PREPARATION AND CHARACTERIZATION OF NITROSYLRUTHENIUM(III) COMPLEXES CONTAINING DIETHYLENETRIAMINE

Some kinds of {Ru(II)-NO+}-type complexes containing a diethylenetriamine ligand were prepared from hydrous RuX3.NO (X=Cl or Br) and diethylenetriamine. Among them, the crystal and molecular structures for trans-mer-[RuCl2(dien)NO]PF6 (1) and mer-[RuBr3(Hdien)NO]Br.H2O (2) (dien=diethylenetriamine) were determined by X-ray diffraction. The crystal of 1 was monoclinic, space group P2(1)/a with a=21.296(4), b=6.602 (2), c=10.079(2) angstrom, beta=97.12(2)-degrees, Z=4, and final R=0.0307, and the crystal of 2 was orthorhombic, space group P2(1)2(1)2(1) with a=11.988(4), b=17.234(9), c=7.141(2) angstrom, Z=4, and final R=0.0825. In 1, the two chloro ligands were in the trans arrangement and the dien was in the meridional arrangement as a tridentate ligand. In 2, the three bromo ligands were in the meridional arrangement with the Hdien coordinated to the ruthenium through one terminal and central nitrogen atoms as a bidentate ligand, and the remaining uncoordinated terminal moiety was -NH3+. The trans-strengthening effect that is expected to be caused by the NO was not observed for the Ru-N(dien) bond. The synthesized complexes were also characterized by IR and NMR spectra.