Abstract The thioanisole-π-complexes (methylthio-η-benzene)-(η-benzene)-chromium (2) and bis(methylthio-η-benzene)chromium (3) have been prepared via lithiation of bis(η-benzene)-chromium and consecutive reaction with dimethyldisulfide. 1H NMR and 13C NMR spectra of 2 and 3 as well as ESR-spectra of the corresponding radical cations 2.+ and 3.+ were recorded and analyzed. In contrast to C(η-arene)-Si and C(η-arene)-P bonds, C(y-arene)-S bonds are stable to solvolysis. With (norbornadiene)tetracarbonylmolybdenum, 3 readily forms [bis(methylthio-η-benzene)chromium]tetracarbonylmolybdenum (6) wherein 3 functions as a chelating ligand. 1H and 13C NMR evidence suggests, that at room temperature 6 undergoes rapid conformational interconversions.

Cocondensation of chromium atoms with phenanthrene vapor affords bisη1,2,3,4,10a,4a- phenanthrene)chromium (4). 1 NMR spectroscopy reveals, that the diastereomers 4 (rac) and 4' (meso) are formed in a 2:1 ratio. Cyclic voltammetric studies on 4 show, that four oxidation states are accessible:[E° ═ -2.235 (rev.), -0.651 (rev.), + 0.82 (irrev.) V vs. SCE]. The radical ions are characterized by ESR spectro­scopy in fluid and rigid solutions. Prominent feature of these species is the inverse relative magnitude of the g-tensor components: .