Coordination Chemistry of Aliphatic, Tripodal Ligands with Zinc Salts

The unsymmetrical, aliphatic tripods N(CH 2 CH 2 CH 2 NH 2 ) 2 (CH 2 CH 2 OH)(H 5 ‐ 2 ) and N(CH 2 CH 2 CH 2 NH 2 ) 2 (CH 2 CH 2 CH 2 OH) (H 5 ‐ 4 ) were prepared and their coordination chemistry with zinc salts was studied. The reactivity of the ligands with zinc chloride, zinc perchlorate and zinc bis(tetrafluoroborate) depends on the anion present. Ligand H 5 ‐ 2 reacts with Zn(ClO 4 ) 2 under formation of the dinuclear centrosymmetric complex [(H 4 ‐ 2 )Zn] 2 (ClO 4 ) 2 ( 5 ) containing bridging η 2 ‐alkoxy functions. Ligand H 5 ‐ 2 reacts with Zn(BF 4 ) 2 under formation of the trigonal‐bipyramidal complex [(H 5 ‐ 2 )ZnF]BF 4 ( 7 ), while the reaction of (H 5 ‐ 4) with ZnCl 2 yields the mononuclear, tetrahedral complex [(H 5 ‐ 4 )ZnCl]Cl ( 8 ) with an uncoordinated alcohol donor group. Complexes 5 , 7 and 8 were characterized by X‐ray diffraction and NMR and IR spectroscopy.