Dinuclear acetylide-bridged ruthenium(ii) complexes with rigid non-aromatic spacers†
Abstract
Rigid dinuclear ruthenium complexes containing non-aromatic caged and polycyclic spacer groups were synthesised and characterised. The complexes, [trans,trans-{Ru(dmpe)2(CCtBu)}2(μ-C
C–X–C
C)], where X = 1,4-bicyclo[2.2.2]octane (C8H12) or 1,12-p-carborane (p-C2B10H10), were formed via the metathesis of terminal organic bisacetylenes with the methylruthenium complex, [trans-Ru(dmpe)2(CH3)(C
CtBu)], under mild conditions. Electrochemical studies demonstrated electronic interactions across the non-aromatic caged and polycyclic spacers was less than in the analogous complex with an aromatic spacer group, [trans,trans-{Ru(dmpe)2(C
CtBu)}2(μ-C
C-p-C6H4-C
C)]. Mononuclear complexes, [trans-Ru(dmpe)2(C
CtBu)(C
C–X–C
CH)], were also synthesised. [trans-Ru(dmpe)2(C
CtBu)(C
C–C8H12–C
CH)] and [trans,trans-{Ru(dmpe)2(C
CtBu)}2(μ-C
C–p-C2B10H10–C
C)] were structurally characterised by X-ray crystallography.