SYNTHESIS, STRUCTURE AND SPECTROSCOPIC PROPERTIES OF NOVEL METAL-METAL BONDED MANGANESE-RUTHENIUM COMPLEXES WITH ALPHA-DIIMINE LIGANDS - X-RAY STRUCTURE OF [(CO)(5)MN-RU(ME)(CO)(2)(SIGMA(N),SIGMA(N')-IPR-PYCA)](IPR-PYCA=PYRIDINE-2 -CARBALDEHYDE-N-ISO

摘要

The synthesis and spectroscopy of the complexes [(CO)(5)Mn-Ru(Me)(CO)(2)(alpha-diimine)] (alpha-diimine = N,N'-diisopropyl-1,4-diaza-1,3-butadiene (iPr-DAB), pyridine-2-carbaldehyde-N-isopropylimine (iPr-PyCa)) are reported. The metal fragments are bonded to each other by an uncommon manganese-ruthenium bond. The single crystal X-ray structure has been determined. The purple crystals of [(CO)(5)Mn-Ru(Me)(CO)(2)(iPr-PyCa)] are monoclinic, space group P2(1), Z = 4, with unit cell dimensions a = 9.6297(7), b = 20.923(1), c = 10.166(1) Angstrom and beta = 92.190(8)degrees. The structure refinement converged to R = 0.035 for 3277 observed reflections. Both complexes show a strong, solvatochromic absorption band in the visible region, which is assigned to Ru (d(p)i)-->alpha-diimine (pi*) transitions. In agreement with this assignment, thed Raman spectra show resonance enhancement of Raman intensity for nu(s)(CO) and nu(s)(CN) of the Ru(Me)(CO)(2)(alpha-diimine) fragment. [References: 32]