A mixed-valence dinuclear ruthenium complex composed of Ru(II)-acetylide and Ru(III)-tropolonato units: Acetylide-vinylidene interconversion in solution and solid state

作者：Yoshida Jun^*; Kuwahara Kyohei; Yuge Hidetaka

来源：Journal of Organometallic Chemistry, 2014, 756: 19-26.

DOI：10.1016/j.jorganchem.2014.01.018

• Ruthenium
• Acetylide
• Vinylidene
• Protonation/deprotonation
• Mixed-valence
• Mechanochemical reaction

A dinuclear Ru(II)-eRu(III) complex, [Ru(acac)(2)(mu(2)-tropC(2))RuCp(dppe)] (2a, acac - acetylacetonato, Cp = cyclopentadienyl, dppe = 1,2-bis(diphenylphosphino)ethane, HtropC(2)H = 5-acetylenyltropolone), has been newly synthesized and fully characterized. 2a is composed of two hetero units, [(RuCp)-Cp-II(dppe)] and [Ru-III(acac)(2)(trop)], and it showed a broad absorption in the NIR region, indicating the electronic communication between the two hetero units. 2a quantitatively converted to the vinylidene form [2aH](TsO) by the addition of p-toluenesulfonic acid monohydrate (TsOH center dot H2O) to the chloroform solution of 2a. The weak NIR absorption exhibited by 2a disappeared in [2aH](TsO). [2aH](TsO) re-converted to the acetylide 2a after the addition of triethylamine to the acetonitrile solution of [2aH](TsO). H-1 NMR and UV-vis-NIR spectroscopy indicated the mutual interconversion and on/off behavior of the electronic communication between the two hetero units. Moreover, structural interconversion also proceeded in the solid state. 2a swiftly converted to [2aH](TsO) after grinding with solid TsOH center dot H2O for 5 min. The conversion yield estimated from IR measurements was 70%. [2aH](TsO) re-converted to 2a after re-grinding with AcONa with a conversion yield of 84%. These results indicate the usability of 2a as a molecular switch triggered by protonation/deprotonation both in solution and solid state.

• 出版日期2014-4-15