2.3 The theoretical reflections and considerations
2.3.2 Reflections on team-oriented safety concepts
A análise elementar (CHN) sugere as seguintes estruturas para os complexos:
trans-[Co(cyclam)Cl2]Cl. 6H2O e trans-Na[Co(cyclam)(tios)2].7H2O. O espectro de
infravermelho dos complexos trans-Na[Co(cyclam)(tios)2] e trans-Na[Co(en)2(tios)2]
apresentaram bandas características que comprovam a forma de coordenação monodentada, via átomo de enxofre, do ligante tiossulfato (620 - 634 cm-1). Também podem ser observadas bandas referentes aos estiramentos N-H do cyclam em 3213 e 3133 cm-1, e para o complexo com a etilenodiamina, em 3283 e 3267 cm-1, comprovando a permanência do ligante macrocíclico e da etilenodiamina na esfera de coordenação do metal após a reação com o íon tiossulfato.
De acordo com a análise de absorção no ultravioleta, banda de transferência de carga LMCT como sendo a de maior comprimento de onda para o trans- Na[Co(cyclam)(tios)2] (350 nm) e trans-Na[Co(en)2(tios)2] (333 nm) comparativamente
ao complexo precursor trans-[Co(cyclam)Cl2]Cl (318 nm), indicando uma maior
facilidade de transferência de densidade eletrônica para o metal dos ligantes tiossulfatos nos complexos. Fato este comprovado na análise eletroquímica, ao analisar o comportamento dos ligantes tiossulfatos e cloretos quanto a sua capacidade doadora de elétrons e , ao se fazer uma comparação dos potenciais meia onda (E1/2) dos
complexos em estudo, trans-[Co(cyclam)Cl2]Cl, trans-Na[Co(cyclam)(tios)2] e trans-
Na[Co(en)2(tios)2], cujos valores são: -86 mV, -247 mV e -476 mV, respectivamente,
como já visto anteriormente, a primeira explicação está no fato da capacidade de doação eletrônica mais intensa do ligante tiossulfato ao centro metálico e a segunda explicação está no fato de se ao fazer um comparativo dos ligantes cyclam e etilenodiamina, o deslocamento de potenciais para valores mais negativos no complexo trans- Na[Co(en)2(tios)2], pode ser atribuído a uma maior proximidade dos átomos de
nitrogênio da etilenodiamina em relação a ligação metal–nitrogênio do cyclam, devido ao efeito do ajuste do anel macrocíclico ao centro metálico (efeito macrocíclico), o que faz com que a ligação metal-nitrogênio não seja tão próximas quanto do ligante etilenodiamina, fato que difere os ligantes em estudo.
Com base nos resultados obtidos é possível evidenciar a coordenação do ligante tiossulfato ao cobalto e identificar uma característica de maior doação de densidade eletrônica ao metal por parte do ligante tiossulfato, comparativamente ao ligante cloreto, tendo em vista o forte deslocamento de E1/2 para valores de potenciais mais negativos.
Tal verificação está também de acordo com a variação de energia da banda LMCT do complexo.
No espectro de emissão do complexo trans-Na[Co(cyclam)(tios)2] foi observada
banda de transferência de carga em 397 nm e bandas d-d em 438, 450, 467, 481 e 492 nm.
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