Heterotrimetallic Iron(II)−Nickel(II)−Manganese(I) Chalcogenolate Complexes Containing a Heteroleptic Hexachalcogenolatonickel(II)/Homoleptic Hexathiolatonickel(II) Core

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 IIthiolate 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)) 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 ] 2fragment is isolobal with the d 6 Fe(II) [(ER) 3 Fe(CO) 3 ]fragment in complexes 4, 3, and 2.To our knowledge, a few examples of complexes containing a homoleptic hexathiolatometal core or hexaselenolatometal core are reported and characterized by X-ray crystallography. 3 Recent work in this laboratory showed that cis-[Mn-(CO) 4 (ER) 2 ]and fac-[Fe(CO) 3 (SePh) 3 ]complexes are useful in the syntheses of heterotrimetallic Mn(I)-Co-(III)-Mn(I)-chalcogenolate complexes [(CO) 4 Mn(µ-ER) 2 -Co(CO)(µ-E′R) 3 Mn(CO) 3 ] (E ) E′ ) Te, R ) Ph; E ) Te, E′ ) Se, R ) Ph; E ) E′ ) Se, R ) Me) with a unique Co(III)-CO bond, 4 and [(CO) 3 M(µ-SePh) 3 M′(µ-SePh) 3 M-(CO) 3 ] -1/0 (M ) Mn, M′ ) Co; M ) Fe, M′ ) Fe, Cd, Zn, Ni) with a homoleptic hexaselenolatometal core. 3b,5 In these reactions, the complexes fac-[Fe(CO) 3 (SePh) 3 ]and cis-[Mn(CO) 4 (ER) 2 ]act as potential "chelating metallo ligands" and selenolate ligand-transfer reagents. 5c,6 A recent report on distorted square planar [Ni(CO)-(SPh) n (SePh) 3-n ] -(n ) 0, 1, 2), in preparations of the biomimetic nickel-site structure of [NiFe] hydrogenases

Dinuclear and Mononuclear Iron(II)−Thiolate Complexes with Mixed CO/CN- Ligands: Synthetic Advances for Iron Sites of [Fe]-Only Hydrogenases

“…Complex 4 exhibits a diagnostic 1 H NMR spectrum with the 1,2-benzenedithiolate proton resonances at 6.60 (t), 6.79 (t), 7.22 (d), and 7.33 (d) ppm which are consistent with the Fe(II) having a low-spin d 6 electronic configuration in an octahedral ligand field. The IR spectrum of complex 4 in the aprotic solvent CH 2 Cl 2 reveals a weak absorption band for the CN - ligands at 2101 cm -1 , and two strong absorption bands for the CO groups at 1960 and 2013 cm -1 , as expected for the existence of centrosymmetry in complex 4 (vibrationally uncoupled CO groups and CN - groups on adjacent iron(II) sites). 12b, When the CH 2 Cl 2 solution of complex 4 was exposed to 13 CO at 0 °C, absorbances at 1968 and 1915 cm -1 appeared within 10 min. Reappearance of the 2013 and 1960 cm -1 bands on removal of the 13 CO and replacement with 12 CO atmosphere demonstrated reversibility of CO ligand lability of complex 4 .…”

Synthesis, Characterization and Coordination Chemistry of Some Selenium‐Containing Macrocyclic Schiff Bases

“…Figure 5 shows the coordination sphere around the Ni II ion and Table 5 -. [45] The C(1A)-Se(1)-C(1B) angle of 97.1(7)°deviates slightly (0.6°) from that in the ligand 2.…”

CORM-EDE1: A Highly Water-Soluble and Nontoxic Manganese-Based photoCORM with a Biogenic Ligand Sphere

“…25,26 The reaction proceeds via intermediate [(OC) 4 Mn(μ-SR)] 2 which can also be directly converted to [(Ph 3 P) 2 N] + [Mn 2 (μ-SR) 3 (CO) 6 ] − by substitution of two carbonyl molecules with [(Ph 3 P) 2 N]SR. 27 Furthermore, phenylthiolato ligands can also be transferred from cobalt complexes to manganese. 28 Mixedmetal Mn/Ni and Mn/Co complexes have also been prepared containing the structural (OC) 3 Mn(μ-SR) 3 M fragments (M = Co, Ni); 29,30 during the reaction cascade of the reaction of [Mn(CO) 5 ] − , disulfane, and Co(ClO 4 ) 2 , also the [Mn 2 (μ-SR) 3 (CO) 6 ] − anion formed. 30 Already in 1966, Hieber and Gscheidmeier 31 reacted [Mn(CO) 5 Br] with cysteamine and reported the formation of the yellow mononuclear Mn(I) complex [(OC) 3 Mn(S-CH 2 CH 2 NH 2 )] with a bidentate anion and a pentacoordinate metal atom, based on IR data and elemental analysis.…”