The reaction of Zn(II) and Co(II) with thiosalicylic acid,
o-HSC
6H
4COOH, and its methyl ester has led to thefollowing complexes: [Zn(SC
6H
4COO)] (
1), (NEt
4)Na[Zn(SC
6H
4COO)
2]·H
2O (
2), (NEt
4)
2Na[Co(SC
6H
4COO)
3]·2H
2O (
3), (NEt
4)
3Na
3[{Co(SC
6H
4COO)
3}
2]·6MeOH (
4), [Zn(SC
6H
4COOMe)
2] (
5), and [Co(SC
6H
4COOMe)
n],
n= 2 (
6), 3 (
7). These ligands have not allowed stabilization of Co(II) in a sulfur-oxygen coordination environment.The structures of complexes
2-
4 and
7 have been determined crystallographically. Those of
2-
4 show significantsimilarities such as the behavior of the
-SC
6H
4COO
- anion as chelating ligand and the involvement of sodiumions as a structural element. Thus, the structure of the [Na{Zn(SC
6H
4COO)
2}(H
2O)]
- anion in complex
2 can bedescribed as infinite chains of consecutive [Zn(SC
6H
4COO)
2]
2- metalloligands linked by [Na(H
2O)]
+ centers,that of the [Na{Co(SC
6H
4COO)
3(H
2O)
2}]
24- anion in
3 as a centrosymmetric tetranuclear Co
2Na
2 dimer with a{Co
III(S
![](/images/entities/cap.gif)
O)
3}Na(
![](/images/entities/mgr.gif)
-H
2O)
2Na{Co
III(S
![](/images/entities/cap.gif)
O)
3} core, and that of the pentanuclear [Na
3{Co(SC
6H
4COO)
3}
2(MeOH)
6]
3-anion in
4 as two dinuclear [{Co
III(S
![](/images/entities/cap.gif)
O)
3}Na(MeOH)
3] fragments linked to a central sodium ion, which appearsto be the first structurally characterized example of a NaS
6 site. The use of the
o-HSC
6H
4COOMe ligand allowedthe synthesis of [Co(SC
6H
4COOMe)
2] (
6) but not its full structural characterization. Instead, [Co(SC
6H
4COOMe)
3](
7) was obtained and structurally characterized. It consists of mononuclear molecules containing an octahedralCo
IIIS
3O
3 core. The selection of 2,2-diphenyl-2-mercaptoacetic acid as ligand with reductive properties has affordedthe first mononuclear complex containing a Co
IIS
2O
2 core and thus an unprecedented model for Co(II)-substitutedmetalloproteins containing tetrahedral MS
2O
2 active sites. The synthesis and full structural characterization ofthe isostructural complexes (NEt
4)
2[Zn{Ph
2C(S)COO}
2] (
8) and (NEt
4)
2[Co{Ph
2C(S)COO}
2] (
9) show that theyconsist of discrete [M{Ph
2C(S)COO}
2]
2- anions, with a distorted tetrahedral coordination about the metal. Inaddition, the stability conferred by the ligand on the Co
IIS
2O
2 core has allowed its characterization in solution byparamagnetic 1D and 2D
1H NMR studies. The longitudinal relaxation times of the hyperfine-shifted resonancesand NOESY spectra have led to the assignment of all resonances of the cobalt complex and confirmed that itmaintains its tetrahedral geometry in solution. Magnetic measurements (2-300 K) for complex
9 and
9·2H
2O arein good agreement with distorted tetrahedral and octahedral environments, respectively.