Heterotrimetallic iron(II)-nickel(II)-manganese(I) chalcogenolate complexes containing a heteroleptic hexachalcogenolatonickel(II) homoleptic hexathiolatonickel(II) core

Complex cis-[Mn(CO)(4)(2-S-C4H3S)(2)](-) was employed as a metallo chelatin g ligand to synthesize [(CO)(4)Mn(mu-2-S-C4H3S)(2)Ni(mu-2-S-C4H3S)(2)Mn(CO) (4)] (1) with a square planar Ni-II-thiolate core. The longer Ni-II... Mn-I distances and electronic population of nickel(II) (d(8)) are adopted to ra tionalize the construction of complex 1. Cleavage of the Mn-I-S bond in com plex 1 by an incoming tridentate metallo ligand fac-[Fe(CO)(3)(ER)(3)](-) ( E = S, R = C4H3S; E = Se, R = Ph), followed by a thiolate group ([2-S-C4H3S ]-) rearranging to bridge two metals, led directly to the anionic [(CO)(3)M n(mu-2-S-C4H3S)(3)Ni(mu-ER)(3)Fe(CO)(3)](-) (E = S, R = C4H3S (2); E = Se, R = Ph (3)) with a homoleptic/heteroleptic hexachalcogenolatonickel(II) cor e, respectively. Dropwise addition of cis-[Mn(CO)(4)(2-S-C4H3S)(2)](-) to t he anionic 2 in THF resulted in formation of a linear trinuclear complex [( CO)(3)Mn(mu-2-S-C4H3S)(3)Ni(mu-2-S-C4H3S)(3)Mn(CO)(3)](2-) (4) possessing a homoleptic hexathiolatonickel(II) core; It seems reasonable to conclude th at the d(6) Mn(I) [(2-S-C4H3S)(3)Mn(CO)(3)](2-) fragment is isolobal with t he d(6) Fe(II) [(ER)(3)Fe(CO)(3)](-) fragment in complexes 4, 3, and 2.