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Reaction of Cp 2 Ti(CO) 2 , Cp=h 5 -C 5 H 5 , with the 1,2-diazenes ROCN = NCOR (R = EtO (1a), tert-BuO (1b), p-MeC 6 H 4 O (1c), p-MeC 6 H 4  (1d)) in the molar ratio of 1:1 yiclds five- membered metallacycles 2 by formal 1,4-addition of 1 to the Cp 2 Ti fragment. When a two-fold excess of Cp 2 Ti(CO) 2  is employed, the initially formed 2 reacts further by N = N-cleavage to give Cp 2 Ti(NCO)(OR), Cp 2 Ti(NCO) 2  and Cp 2 Ti(OR) 2  resp., in the case of 1a-1c. The bis(p-methyl- benzoyI)diazene (1d) does not afford analogous cleavage products. Dimethyl- and pentamethy- lenediazirine also react by cleavage of the N = N-bond to afford Cp 2 Ti(NCO)(N=CR 2 ).

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Übergangsmetallkomplexe von Diazenen, XXIV [1]. Komplexierung und N=N-Spaltung von Diazenen durch Dicarbonylbis(cyclopentadienyl)titan / Transition Metal Complexes of Diazenes, XXIV [1] Complexation and N = N-Cleavage of Diazenes by Dicarbonylbis(cyclopentadienyl)titanium