Dithiolate-bridged Fe-Ni-Fe trinuclear complexes consisting of Fe(CO)(3-n)(CN)(n) (n = 0, 1) components relevant to the active site of [NiFe] hydrogenase.
A dithiolate-bridged Fe-Ni-Fe trinuclear carbonyl complex [(CO)(3)Fe(mu-ndt)Ni(mu-ndt)Fe(CO)(3)] (1, ndt = norbornane-exo-2,3-dithiolate) has been synthesized from the reaction of [Fe(CO)(4)I(2)] and Li(2)[Ni(ndt)(2)]. This reaction was found to occur with concomitant formation of a tetranuclear cluster [Ni(3)(mu-ndt)(4)FeI] (2). Treatment of 1 with Na[N(SiMe(3))(2)] transforms some of the CO ligands into CN(-), and the monocyanide complex (PPh(4))[(CO)(2)(CN)Fe(mu-ndt)Ni(mu-ndt)Fe(CO)(3)] (3) and the dicyanide complex (PPh(4))(2)[(CO)(2)(CN)Fe(mu-ndt)Ni(mu-ndt)Fe(CO)(2)(CN)] (4) were isolated. X-ray structural analyses of the trinuclear complexes revealed a Fe-Ni-Fe array in which the metal centers are connected by the ndt sulfur bridges and direct Fe-Ni bonds. Hydrogen bonding between the CN ligand in 3 and cocrystallized ethanol was found in the solid-state structure. The monocyanide complex 3 and dicyanide complex 4 reacted with acids such as HOTf or HCl generating insoluble materials, whereas complex 1 did not react.
Pal
Satyanarayan
S
Department of Chemistry, Graduate School of Science and Research Center for Materials, Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602 (Japan), Fax: (+81) 52-789-2943.
Ohki
Yasuhiro
Y
Department of Chemistry, Graduate School of Science and Research Center for Materials, Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602 (Japan), Fax: (+81) 52-789-2943.
Yoshikawa
Teppei
T
Department of Chemistry, Graduate School of Science and Research Center for Materials, Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602 (Japan), Fax: (+81) 52-789-2943.
Kuge
Katsuaki
K
Department of Chemistry, Graduate School of Science and Research Center for Materials, Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602 (Japan), Fax: (+81) 52-789-2943.
Tatsumi
Kazuyuki
K
Department of Chemistry, Graduate School of Science and Research Center for Materials, Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602 (Japan), Fax: (+81) 52-789-2943.
D020134:Catalytic Domain; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D007501:Iron / Q000737:chemistry*; D009532:Nickel / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D013438:Sulfhydryl Compounds; D009532:Nickel; D007501:Iron; C043296:nickel-iron hydrogenase; D006864:Hydrogenase