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Seven novel imidazole and thiazole derivatives of diphos-type ligands are presented. They are of the general structure R2P(CH2)(2)PR2, where R is imidazol-2-yl (1), 1-methylimidazol-2-yl (2), 1-methyl-benzimidazol-2-yl (3), 1-methylimidazol-5-yl (4), 2-isopropylimidazol-4(5)-yl (5), thiazol-2-yl (6), benzothiazol-2-yl (7), thiazol-4-yl (8) or thiazol-5-yl (9). Syntheses involved direct metallation or halogenmetal exchange reactions. Their solubility, especially in aqueous solution, is strongly dependent on the nature of the substituents as is their partition coefficient log D. The crystal structures of compounds 2, 3, 7a and 9 as well as the structure of the rhodium complex (2)(2) , Corinna Wetzel [a] , Melanie Bongartz [a] , Anna-Louisa Noffke [a] and Bernhard Spingler

A variety of piano-stool complexes of cyclopentadienyl ruthenium(II) with imidazole-based PN ligands have been synthesized starting from the precursor complexes CpRu(C10H8)]PF6, CpRu(NCMe)(3)]PF6 and CpRu(PPh3)(2)Cl]. PN ligands used are imidazol-2-yl, -4-yl and -5-yl phosphines. Depending on the ligand and precursor different types of coordination modes were observed; in the case of polyimidazolyl PN ligands these were kappa P-1-monodentate, kappa P-2,N-, kappa N-2,N-and kappa N-3,N,N-chelating and mu-kappa P:kappa N-2,N-brigding. The solid-state structures of CpRu(1a)(2)Cl]center dot H2O (5 center dot H2O) and CpRu(mu-kappa(2)-N,N-kappa('1)-P-2b)(2)](C6H5PO3H)(2)(C6H5PO3H2)( 2), a hydrolysis product of the as well determined CpRu(2b) (2)](PF6)(2)center dot 2CH(3)CN (7b center dot 2CH(3)CN) were determined (1a = imidazol-2-yldiphenyl phosphine, 2b = bis(1-methylimidazol-2-yl) phenyl phosphine, 3a = tris(imidazol-2-yl) phosphine). Furthermore, the complexes CpRu(L) (2) [e] Anorganisch-Chemisches Institut, Universität Zürich-Irchel, Winterthurerstr. 190, CH-8057 Zürich, Switzerland.[ ‡] X-ray structure analysis.

The tetranuclear ruthenium arene compound [(cym)4Ru4(2)Cl6]Cl2 (3) (cym = 6-p-cymene, 2 = 1,2-bis(di-N-methylimidazol-2-ylphosphino)ethane) was prepared and characterised by one-and twodimensional NMR techniques. Its cytotoxicity against four different cell lines was determined and, with an approximate IC50 of >100 M 3 can be regarded as non-toxic. Its partition coefficient in n-octanol/water (log D7.4) was also determined. The structures of complex 3 as well as of the related compound [(cym)2Ru2(4)Cl2]Cl2 (5) (4 = 1,2-bis(di-N-methylimidazol-2-ylphosphino)ethane dioxide) were determined by single crystal structure analysis. Upon oxidation in protic solvents, ligand 2 shows P-C bond cleavage reactions to yield P,P-bis(N-methylimidazol-2-yl)ethylene diphosphinic acid (6). [ ‡] X-ray structure analysis. KeywordsImidazolylphosphanes, Phosphane Ligands, PN Ligands, Ruthenium AbstractThe tetranuclear ruthenium arene compound [(cym) 4 Ru 4 (2)Cl 6 ]Cl 2 (3) (cym = η

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