Orthometallated oximes containing phosphines: synthesis, structural characterization and biological studies
| العنوان: | Orthometallated oximes containing phosphines: synthesis, structural characterization and biological studies |
|---|---|
| المؤلفون: | Ricci, Gabriela Francini Bozza |
| المساهمون: | Universidade Estadual Paulista (Unesp), Netto, Adelino Vieira de Godoy [UNESP], Almeida, Eduardo Tonon de |
| المصدر: | Repositório Institucional da UNESP Universidade Estadual Paulista (UNESP) instacron:UNESP |
| بيانات النشر: | Universidade Estadual Paulista (Unesp), 2018. |
| سنة النشر: | 2018 |
| مصطلحات موضوعية: | Cyclopalladated, Phosphines, Oximes, Oximas, Compostos ciclopaladados, Fosfinas |
| الوصف: | Submitted by GABRIELA FRANCINI BOZZA RICCI null (gabrielafrancini@gmail.com) on 2018-09-28T02:39:14Z No. of bitstreams: 1 Ricci_GFB-Tese_2018.pdf: 17373855 bytes, checksum: 90d67387576c4e8408e13aecc7dcc8ac (MD5) Approved for entry into archive by Ana Carolina Gonçalves Bet null (abet@iq.unesp.br) on 2018-09-28T13:20:11Z (GMT) No. of bitstreams: 1 ricci_gfb_dr_araiq_int.pdf: 17344506 bytes, checksum: 2c9d3a77dca087440b81022ef3bed113 (MD5) Made available in DSpace on 2018-09-28T13:20:11Z (GMT). No. of bitstreams: 1 ricci_gfb_dr_araiq_int.pdf: 17344506 bytes, checksum: 2c9d3a77dca087440b81022ef3bed113 (MD5) Previous issue date: 2018-09-14 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Ciclopaladados constituem uma classe de organometálicos de grande interesse, sobretudo por suas extensas aplicações em diversas áreas da Química. Dentre os compostos susceptíveis a reação de ortometalação destacam-se as oximas, onde apesar do frequente emprego de complexos ciclopaladados contendo derivados das oximas, como catalisadores ou pré-catalisadores eficientes, pouco se sabe sobre as potencialidades biológicas dos mesmos. Foram sintetizados doze compostos quelatos de paládio inéditos pela clivagem em ponte de compostos do tipo [PdCl(C2,N-oxima)]2 e fosfinas terciárias (L) {C2,N-oxima = acetofenonaoxima ou benzaldeidoxima; L = trifenilfosfina (PPh3), tri(p-toluil)fosfina (tpf), tris-(4-fluorfenilfosfina) (tfpp), tris-(4-metoxifenil)fosfina (tmf), difenil-(p-toluil)-fosfina (dpt) e triciclohexilfosfina (PCy3)}. Os compostos foram caracterizados por análise elementar, análise térmica (termogravimétrica e diferencial), espectroscopia vibracional na região do infravermelho e espectroscopia de ressonância magnética nuclear de 1H, 13C e 31P. As estruturas cristalinas e moleculares de nove compostos foram determinadas por difratometria de raios X de monocristal, onde [PdCl(C2,N-afox)(L)], onde {L = (PPh3), (tfpp), (tmf), (dpt) e (PCy3)} e [PdCl(C2,N-bzox)(L)], em que {L = (PPh3), (tpf), (tfpp) e (PCy3)}. Além disso, cálculos da superfície de Hirshfeld foram realizados para explorar a natureza e as principais contribuições de diferentes contatos intermoleculares na estabilidade do empacotamento do cristal. Experimentos preliminares para determinar o potencial citotóxico dos compostos foram realizados frente a MCF-7 (adenocarcinoma mamário humano), LM3 (adenocarcinoma mamário murino), A549 (adenocarcinoma epitelial de pulmão humano) e MCR5 (fibroblasto de pulmão humano) e ensaios preliminares a respeito da atividade inibitória frente as catepsinas B e L também foram avaliados, sugerindo um possível modo de ação para os compostos obtidos e testados. Cyclopalladated complexes represent an interesting class of organometallic compounds, mainly for their extensive uses in several areas of Chemistry. Among the organic compounds prone to orthometallation reaction, oximes have attracted considerable attention since their cyclopalladated derivatives have been employed as catalysts in many organic reactions. Despite the intensive work on this area, studies on the biological activity of these compounds remain scarce in the literature. In this context, this work deals with the synthesis, spectroscopic and structural investigation on a series of cyclopalladated compounds of general formulae [PdCl(C2,N-oxime)(L)] (C2,N-oxime = orthometallated acetophenoneoxime (afox) or benzaldehydeoxime (bzox); L = monodentate phosphines). Bridge-splitting reactions between [Pd(C2,N-oxime)(μ-Cl)]2 and phosphines (L = triphenylphosphine (PPh3), tri(p-tolyl)phosphine (tpf), tris(4-fluorophenyl)phosphine (tfpp), tris-(4-methoxyphenyl)phosphine (tmf), diphenyl(p-tolyl)phosphine (dpt) and tricyclohexylphosphine (PCy3)} in a 1:2 ratio, yielded neutral mononuclear cyclopalladated compounds of the type [PdCl(C2,N-oxime)(L)]. The compounds have been characterized by elemental analyses, IR and 1H-, 13C and 31P{1H}-NMR spectroscopies, and thermal analysis TG-DTA. The crystal and molecular structures of the compounds [PdCl(C2,N-afox)(L)] {L = (PPh3), (tfpp), (tmf), (dpt) and (PCy3)} and [PdCl(C2,N-bzox)(L)] { L = (PPh3), (tpf), (tfpp) and (PCy3)} have been determined by single-crystal X-ray diffraction. Hirshfeld surface calculations have been carried out to explore the nature and major contributions of different intermolecular contacts towards crystal packing stability. Preliminary cytotoxic evaluation of the compounds towards MCF-7 (human breast adenocarcinoma), LM3 (murine mammary adenocarcinoma), A549 (human lung epithelial adenocarcinoma) and MCR5 (human lung fibroblast) have been carried out. The ability of the compounds to induce the inhibition of cathepsins B and L have also been evaluated in this work. CAPES: 1570789 |
| اللغة: | Portuguese |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=od______3056::6871c9ff78f9b595b6d614cf13599221 |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.od......3056..6871c9ff78f9b595b6d614cf13599221 |
| قاعدة البيانات: | OpenAIRE |
| الوصف غير متاح. |