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Reactions of (η6-C6Me6)RuCl(MDMPP-P,O) and (η6-C6Me6)RuCl(BDMPP-P,O,O) complexes with Lewis bases or alkynes, where MDMPP-P,OP(2-O-6-MeOC6H3)Ph2and BDMPP-P,O,OP(2-O-6-MeOC6H3)2{2,6-(MeO)2C6H3}1 Dedicated to Professor Akira Nakamura on the occassion of his retirement from Osaka University.1

Journal of Organometallic Chemistry
Publication Date
DOI: 10.1016/s0022-328x(98)00771-2
  • Bis[Dichloro(η6-Arene)Ruthenium(Ii)]
  • (2
  • 6-Dimethoxyphenyl)Diphenylphosphine
  • Ruthenium Alkyne Complexes


Abstract Reaction of [( η 6-C 6Me 6)RuCl(MDMPP- P, O)] 1 (MDMPP- P, OP(2-O-6-MeOC 6H 3)Ph 2] with CO under high pressure at 95° gave RuCl(CO) 3(MDMPP- P, O) 2. [( η 6- p-cymene)Ru(TDMPP- P, O, O)] (TDMPP- P, O, OP(2-O-6-MeOC 6H 3) 2{2,6-(MeO) 2C 6H 3}) reacted with CO or CO/2,6-xylyl isocyanide under high pressure to form Ru(CO) 3(TDMPP- P, O, O) 4 or Ru(CO) 2(XyINC)(TDMPP- P, O, O) 5 (Xyl=2,6-Me 2C 6H 3), respectively. Reactions of 1 with Lewis bases in the presence of NH 4PF 6 gave [( η 6-C 6Me 6)RuL(MDMPP- P, O)](PF 6) 6 (L=CO, XylNC). Complex 1 reacted with mono-substituted acetylenes in acetone in the presence of bases to form the metal alkynyl complexes [( η 6-C 6Me 6)Ru(CCR)(MDMPP- P, O)] 7. Similar reaction of 1 with PhCCH in the presence of NaPF 6 in acetone or MeOH gave a vinylidene 8a (R=CCHPh) and a carbene complex 9a (R=CCH 2Ph(OMe)) [( η 6-C 6Me 6)Ru(R)(MDMPP- P, O)](PF 6), respectively. A reaction of 1 with HCCCMe 2OH and NaPF 6 in MeOH gave a metallabutadiene complex 10c [( η 6-C 6Me 6) Ru{C(OMe)CHCMe 2}(MDMPP- P, O)]. X-ray analyses of 6b (L=XylNC), 7a (R=Ph) and 7e (R=CH 2OH) were carried out to confirm the structures; 6b, monoclinic, space group P2 1/ c (No. 14), a=9.910(8) Å, b=25.370(7) Å, c=16.020(7) Å, β=105.29(5)°, V=3885(7) Å 3, Z=4, R=0.050, R w=0.053 for 4064 reflections ( I>3.0 σ( I)); 7a, orthorhombic, space group Pbca, a=17.222(4) Å, b=23.772(8) Å, c=16.003(8) Å, V=6552(7) Å 3, Z=8, R=0.052, R w=0.052 for 1836 reflections ( I>3.0 σ( I)); 7e, triclinic, space group P 1 (No. 2), a=10.639(4) Å, b=14.778(3) Å, c=10.214(3) Å, α=97.05(2)°, β=113.01(2)°, γ=79.12(2)°, V=1449(2) Å 3, Z=2, R=0.041, R w=0.040 for 3270 reflections ( I>3.0 σ( I)).

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