Koordinationschemie perhalogenierter Cyclopentadiene und Alkine, XXVI. . Umsetzung von lithiierten Halogencymantrenen mit N-Elektrophilen. Molekülstrukturen von (OC)3Mn[η5-C5Cl4NHNC5Cl4] und (OC)3Mn[η5-C5H3Cl(NH2)-1,2]

Treatment of the lithiated cymantrene [C5Cl4Li]Mn(CO)3 (1a) with tetrachlorodiazocyclopentadiene yields, after work-up, the organometallic hydrazone (OC)3Mn[η5-C5Cl4NHNC5Cl4] (2). The reaction of tosyl azide with 1a or the in situ generated [C5X5−nLin]Mn(CO)3 (X=Cl, n=2: 1b; X=Br, n=1: 1c; X=Br, n=2: 1d) and [C5H3X(Li)]Mn(CO)3 (X=Cl: 1e, X=H: 1f) gave the corresponding azidocymantrenes [C5X5−n(N3)n]Mn(CO)3 (3a,c,d), [C5Cl3H(N3)]Mn(CO)3 (3b′), and [C5H3X(N3)]Mn(CO)3 (3e,f), respectively. Reduction of 3a and 3e with NaBH4 led to the formation of the aminocymantrenes [C5Cl4−nHn(NH2)]Mn(CO)3 (n=0: 4a; n=1: 4b′, n=3: 4e) in high yield. The molecular structures of 2 and 4e in the crystal were determined by X-ray diffraction.