1,3,5‐Triamino‐1,3,5‐trideoxy‐ cis ‐inositol, a Ligand with a Remarkable Versatility for Metal Ions. Part XIII

The two neutral complexes [Re(CO) 3 (H −1 taci)] ( 1 ) and [ReO 3 (H −1 taci)] ( 2 ) (taci=1,3,5‐triamino‐1,3,5‐trideoxy‐ cis ‐inositol) were synthesized from the conventional Re I and Re VII precursors (Et 4 N) 2 [ReBr 3 (CO) 3 ] and [ReO 3 (OSnMe 3 )]. The crystal structures of 1 and 2 , which were determined by single crystal X‐ray analysis, are virtually isomorphous. Both compounds crystallize in the orthorhombic space group Pnma, Z =4; 1 : a =14.806(3), b =8.466(2), c =9.781(2) Å, 2 : a =13.050(2), b =8.732(1), c =9.061(1) Å. In both complexes, the monodeprotonated H −1 taci ligand is bonded to the Re center in an N,O,N‐coordination mode. The resulting molecular C s symmetry is retained in the crystal structure and confirmed by IR spectroscopy of solid‐state samples. The observed binding mode of the ligand is discussed in terms of steric and electronic effects.