Thiolate-bridged dinuclear iron(tris-carbonyl)-nickel complexes relevant to the active site of [NiFe] hydrogenase.

The reaction of NiBr(2)(EtOH)(4) with a 1:2-3 mixture of FeBr(2)(CO)(4) and Na(SPh) generated a linear trinuclear Fe-Ni-Fe cluster (CO)(3)Fe(mu-SPh)(3)Ni(mu-SPh)(3)Fe(CO)(3), 1, whereas the analogous reaction system FeBr(2)(CO)(4)/Na(S(t)Bu)/NiBr(2)(EtOH)(4) (1:2-3:1) gave rise to a linear tetranuclear Fe-Ni-Ni-Fe cluster [(CO)(3)Fe(mu-S(t)Bu)(3)Ni(mu-Br)](2), 2. By using this tetranuclear cluster 2 as the precursor, we have developed a new synthetic route to a series of thiolate-bridged dinuclear Fe(CO)(3)-Ni complexes, the structures of which mimic [NiFe] hydrogenase active sites. The reactions of 2 with SC(NMe(2))(2) (tmtu), Na{S(CH(2))(2)SMe} and ortho-NaS(C(6)H(4))SR (R = Me, (t)Bu) led to isolation of (CO)(3)Fe(mu-S(t)Bu)(3)NiBr(tmtu), 3, (CO)(3)Fe(S(t)Bu)(mu-S(t)Bu)(2)Ni{S(CH(2))(2)SMe}, 4, and (CO)(3)Fe(S(t)Bu)(mu-S(t)Bu)(2)Ni{S(C(6)H(4))SR}, 5a (R = Me) and 5b (R = (t)Bu), respectively. On the other hand, treatment of 2 with 2-methylthio-phenolate (ortho-O(C(6)H(4))SMe) in methanol resulted in (CO)(3)Fe(mu-S(t)Bu)(3)Ni(MeOH){O(C(6)H(4))SMe}, 6a. The methanol molecule bound to Ni is labile and is readily released under reduced pressure to afford (CO)(3)Fe(S(t)Bu)(mu-S(t)Bu)(2)Ni{O(C(6)H(4))SMe}, 6b, and the coordination geometry of nickel changes from octahedral to square planar. Likewise, the reaction of 2 with NaOAc in methanol followed by crystallization from THF gave (CO)(3)Fe(mu-S(t)Bu)(3)Ni(THF)(OAc), 7. The dinuclear complexes, 3-7, are thermally unstable, and a key to their successful isolation is to carry out the reactions and manipulations at -40 degrees C.