Abstract
[G-1]-Br (3) and [G-2]-Br (5) ([G-x]-Br stands for x generation dendron with Br at the focal point) can be synthesized from the monomer, 3,5-dihydroxybenzyl alcohol by Hawker and Fre´chet’s ”convergent methodology”. Reaction of compound 3 ( or compound 5 ) and [K-18-crown-6-ether]2[Fe2S2(NO)4] (6) in a 2:1 molar ratio in THF yielded the dinuclear [{Fe(NO)2}9-{Fe(NO)2}9] dinitrosyl iron complex (DNIC) [Fe(SR)(NO)2]2 (R= [G-2] (7) or [G-1] (10) ). Reaction of compound 7 and NaIm (or NaSPh, [PPN][NO2] ) led to the production of [Fe(S-[G-2])(Im)(NO)2]- (8a) (or [Fe(S-[G-2])(SPh)(NO)2]- (8b), [Fe2(μ-S-[G-2])(μ-S)(NO)4]- (9) ). Reaction of compound 10 and NaNSi2(CH3)6 led to the production of anti-[Fe(μ-S-[G-1])(NO)2]2- (11). Complex 8,9 and 11 were characterized by IR、UV-vis、EPR and X-ray diffraction. Complex 11 is best decribed as the anionic [{Fe(NO)2}9-{Fe(NO)2}10] Roussin’s Red Ester with the fully delocalized mixed-valence core. The better water soluble’s complex [Fe(μ-SCys)(NO)2]2 (12), [Fe(μ-SCysMe)(NO)2]2 (13) and [Fe(SCysMe)2(NO)2] (14) were then synthesized. Complex 12 - 14 were characterized by IR、UV-vis. Reaction of complex 12 and excess L-Cysteine in DI-water produces the 13-line hyperfine splitting spectra－[H3O+][Fe(SCys)2(NO)2]. The transformation of complex 14 into complex 13 in DI-water was observed identified with EPR spectroscopy.