Synthesis and Characterization of Bimetallic Ruthenium Complexes with (CH)6and Related Bridges

Abstract

Treatment of RuHCl(CO)(PPh3)3 with (E)-HC⋮CCHCHC⋮CH produces [RuCl(CO)(PPh3)2]2(μ-(E,E,E)-CHCHCHCHCHCH). The latter complex reacts with PMe3, 4-phenylpyridine (PhPy), and 2,6-(Ph2PCH2)2C5H3N (PMP) to give [RuCl(CO)(PMe3)3]2(μ-CHCHCHCHCHCH), [RuCl(CO)(PhPy)(PPh3)2]2(μ-CHCHCHCHCHCH), and [RuCl(CO)(PMP)]2(μ-CHCHCHCHCHCH), respectively. Treatment of [RuCl(CO)(PPh3)2]2(μ-(E,E,E)-CHCHCHCHCHCH) with t-BuNC and NaBPh4 gives {[Ru(t-BuNC)3(PPh3)2]2(μ-COCHCHCHCHCHCHCO)}(BPh4)2, the structure of which has been confirmed by X-ray diffraction. Treatment of RuHCl(CO)(PPh3)3 with excess (Z)-HC⋮CCHCHC⋮CH followed by PMe3 produces RuCl((E,Z)-CHCHCHCHC⋮CH)(CO)(PMe3)3. The mononuclear complex reacts with RuHCl(CO)(PPh3)3 to give (PMe3)3(CO)ClRu−CHCHCHCHC(CH2)−RuCl(CO)(PPh3)2, which reacts with t-BuNC to give [(PMe3)3(CO)ClRu−CHCHCHCHC(CH2)CO−Ru(t-BuNC)3(PPh3)2]Cl.