Kalium‐μ‐dithio‐bis(pentacyanokobaltat(III)) und Kalium‐μ‐diseleno‐bis(pentacyanokobaltat(III))

Abstract

Bei der Oxydation von [Co(CN)5]3− mit Schwefel bzw. Selen werden [Co2S2(CN)10]6− bzw. [Co2Se2(CN)10]6− erhalten, die als Kaliumsalze K6[Co2S2(CN)10]· 4 H2O und K6[Co2Se2(CN)10] · 5 H2O isoliert wurden. Der μ‐Dithiokomplex wurde auch aus [Co(CN)5]3− mit Polysulfid, aus [CoOH(CN)5]3− mit H2S + O2 sowie aus [Co2O2(CN)10]6− mit H2S erhalten. Aus den Schwingungsspektren wird eine Brückenstruktur CoSSCo und CoSeSeCo für die neuen Komplexe abgeleitet.

Oxidative Additions ofcyclo-Octasulfur andcyclo-Octaselenium to the Cobalt(II) Complex of 1,3-Bis(dimethylphosphino)propane (dmpp): Crystal Structures and Spectroscopic Properties of [Co(S2O)(dmpp)2]PF6and [Co(Se2)(dmpp)2]BF4

“…10 000 dm 3 mol -1 cm -1 ). This suggests that the S(σ) (6), which shows a ν(Se-Se) band at 301 cm -1 and a ν(Co-Se) band at 173 cm -1 in the IR spectrum. These values are similar to those of [4]BF 4 .…”

“…These values are similar to those of [4]BF 4 . An X-ray analysis was also attempted for [6]PF 6 , 19 but a satisfactory refinement could not be achieved owing to severe positional disorders for the C atoms of dmpe, related to chelate ring deformations, and for the F atoms of PF 6 -.…”

Sulfur Atoms as Ligands in Metal Complexes

“…Thus, there is no difference between the various bonds from the sulfur, as indicated by the individual resonance formulas of the valence-bond descrip tion (20). It is justifiable, both qualitatively and quantitatively, to state that the sulfur contributes four electrons to three covalent bonds, without specifying the exact distribution of these electrons.…”

“…The sulfur no longer has any lone pairs because all six of its valence electrons are required for the four metalsulfur bonds. The bonding relationships can be represented schematically as (39), which, however, like (20), is a crude simplification of the mostly symmetrical bonding system. (38) the coordination of the sulfur with four metal atoms corresponds to that in zinc sulfide, i.e.…”

Novel C–H activation and C–S formation reactions on disulfide and diselenide ligands in dinuclear ruthenium complexes

“…The variety of coordination modes available for disulfide is another attractive point to be studied. The l-g 1 :g 1 -disulfide [41][42][43][44][45][46][47][48][49][50][51][52] coordination mode in ruthenium complexes is the primary focus of this article. Due to the strong backdonation of Ru III and Ru II the disulfide exhibits novel properties.…”