Novel multitopic diphos-type ligands.

Seven novel imidazole and thiazole derivatives of diphos-type ligands are presented. They are of the general structure R(2)P(CH(2))(2)PR(2), 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 halogen-metal 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)Rh(2)Cl(2)]Cl(2) (10) have been determined. (C) 2010 Elsevier B. V. All rights reserved.