Reaction of Cp 2Cr 2(SCMe 3) 2S (I) with Fe 3S 2(CO) 9 gives the novel metallospirane cluster Cp 2Cr 2(μ-SCMe 3)(μ 3-S) 2Fe(μ 3-S) 2Fe 2(CO) 6 (II). Analogous clusters with Co and Rh as central ions (III and IV respectively) have been obtained from the reaction of (MeC 5H 4) 2Cr 2(μ-SCMe 3)(μ 3-S) 2Co(CO) 2 or Cp 2Cr 2(μ-SCMe 3)(μ 3-S) 2RhL 2 (L = CO, L 2 = COD) with Fe 2(CO) 6S 2. The X-ray diffraction study of II (space group P 1 , a 9.691(4), b 12.294(3), c 14.515(5) Å, α 66.25(2), β 74.89(3), γ 78.61(3)°, V 1519.8 Å 3, Z = 2) reveals Cr 2Fe and Fe 3 triangles in the Cr 2FeFe 2 metallospirane core at a dihedral angle of 106.8°, and the geometry of dichromium disulfide thiolate fragment remains unchanged as compared to I, III and IV (CrCr 2.689; 2.610(2); 2.598(2); 2.608(5) Å in IIV, respectively). II has strong CrFe bonds (2.717(2) and 2.727(2) Å, but the two bonds between the central and peripheral Fe atoms (3.018(2) and 3.032(2) Å) are relatively weak. The peripheral FeFe bond (2.503(2) Å) is still rather short. Formal replacement of the Fe atom in II by the Co atom in III (space group Pnam, a 14.549(2), b 14.480(2), c 14.146(2) Å, V 2980.1 A 3, Z = 4) results in the rupture of the FeFe bond (Fe…Fe 3.399(2) Å) and formation of the two single CoFe bonds (2.554 (2) and 2.538(2) Å). The dihedral angle between the planes of the metal triangles Cr 2Co and CoFe 2 in III is 90°. The geometry of the Rh(S) 2Fe 2(CO) 6 moiety in the Rh-containing metall-spirane IV (space group P2 1/ n, a 9.800(2), b 12.983(3), c 22.606(5) Å, β 97.05(2)°, V 2854.3 Å 3, Z = 4) is not significantly different from that of the Co(S) 2Fe 2(CO) 6 fragment in III (RhFe 2.650(4) Å, Fe…Fe 3.344(4) Å), the main difference involves the dihedral angle between the Cr 2Rh and RhFe 2 planes, which is 129.1° in IV. This difference being due to the tendency of the Rh I atom to form the square planar complexes on one hand, and to decreasing the repulsion between the S atoms and the strengthening the RhCr bonds in the nonplanar ligand environment of the Rh atom on the other.