O NTOLOGISK DIFFERENS OG TRANSCENDENS . K RITIKK AV ONTOTEOLOGIEN

As amostras dos compostos organometálicos foram sintetizadas no grupo da Professora Maria José Calhorda e foram preparadas para análise por NMR em tubos de 10 mm contendo cerca de 2,5 ml de solvente deuterado. Às que foram analisadas por NMR de silício adicionou-se 20 μl de TMS. Para a análise de NMR de molibdénio, introduziu-se no tubo de NMR um capilar fechado contendo uma solução de molibdato de sódio (Na2MoO4) 2 mol/l em D2O a pD = 11. Em geral, os compostos eram pouco

solúveis e utilizaram-se soluções saturadas. Os espectros foram obtidos à temperatura ambiente (293 K). As amostras sensíveis ao ar foram preparadas nos tubos de NMR recorrendo a técnicas de schlenk sob vácuo, com três ciclos de congelação/descongelação em atmosfera de azoto.

Os impulsos de 90º foram p90(29Si)=27 μs e p90(95Mo)=31 μs.

As experiências de 29Si foram feitas seguindo o programa de impulsos da Figura 3.2 e o protocolo da Bruker(30) e considerando JSiH = 7 Hz. As experiências de 95

Mo foram feitas seguindo o programa de impulsos da Figura 3.3 e o protocolo da Bruker(30), com DE = 20 μs.

Os espectros de NMR foram processados com correcção do FID por apodização exponencial para aumento da razão sinal/ruído. Para os espectros de NMR de 95Mo, utilizou-se um factor LB de 50,0 Hz.

Indicam-se também os parâmetros experimentais D1, TD (número de pontos para amostragem FID), SW (largura da janela espectral) e AQ (tempo de aquisição).

Página 69 Composto 1: T8[(CH2)3Cl]8 NMR de 29Si{1H}: [CDCl3; 79,5 MHz; δ (ppm): -67,0]; D1 = 5 s; TD = 65536; SW = 31,8 KHz; AQ = 1,029 s; LB = 1,00; Composto 2: T8[(CH2)3DPA]8 NMR de 29Si{1H}: [CDCl3; 79,5 MHz, δ (ppm): -21,9]; D1 = 2 s; TD = 65536; SW = 19,8 KHz; AQ = 1,652 s; LB = 3,00; Composto 3:

T8[(CH2)3DPA]7[Mo(CO)2(η3-C3H5)(Br)DPA(CH2)3)]

NMR de 29Si{1H}: [CDCl3; 79,5 MHz; δ (ppm): -21,9]; D1 = 2 s; TD = 65536; SW = 19,8 KHz; AQ = 1,652 s; LB = 3,00; NMR de 95Mo: [CDCl3; 26,1 MHz; δ (ppm): -784 (w1/2=1067 Hz), -677 (w1/2=1899 Hz), -615 (w1/2=1147 Hz)]; D1 = 0,010 s; TD = 16384; SW = 57,5 KHz; AQ = 0,143 s; Composto 4: [Mo(CO)2(η3-C3H5)(Br)DPA]: NMR de 95Mo: [acetona-d6 e DMF (1:1); 26,1 MHz, δ (ppm): -790 (w1/2=410 Hz), -696, -620]; D1 = 1 s; TD = 16384; SW = 57,5 KHz; AQ = 0,143 s] Composto 5: [Mo(CO)2(η3-C3H5)(Br)(NCCH3)2]: NMR de 95Mo: [CDCl3; 26,1 MHz, δ (ppm): -790 (w1/2=551 Hz), -743 (w1/2=1189 Hz), -568 (w1/2=731 Hz)]; D1 = 0,100 s; TD = 16384; SW = 73,0 KHz; AQ = 0,112 s]

Página 70 Composto 6 : [Mo(CO)2(η3-C3H5)(Br)(pypim)] NMR de 95Mo: [CDCl3; 26,1 MHz, δ (ppm): -786 (w1/2=367 Hz)]; D1 = 0,100 s; TD = 16384; SW = 73,0 KHz; AQ = 0,112 s; LB = 1,00; Composto 7: [Mo(CO)2(η3-C3H5)(Br)(pypimSi(OEt)3)] NMR de 29Si{1H}: [acetona-d6; 79,5 MHz, δ (ppm): -62,6]; D1 = 1 s; TD = 32768; SW = 15,9 KHz; AQ = 1,029 s; LB = 2,00; Composto 8 pypimSi(OEt)3: NMR de 29Si{1H}: [CDCl3; 79,5 MHz], δ (ppm): -46,6; D1 = 1 s; TD = 65536; SW = 19,8 KHz; AQ = 1,652 s; LB = 3,00];

Página 71

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