REACTIONS OF (ETA(6)-C6ME6)RUCL(MDMPP-P,O) AND (ETA(6)-C6ME6)RUCL(BDMPP-P,O,O) COMPLEXES WITH LEWIS-BASES OR ALKYNES, WHERE MDMPP-P,O = P(2-O-6-MEOC6H3)PH-2 AND BDMPP-P,O,O = P(2-O-6-MEOC6H3)(2)(2,6-(MEO)(2)C6H3)

Reaction of [(eta(6)-C6Me6)RuCl(MDMPP-P,O)] 1 (MDMPP-P, O=P(2-O-6-MeOC 6H3)Ph-2] with CO under high pressure at 95 degrees gave RuCl(CO)(3)(M DMPP-P,O) 2. [(eta(6)-p-cymene)Ru(TDMPP-P,O,O)] TDMPP-P,O,O=P(2-O-6-Me OC6H3)(2){2,6-(MeO)(2)C6H3}) reacted with CO or CO/2,6-xylyl isocyanid e under high pressure to form Ru(CO)(3)(TDMPP-P,O,O) 4 or Ru(CO)(2)(Xy INC)(TDMPP-P,O,O) 5 (Xyl = 2,6-Me2C6H3), respectively. Reactions of 1 with Lewis bases in the presence of NH,PF, gave [(eta(6)-C6Me6)RuL(MDM PP-P,O)](PF6) 6 (L = CO, XylNC). Complex 1 reacted with mono-substitut ed acetylenes in acetone in the presence of bases to form the metal al kynyl complexes [(eta(6)-C6Me6)Ru(C equivalent to CR)(MDMPP-P,O)] 7. S imilar reaction of 1 with PhC equivalent to CH in the presence of NaPF 6 in acetone or MeOH gave a vinylidene 8a (R=C=CHPh) and a carbene com plex 9a (R = CCH2Ph(OMe)) [(eta(6)-C6Me6)Ru(=R)(MDMPP-P,O)](PF6), resp ectively. A reaction of 1 with HC equivalent to CCMe2OH and NaPF6 in M eOH gave a metallabutadiene complex 10c [(eta(6)-C6Me6) Ru{=C(OMe)CH=C Me2} (MDMPP-P,O)]. X-ray analyses of 6b (L = XylNC), 7a (R = Ph) and 7 e (R = CH2OH) were carried out to confirm the structures; 6b, monoclin ic, space group P2(1)/c (No. 14), a = 9.910(8) Angstrom, b = 25.370(7) Angstrom, c = 16.020(7) Angstrom, beta = 105.29(5)degrees, V = 3885(7 ) Angstrom(3), Z = 4, R = 0.050, R-W = 0.053 for 4064 reflections (I > 3.0 sigma(I)); 7a, orthorhombic, space group Pbca, a = 17.222(4) Angs trom, b = 23.772(8) Angstrom, c = 16.003(8) Angstrom, V= 6552(7) Angst rom(3), Z = 8, R = 0.052, R-W = 0.052 for 1836 reflections (I > 3.0 si gma(I)); 7e, triclinic, space group P-1 (No. 2), a = 10.639(4) Angstro m, b = 14.778(3) Angstrom, c = 10.214(3) Angstrom, alpha = 97.05(2)deg rees, beta = 113.01(2)degrees, gamma = 79.12(2)degrees, V = 1449(2) An gstrom(3), Z = 2, R = 0.041, R-W = 0.040 for 3270 reflections. (I > 3. 0 sigma(I)). (C) 1998 Elsevier Science S.A. All rights reserved.