N,O, or O,O': 1,10-phenanthroline, 2,2'-bipydine, 2-picolinate, 2-quinolinate, 2,4-dipicolinate, 2,4-diquinolinate, tribromotropolonate, and hydroxyflavonate; n = 0, +1) has been synthesized and the aqua/methanol substitution has been investigated. The complexes were characterized by UV-vis, IR and NMR spectroscopy and X-ray crystallographic studies of the compounds fac-[Re(CO)(3)(Phen)(H(2)O)]NO(3)·0.5Phen, fac-[Re(CO)(3)(2,4-dQuinH)(H(2)O)]·H(2)O, fac-[Re(CO)(3)(2,4-dQuinH)Py]Py, and fac-[Re(CO)(3)(Flav)(CH(3)OH)]·CH(3)OH are reported. A four order-of-magnitude of activation for the methanol substitution is induced as manifested by the second order rate constants with (N,N'-Bid) < (N,O-Bid) < (O,O'-Bid). Forward and reverse rate and stability constants from slow and stopped-flow UV/vis measurements (k(1), M(-1) s(-1); k(-1), s(-1); K(1), M(-1)) for bromide anions as entering nucleophile are as follows: fac-[Re(CO)(3)(Phen)(MeOH)](+) (50 ± 3) × 10(-3), (5.9 ± 0.3) × 10(-4), 84 ± 7; fac-[Re(CO)(3)(2,4-dPicoH)(MeOH)] (15.7 ± 0.2) × 10(-3), (6.3 ± 0.8) × 10(-4), 25 ± 3; fac-[Re(CO)(3)(TropBr(3))(MeOH)] (7.06 ± 0.04) × 10(-2), (4 ± 1) × 10(-3), 18 ± 4; fac-[Re(CO)(3)(Flav)(MeOH)] 7.2 ± 0.3, 3.17 ± 0.09, 2.5 ± 2. Activation parameters (ΔH(k1)(++), kJmol(-1); ΔS(k1)(), J K(-1) mol(-1)) from Eyring plots for entering nucleophiles as indicated are as follows: fac-[Re(CO)(3)(Phen)(MeOH)](+) iodide 70 ± 1, -35 ± 3; fac-[Re(CO)(3)(2,4-dPico)(MeOH)] bromide 80.8 ± 6, -8 ± 2; fac-[Re(CO)(3)(Flav)(MeOH)] bromide 52 ± 5, -52 ± 15. A dissociative interchange mechanism is proposed. |
| [Mh] Termos MeSH primário: |
Compostos Organometálicos/síntese química
Compostos Radiofarmacêuticos/síntese química
Rênio/química
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| [Mh] Termos MeSH secundário: |
2,2'-Dipiridil/química
Ácido 4-Acetamido-4'-isotiocianatostilbeno-2,2'-dissulfônico/análogos & derivados
Ácido 4-Acetamido-4'-isotiocianatostilbeno-2,2'-dissulfônico/química
Cristalografia por Raios X
Cinética
Ligantes
Espectroscopia de Ressonância Magnética
Metanol/química
Modelos Moleculares
Estrutura Molecular
Fenantrolinas/química
Ácidos Picolínicos/química
Espalhamento a Baixo Ângulo
Termodinâmica
Água/química
Difração de Raios X
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| [Pt] Tipo de publicação: | JOURNAL ARTICLE; RESEARCH SUPPORT, NON-U.S. GOV'T |
[Nm] Nome de substância:
| 0 (Ligands); 0 (Organometallic Compounds); 0 (Phenanthrolines); 0 (Picolinic Acids); 0 (Radiopharmaceuticals); 059QF0KO0R (Water); 27816-59-7 (4-Acetamido-4'-isothiocyanatostilbene-2,2'-disulfonic Acid); 551W113ZEP (2,2'-Dipyridyl); 7440-15-5 (Rhenium); 78543-24-5 (4-benzamido-4'-isothiocyanostilbene-2,2'-disulfonate); QZV2W997JQ (picolinic acid); UE81S5CQ0G (dipicolinic acid); W4X6ZO7939 (1,10-phenanthroline); Y4S76JWI15 (Methanol) |
| [Em] Mês de entrada: | 1204 |
| [Cu] Atualização por classe: | 151119 |
[Lr] Data última revisão:
| 151119 |
| [Sb] Subgrupo de revista: | IM |
| [Da] Data de entrada para processamento: | 111125 |
| [St] Status: | MEDLINE |
| [do] DOI: | 10.1021/ic2013792 |
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