Charge-Transfer Salts of Octamethylferrocenyl Thioethers and [M(mnt)2]- Complexes (M = Ni, Co, Pt). Synthesis, Structure, and Physical Properties

The new ferrocene derivatives Fe(η5-C5Me4SR)2 (R = Me, 4:  R = t-Bu, 5) have been prepared from the corresponding cyclopentadiene and FeCl2. 5 may be converted to the bis(thiobenzoate) 6, a protected form of dithiol 8. From 6 the octamethyl trithiaferrocenophane 9 may be obtained in good yields. Com...

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Published in:Inorganic chemistry 1998-08, Vol.37 (16), p.4015-4021
Main Authors: Zürcher, Stefan, Gramlich, Volker, von Arx, Dieter, Togni, Antonio
Format: Article
Language:English
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Summary:The new ferrocene derivatives Fe(η5-C5Me4SR)2 (R = Me, 4:  R = t-Bu, 5) have been prepared from the corresponding cyclopentadiene and FeCl2. 5 may be converted to the bis(thiobenzoate) 6, a protected form of dithiol 8. From 6 the octamethyl trithiaferrocenophane 9 may be obtained in good yields. Compounds 4 and 5 are easily oxidized and form paramagnetic salts containing [M(mnt)2]- anions (M = Co, Ni, Pt). The derivatives [Fe(η5-C5Me4SMe)2][Ni(mnt)2], 14, [Fe(η5-C5Me4SMe)2][Pt(mnt)2], 15, [Fe(η5-C5Me4SMe)2][Co(mnt)2], 16, [Fe(η5-C5Me4St-Bu)2][Ni(mnt)2], 17, [Fe(η5-C5Me4St-Bu)2][Pt(mnt)2], 18, and [Fe(η5-C5Me4St-Bu)2][Co(mnt)2], 19, have been prepared and fully characterized. X-ray crystal structural studies of 14 and 16−19 have been carried out. 14 and 16 display stacks of strongly interacting [M(mnt)2]- anions, whereas 19 contains discrete [Co(mnt)2] dimers. 17 and 18 are isomorphous and display a typical D+A-D+A- structural motif. SQUID susceptibility measurements indicate a weak ferromagnetic ordering at low temperature for these two compounds.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic9802045