With the goal of realizing novel organometallic molecular wires for molecular electronic devices, electron delocalization in transition metal complexes containing linear s-polyynyl ligands have received a great deal of attention over the last decade. Largely unexplored are metal compounds containing cross-conjugated polyynes, the simplest of which being iso-triacetylene (geminal-diethynylethene or gem-DEE). However, the metallation chemistry of gem-DEE ligands is limited to Pt(II) compounds which limits the investigation of the p-conjugation therein. Hence, the preparation of gem-DEE complexes of redox active and photoactive transition metals will help unravel the cross-conjugation effect. Presented here are the syntheses and characterizations of the first transition metal complexes containing cross-conjugated ligands beyond Pt(II). An investigation of the p-conjugation within was performed on photoactive trans-[Cr(III)(cyclam)(X-gem-DEE)2]OTf) (X = iPr3Si and ferrocenyl (Fc)) and redox active trans-Ru2(III,III)(DMBA)4(X-gem-DEE)2 and Ru2(II,III)(ap)4(X-gem-DEE)) (X = iPr3Si, Fc, C6H4-p-N(Me)2, C6H4-p-NO3) compounds in hopes of elucidating the cross-conjugation effect.

Redox and photoactive metallyne [sigma]-acetylide complexes with <i>cross</i>-<i>conjugated</i> ligands

243rd National Meeting (2012)

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Redox and photoactive metallyne [sigma]-acetylide complexes with cross-conjugated ligands