RHODIUM(I) COMPLEXES WITH UNSYMMETRIC ALIPHATIC DIAMINES - CRYSTAL-STRUCTURE OF [RH(C8H12)(C7N2H16)][RHCL2(C8H12)] AND [RH(C8H12)(C7N2H16)]CLO4

Reactions of [Rh(COD)Cl]2 with unsymmetric aliphatic diamines (LL') have been studied. The 1:1 ligand:dimer reactions yield ionic products [Rh(C8H12)(LL')][RhCl2(C8H12)] that in solution are in equilibrium with the respective binuclear compounds {[RhCl2(C8H12)]2(mu-LL')}. The X-ray structure of [Rh(C8H12)(C7N2H16)][RhCl2(C8H12)] is presented. When the reactions are performed in media saturated with CO, carbonylated ion-pair complexes are obtained. The 2:1 ligand:dimer reactions afford neutral tetracoordinated [Rh(COD)(LL')Cl] compounds bonded through the primary amino group, and show rapid interchange of olefinic protons at room temperature. The synthesis and properties of cationic complexes of general formulae [Rh(COD)(LL')]ClO4 and [Rh(CO)(PPh3)(LL')]ClO4 are also discussed. Cyclooctadiene compounds show association processes in acetone solution, though they are monomeric in the solid state. The X-ray structure of [Rh(C8H12)(C7N2H16)]ClO4 indicates the existence of hydrogen bonding between the oxygens in the perchlorate anion and the primary amino group in the cation.