Abstract
Palladium(II) and platinum(II) chloro complexes of novel water-soluble cage-like phosphane CAP (1,4,7-triaza-9-phosphatricyclo[5.3.2.14,9]tridecane) have been synthesized and characterized in comparison with their counterparts bearing well known PTA (1,3,5-triaza-7-phosphaadamantane) ligand. A peculiar structural feature of studied cis-[MCl2L2] complexes is the occurrence of interligand C−Hσ+⋅⋅⋅σ+H−C interactions (hydrogen-hydrogen bonds) between the phosphane cages: the first case encountered so far among metal-phosphane complexes. Due to substantial stabilizing contribution to the net molecular energy of the complexes (∼ 20 kcal mol−1), hydrogen-hydrogen bonding is sufficient to maintain sterically overcrowded cis conformations of the complexes. The interplay between protonation stage of the ligands and their conformations can be a reason of significant differences in in-vitro cytotoxicity between CAP complexes and their PTA-bearing counterparts.
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