The antitumor activity of titanocene dihalides (C5H5)2TiX2 with X=F, Cl, Br, I, NCS is investigated against Ehrlich ascites tumor in CF 1 mice. Varying doses of the compounds are applied as single i.p. injections 24 h p.t.t. both in non-buffered (pH 1.4-3.9) and buffered (pH 4.2-5.9) solutions or suspensions, all of the substances achieving in optimum doses cure rates of 100% on day 120 p.t.t. This corresponds to I.L.S. values of 600-750% referred to the untreated controls. Some drug-induced side effects, especially the appearance of postperitonitic symptoms several weeks after i.p. application of higher doses of titanocene dihalides, are strikingly reduced by pH elevation in the injected drug solutions.

Metallocen-&chloride (C,H3,MCI2 (M = Ti, Zr, Hf; 1-3) reagieren in Dioxan/Toluol oder THF mit Dikalium-poly(organophosphanen) K, [PR], unabhtingig von der angebotenen Kettenl h g e (n = 3 -5) und vom Organosubstituenten zu luftempfindlichen Triphosphanato-P',P3-. ,'P-NMR-und Massenspektren besttitigen das Vorliegen viergliedriger MP,-Ringe. Es wird ein Strukturmodell G idealisierter C,-Symmetrie mit gefaltetem Chelatring und tiquatorialen Substituenten R an den P-Atomen vorgeschlagen, das auch mit 'H-NMR-Daten in Einklang ist.Anionoidal Polyphosphanes as Chelate Ligands: Triphosphanato-P',P3 Complexes of the Titanocene, Zirconocene, and Hafnocene System Metallocene dichlorides (C,H,),MCI, (M = Ti, Zr, Hf; 1-3) react in dioxane/toluene or THF with dipotassium poly(organophosphanes) K2 [PR], to give, regardless of the chain length offered (n = 3 to 5) and of the organic substituent, the air-sensitive triphosphanato-P',P3 chelates (C5H3,M[PR],, R beingphenyl(1a-3a), ethyl (lb-3b),methyl(lc-3c),or tert-butyl(1d-3d). ,'P NMR and mass spectra confirm the presence of four-membered MP, rings. In accordance also with 'H NMR data, a structure model G of idealized C, symmetry is proposed containing a folded chelate ring and an equatorial arrangement of the substituents R at the P atoms.Polyphosphane kdnnen auf dreierlei Weise rnit Ubergangsmetallzentren M zu Chelatkomplexen zusammentreten:Den Bicyclen A und den Monocyclen B, welche vierbindige Phosphor-Donoratome enthalten, liegen intakte Cyclo-bzw. Catenapolyphosphane als zweiahnige MolekillChem. Ber. 114(1981)

The antitumor activity of molybdocene dichloride is tested against Ehrlich ascites tumor in CF1 mice. The application of 75 or 100 mg/kg 24 h after transplantation achieves 100% tumor inhibi­tion until day 30. Following the d0 and d1 metallocene dichlorides of titanium and vanadium, molybdocene dichloride is the First analogous d2 system revealing similar antineoplastic properties.

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