Complex cis-[Mn(CO)4(2-S-C4H3S)2] - was employed as a metallo chelating ligand to synthesize [(CO)4Mn(μ-2-S-C4H3S) 2Ni(μ-2-S-C4H3S)2Mn(CO) 4] (1) with a square planar NiII-thiolate core. The longer NiII-MnI distances and electronic population of nickel(II) (d8) are adopted to rationalize the construction of complex 1. Cleavage of the MnI-S bond in complex 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)3Mn(μ-2-S-C4H3S) 3Ni(μ-ER)3Fe(CO)3]- (E = S, R = C4H3S (2); E = Se, R = Ph (3)) with a homoleptic/heteroleptic hexachalcogenolatonickel(II) core, respectively. Dropwise addition of cis-[Mn(CO)4(2-S-C4H3S)2] to the anionic 2 in THF resulted in formation of a linear trinuclear complex [(CO)3Mn(μ-2-S-C4H3S) 3Ni(μ-2-S-C4H3S)3Mn-(CO) 3]2- (4) possessing a homoleptic hexathiolatonickel(II) core. It seems reasonable to conclude that the d6 Mn(I) [(2-S-C4H3S)3Mn(CO)3]2- fragment is isolobal with the d6 Fe(II) [(ER)3Fe(CO)3]- fragment in complexes 4, 3, and 2.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry