A novel type of organometallic 2-R-2,4-dihydro- 1H-3,1-benzoxazine with R = [M(η5-C5H4)(CO)3] (M = Re or Mn) units. Experimental and computational studies of the effect of substituent R on ring-chain tautomerism

The syntheses, characterization, X-ray crystal structures, electrochemical properties and anticancer and 35 antichagasic activities of the first examples of 2-substituted 2,4-dihydro-1H-3,1-benzoxazines with 36 halfsandwich organometallic arrays, [M(η5-C5H4)(CO)3] (M = Re or Mn), at position-2 are d...

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Bibliographic Details
Authors: Oyarzo, Juan, Bosque Pueyo, Ramón, Toro, Patricia, Silva, Carlos P., Arancibia, Rodrigo, Font Bardia, Ma. Mercedes, Artigas, Vania, Calvis, Carme, Messeguer i Peypoch, Ramon, Klahn, A. Hugo, López, Concepción
Format: article
Status:Versión aceptada para publicación
Publication Date:2019
Country:España
Institution:Universidad de Barcelona
Repository:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/160886
Online Access:https://hdl.handle.net/2445/160886
Access Level:Open access
Keyword:Cristal·lografia
Estructura cristal·lina (Sòlids)
Crystallography
Layer structure (Solids)
Description
Summary:The syntheses, characterization, X-ray crystal structures, electrochemical properties and anticancer and 35 antichagasic activities of the first examples of 2-substituted 2,4-dihydro-1H-3,1-benzoxazines with 36 halfsandwich organometallic arrays, [M(η5-C5H4)(CO)3] (M = Re or Mn), at position-2 are described. 37 Experimental and computational studies based on DFT calculations on the open forms [Schiff bases of 38 general formulae R-CHvN-C6H4-2-CH2OH] (5), with R = ferrocenyl (a), phenyl (b), cyrhetrenyl (c) or 39 cymantrenyl (d), and their tautomeric forms (2-substituted 2,4-dihydro-1H-3,1 benzoxazines) 40 haveallowed us to establish the influence of substituents a-d and solvents on: (a) the extent of 41 tautomeric equilibria (5a-5d) ↔ (6a-6d) and (b) their electrochemical properties and the electronic 42 distribution on the open and closed forms. Despite the formal similarity between 6c and 6d, their 43 anticancer and antiparasitic activities are markedly different. Compound 6d is inactive in the HCT116, 44 MDA-MB231 and MCF7 cancer cell lines, but 6c shows moderate activity in the latter cell line, while 45 the Mn(I) complex (6d) is a more potent anti-Trypanosoma cruzi agent than its Re(I) analogue (6c).

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