Nitric oxide plays an important role in many biological functions. A metallo derivative in biological systems is a protein-bound dinitrosyl iron complex (DNIC), which results from iron-sulfur cluster degradation in the presence of excess NO. Through model complexes I have examined the fundamental properties of a dithiolato-Fe(NO)2 complex, bismercaptoethandiazacyclooctane iron dinitrosyl or (H+bme-daco)Fe(NO)2 as a biomimic of dicysteinate coordination of [Fe(NO)2]. This complex was prepared and fully characterized in my studies. The DNIC moiety is in its oxidized state, {Fe(NO)2}9. Through reaction studies, monitored by IR spectroscopy (H+N2S2)Fe(NO)2 (N2S2 = bme-dach. Bme-pda) has been shown to transfer NO to FeIII in (TPP)FeCl (TPP = meso-tetraphenylporphyrin) as NO-. The remaining mononitrosyl converts into complex (N2S2)Fe(NO). The (N2S2)Fe(NO) complexes (N2S2 = bme-daco, bme*-daco, bme-dach) were prepared by direct reaction of dimeric [(N2S2)Fe]2 and NO gas. The analogous (N2S2)Co(NO) complex (N2S2 = bme-dach) has also been prepared. The series of square pyramidal (N2S2)M(NO) have been studied by cyclic voltammetry and ν(NO) IR spectroscopy.

Nitric oxide plays an important role in many biological functions. A metallo derivative in biological systems is a protein-bound dinitrosyl iron complex (DNIC), which results from iron-sulfur cluster degradation in the presence of excess NO. Through model complexes I have examined the fundamental properties of a dithiolato-Fe(NO)2 complex, bismercaptoethandiazacyclooctane iron dinitrosyl or (H+bme-daco)Fe(NO)2 as a biomimic of dicysteinate coordination of [Fe(NO)2]. This complex was prepared and fully characterized in my studies. The DNIC moiety is in its oxidized state, {Fe(NO)2}9. Through reaction studies, monitored by IR spectroscopy (H+N2S2)Fe(NO)2 (N2S2 = bme-dach. Bme-pda) has been shown to transfer NO to FeIII in (TPP)FeCl (TPP = meso-tetraphenylporphyrin) as NO-. The remaining mononitrosyl converts into complex (N2S2)Fe(NO). The (N2S2)Fe(NO) complexes (N2S2 = bme-daco, bme*-daco, bme-dach) were prepared by direct reaction of dimeric [(N2S2)Fe]2 and NO gas. The analogous (N2S2)Co(NO) complex (N2S2 = bme-dach) has also been prepared. The series of square pyramidal (N2S2)M(NO) have been studied by cyclic voltammetry and ν(NO) IR spectroscopy.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal