名称:
                                Koordinationschemie perhalogenierter Cyclopentadiene und Alkine, XXVI. . Umsetzung von lithiierten Halogencymantrenen mit N-Elektrophilen. Molekülstrukturen von (OC)3Mn[η5-C5Cl4NHNC5Cl4] und (OC)3Mn[η5-C5H3Cl(NH2)-1,2]
                             
                            
                                摘要:
                                Treatment of the lithiated cymantrene [C5Cl4Li]Mn(CO)(3) (1a) with tetrachlorodiazocyclopentadiene yields, after work-up, the organometallic hydrazone (OC)(3)Mn[eta(5)-C5Cl4-NH-N=C5Cl4] (2). The reaction of tosyl azide with la 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(N-3)(n)]Mn(CO)(3) (3a,c,d), [C5Cl3H(N-3)]Mn(CO)(3) (3b'), and [C5H3X(N-3)]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.