Organische Synthesen mit Uebergangsmetallkomplexen XXXIX *. Thio- und Selenoketenimine aus Thio- und Selenocarben-Komplexen von Chrom, Wolfram, Mangan und Isocyaniden

Article abstract of DOI:10.1016/0022-328X(89)80007-5

Thio- and selenocarbene complexes L_nM=C(XR)C6H5 (I) (XR = S-C6H5, S-c-C6H11, S-t-C4H9, SCH2C6H5, SeC6H5) of chromium, tungsten and mangenese nM = Cr(CO)5, W(CO)5, Mn(CO)2(CH3C5H4)> give thio-and selenoketene imine complexes L_nM1N=C=C(XR)C6H5> (III) on addition of isocyanides R¹NC II (R¹ = CH3, c-C6H11, t-C4H9, C6H5) by an insertion of II into the M=C bond of I.The ketene imine ligand is coordinated through the lone pair of the heteroatom X.Novel thio- and selenoketene imines V can be readily obtained from III in good yields by disengagement with aprotic nucleophiles such as II or pyridine.V can also be directly obtained from the reaction of I with two equivalents of II.