ORGANOMETALLIC COMPLEXES FOR NONLINEAR OPTICS .6. SYNTHESES OF RIGID-ROD RUTHENIUM SIGMA-ACETYLIDE COMPLEXES BEARING STRONG ACCEPTOR LIGANDS - X-RAY CRYSTAL STRUCTURES OF TRANS-[RU(C-CC6H4NO2-4)(2)(DPPM)(2)] AND TRANS-[RU(C-CC6H4C6H4NO2-4,4')(2)(DPPM

摘要

A series of systematically-varied 'rigid-rod' octahedral ruthenium acetylide complexes, bearing the strong acceptor substituent -NO2, of general formula trans-[Ru(C=CC(6)H(4)R-4)(2)(dppm)(2)] (R = NO2, C6H4NO2-4, C6H4CH=CHC6H4NO2-4, (E)) has been synthesized. X-ray structural studies of trans-[Ru(C=CC(6)H(4)R-4)(2)(dppm)(2)] (R = NO2, C6H4NO2-4) confirm the trans-disposed geometry of the acetylide ligands and, for the latter, non-planarity of the biphenylene groups. The mixed acetylide 'rigid-rod' complex trans-[Ru(C=CPh)(C=CC6H4NO2-4)(dppm)(2)] has also been prepared, Semiempirical calculations employing ZINDO were performed on the mixed-acetylide complex, the results suggesting that the effect of trans-disposed ligands on the molecular quadratic hyperpolarizability beta is not additive. [References: 24]