Organische synthesen mit übergangsmetallkomplexen: XXXVII. Einfache darstellungsverfahren für thio- und selenocarben-komplexe von Chrom, Wolfram und Mangan

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A wide variety of thio- and selenocarbene complexes L n MC(XR)C 6H 5 (VI) (XR = SCH 2CH 3, SCH 2CHCH 2, SCH 2CCH, SCH 2C 6H 5, S-c-C 6H 11, S-t-C 4H 9, SC 6H 5, SCH 2CH 2NHC(C 6H 5)W(CO) 5, SeC 6H 5) of chromium, tungsten and manganese [L n M = Cr(CO) 5 (a), W(CO) 5 (b), Mn(CO) 2(CH 3C 5H 4) (c)] have been obtained from the corresponding benzoylmetallates in straightforward two-step procedures via acetylation and thiolysis (selenolysis). The manganese compounds VIn–p can be prepared in high yields from the lithium salt (IIIc) directly, if this is activated with HMPTA in dichloromethane. On the other hand, the chromium and tungsten compounds VIa–m are obtained in much better yields from the tetramethylammonium salts in dichloromethane rather than from the lithium salt (IIIa, b).