Organometallic complexes for nonlinear optics VI: Syntheses of rigid-rod ruthenium σ-acetylide complexes bearing strong acceptor ligands; X-ray crystal structures of trans-[Ru(C≡CC<sub>6</sub>H<sub>4</sub>NO<sub>2</sub>-4)<sub>2</sub> (dppm)<sub>2</sub>]
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McDonagh, Andrew M.
Whittall, Ian R.
Humphrey, Mark G.
Hockless, David C.R.
Skelton, Brian W.
White, Allan H.
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A series of systematically-varied 'rigid-rod' octahedral ruthenium acetylide complexes, bearing the strong acceptor substituent -NO2, of general formula trans-[Ru(C≡CC6H4R-4)2(dppm)2] (R = NO2, C6H4NO2-4, C6H4CH=CHC6H4NO2-4, (E)) has been synthesized. X-ray structural studies of trans-[Ru(C≡CC6H4R-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 β is not additive.
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Journal of Organometallic Chemistry
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