Chemistry Letters
Online ISSN : 1348-0715
Print ISSN : 0366-7022
ISSN-L : 0366-7022
Letter
Synthesis of Bidentate σ-Borane–Ruthenium Complexes [Cp*Ru(PiPr3)(η2-BH3·L)]+ (L = Amines or Phosphines): Structures, Properties, and Reactivities
Yasuro KawanoYoshiki AsakaMamoru Shimoi
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2017 Volume 46 Issue 8 Pages 1200-1203

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Abstract

Chloride abstraction from [Cp*RuCl(PiPr3)] using Na[BArf4] in the presence of BH3·L afforded bidentate σ-borane complexes [Cp*Ru(PiPr3)(η2-BH3·L)][BArf4], where L = quin (N(C2H4)3CH), NMe3, NHMe2, NHiPr2, NH2Me, PMe3, PMe2Ph; Cp* = η5-C5Me5; [BArf4] = [B{3,5-C6H3(CF3)2}4]. In these compounds, the borane ligand is coordinated to the ruthenium atom through two B–H–Ru three-center two-electron bonds. Phosphine–borane complexes exhibit fluxional behavior due to the site exchange between the bridging and terminal BH hydrogen atoms at room temperature. Secondary amine–borane derivatives release H2 on heating. BH3·NHMe2 and BH3·NHiPr2 undergo dehydrogenation even with use of a catalytic amount of [Cp*RuCl(PiPr3)] and Na[BArf4] to ultimately yield [BH2NMe2]2 and BH2=NiPr2, respectively.

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© 2017 The Chemical Society of Japan
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