REACTIONS OF TERTIARY-AMINES WITH TRINUCLEAR CLUSTERS .3. REACTIONS OF N-METHYLPYRROLIDINE WITH RU3(CO)12 AND OS3(CO)10(CH3CN)2

The reaction of N-methylpyrrolidine with Ru3(CO)12 in the presence of the three reaction promoters Fe2(CO)4(mu-SCH2CH3)2(P(C6H5)3)2 (iron dimer), (CH3)3NO, and (C6H5)2C equal sign with dot above O-Na+ was studied in the temperature range 65-80-degrees-C. In the presence of the iron dimer catalyst, in hexane at 68-degrees-C, one major trinuclear product isolated in 15-20% yield proved to be (mu-H)2Ru3(CO)9(mu-3-eta-2-CH-N activated = CCH2CHCH2) (1). In the presence of trimethylamine N-oxide or sodium benzophenone ketyl in benzene at 80-degrees-C a different trinuclear product isolated in 30% yield, (mu-H)Ru3(CO9(mu-3-eta-2-N activated = CCH2CH2CH2) (2), is a structural analogue of the major product obtained from the reaction of triethylamine with Ru3(CO)12 in the presence of the above mentioned diiron reaction promoter. A minor product isolated in the reaction of Ru3(CO)12 with N-methylpyrrolidine in the presence of (CH3)3NO is the tetranuclear eta-1-carbene species (mu-H)4Ru4(CO)11(eta-1-C activated = N(CH3)CH2CH2CH2) (3). Thermolysis of 1 in heptane at 100-degrees-C gave moderate yields of the compound (mu-H)Ru3(CO)9(mu-3-eta-3-CH3N activated-CH = CHCH2CH2) (4), in which two hydrogens have been transferred to the methyne carbon and further rearrangement of the ligand has occurred. The lightly stabilized cluster Os3(CO)10(CH3CN)2 was reacted with N-methylpyrrolidine in refluxing benzene to give (mu-H)Os3(CO)10(mu-eta-2-CH3N activated = CC(H)CH2CH2) (5) and (mu-H)Os3(CO)10(mu-eta-1-CH3N activated = C(H)CCH2CH2) (6). Compounds 1-5 were characterized by X-ray diffraction methods in the solid state, and 1-6, by H-1 NMR and infrared spectroscopy in solution. Compound 1 crystallizes in the monoclinic space group P2(1)/n, with a = 9.015 (2) angstrom, b = 16.759 (4) angstrom, c = 13.266 (3) angstrom, and beta = 95.98 (2)-degrees. Least-squares refinement of 3822 observed reflections gave a final agreement factor of R = 0.048 (R(w) = 0.055). Compound 2 crystallizes in the monoclinic space group P2(1)/m, with a = 7.657 (1) angstrom, b = 14.910 (3) angstrom, c = 8.172 (2) angstrom, and beta = 106.32 (2)-degrees. Least-squares refinement of 1938 observed reflections gave a final agreement factor of R = 0.026 (R(w) = 0.031). Compound 3 crystallizes in the monoclinic space group P2(1)/c, with a = 10.198 (1) angstrom, b = 14.229 (2) angstrom, c = 16.512 (3) angstrom, and beta = 102.34 (1)-degrees. Least-squares refinement of 2033 observed reflections gave a final R = 0.025 (R(w) = 0.036). Compound 4 crystallizes in the monoclinic space group P2(1)/c, with a = 8.858 (2) angstrom, b = 13.455 (5) angstrom, c = 18.400 (4) angstrom, and beta = 118.70 (2)-degrees. Least-squares refinement of 2254 observed reflections gave a final R = 0.043 (R(w) = 0.045). Compound 5 crystallizes in the orthorhombic space group P2(1)2(1)2(1), with a = 11.567 (2) angstrom, b = 17.653 (6) angstrom, and c = 9.900 (2) angstrom. Least-squares refinement of 2600 observed reflections gave a final R = 0.074 (R(w) = 0.065).