Linear-Type S-Bridged Trinuclear Complexes with Ru^III Ion and Octahedral fac(S)-[M(aet)₃] Units (M = Rh^III, Ir^III; aet = 2-Aminoethethiolate)

Synthesis of Novel S‐Bridged Heterotrinuclear Complexes Containing Six‐Membered Chelate Rings: Structural, Spectroscopic, and Electrochemical Properties of [Co{Rh(apt)3}2]3+ (apt = 3‐Aminopropanethiolate)

“…[10] Moreover, the absorption maxima in the first dd transition region in the tn complexes shift to lower energies than those in the corresponding en complexes. [12,13] Similar to the complexes [Co(tn) 3 ] 3+ and [Co(en) 3 ] 3+ with N-N donor ligands, complexes containing five-and sixmembered chelate rings with N-S donor ligands also show interesting differences in properties. For example, an additional methylene group led to differences in reactivity: all the attempts to synthesize [Co(apt) 3 ] (apt = 3-aminopropanethiolate) were unsuccessful, unlike the corresponding complex [Co(aet) 3 ], which was obtained easily.…”

“…3+ than in [M(en) 3 ] 3+ (M = Co III or Cr III ion). [10,11] It was also observed that the ring-ring interactions, which give rise to the energy differences between conformations, are more severe and more numerous in the sixmembered chelate ring complexes than in five-membered systems.…”

“…[6][7][8][9][10][11][12][13] For example, six-membered chelate rings give rise to a larger bite angle (N···N distances in chelates) than fivemembered rings. [6][7][8][9] It was reported that both the conformational flexibility and the structural bulkiness are larger in [M(tn) 3 ]…”

“…The complex [Co(tn) 3 ] 3+ (tn = 1,3-propanediamine) containing an additional methylene group shows some interesting differences in properties when compared with the corresponding complex [Co(en) 3 ] 3+ (en = ethylenediamine). [6][7][8][9][10][11][12][13] For example, six-membered chelate rings give rise to a larger bite angle (N···N distances in chelates) than fivemembered rings.…”

“…It has been recognized that, because of their high Lewis basicity, coordinated thiolato groups have an affinity to form S-bridged polynuclear structures with transition-metal ions. Therefore, mononuclear complexes, fac(S)- [M(aet) 3 ] (M = Co III , Rh III , Ir III ; aet = 2-aminoethanethiolate), could function as metalloligands to other transition-metal ions, using sulfur atoms. [1] The polynuclear complexes obtained so far have shown unique stereochemical, spectrochemical, and electrochemical properties, depending highly upon the nature of mined.…”