Abstract
Complex cis-[Mn(CO) 4 (2-S-C 4 H 3 S) 2 ] - was employed as a metallo chelating ligand to synthesize [(CO) 4 Mn(μ-2-S-C 4 H 3 S) 2 Ni(μ-2-S-C 4 H 3 S) 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 rationalize the construction of complex 1. Cleavage of the Mn I -S bond in complex 1 by an incoming tridentate metallo ligand fac-[Fe(CO) 3 (ER) 3 ] - (E = S, R = C 4 H 3 S; E = Se, R = Ph), followed by a thiolate group ([2-S-C 4 H 3 S] - ) rearranging to bridge two metals, led directly to the anionic [(CO) 3 Mn(μ-2-S-C 4 H 3 S) 3 Ni(μ-ER) 3 Fe(CO) 3 ] - (E = S, R = C 4 H 3 S (2); E = Se, R = Ph (3)) with a homoleptic/heteroleptic hexachalcogenolatonickel(II) core, respectively. Dropwise addition of cis-[Mn(CO) 4 (2-S-C 4 H 3 S) 2 ] to the anionic 2 in THF resulted in formation of a linear trinuclear complex [(CO) 3 Mn(μ-2-S-C 4 H 3 S) 3 Ni(μ-2-S-C 4 H 3 S) 3 Mn-(CO) 3 ] 2- (4) possessing a homoleptic hexathiolatonickel(II) core. It seems reasonable to conclude that the d 6 Mn(I) [(2-S-C 4 H 3 S) 3 Mn(CO) 3 ] 2- fragment is isolobal with the d 6 Fe(II) [(ER) 3 Fe(CO) 3 ] - fragment in complexes 4, 3, and 2.