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Organometallics 2009, 28 , 6020.

Reactivity of [TpRuCl(PTA)(PPh 3 )] with Alkynes and Propargylic Alcohols: Occurrence of Structurally Related Cationic vs Neutral Allenylidene Complexes with the Ruthenium Hydrotris(pyrazolyl)borate Moiety.

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Organometallics 2009, 28 , 6020.

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  1. Reactivity of [TpRuCl(PTA)(PPh3)] with Alkynes and Propargylic Alcohols: Occurrence of Structurally Related Cationic vs Neutral Allenylidene Complexes with the Ruthenium Hydrotris(pyrazolyl)borate Moiety Sandra Bolano, M. Mar Rodriguez-Rocha, Jorge Bravo, Jesus Castro, Enrique Onate, and Maurizio Peruzzini* Organometallics 2009, 28,6020. Advisor: Yih-Hsing Lo Ph.D (羅義興) Student:

  2. ◆ Introdution ◆Results and Discussion ◆ Conclusions

  3. Introdution ★ What is Tp ★ Tp[M] Complexes ★Tp & Cp ★1,3,5-triaza-7-phosphaadamantane (PTA)

  4. What is Tp The Tp as a ligand in transition metal complexes has been introduced by Trofimenko in 1966. Tp: tris(pyrazolylborate) anion J. Am. Chem. Soc.1966, 88, 1842

  5. Tp[M] Complexes Inorg. Chem. 1992, 31, 2906

  6. Tp & Cp Inorg. Chem.1987, 26, 1507

  7. PTA PTA first reported in 1974 by Daigle et al. has seen only sparingly use since its discovery. J. Heterocycl. Chem. Rev.1974, 11, 407 Coord. Chem. Rev.2004, 248, 955

  8. PTA Catalyst Catalytic Activity in Hydrogenation of HCO3- in Aqueous Solution using RuCl2(PTA)4 HCO3- + H2 → HCO2-+ H2O Inorg. Chem. 2000, 39, 5083

  9. PTA Complexes Effects of compounds CpRuCl(PTA)2 and Cp∗RuCl(PTA)2 on tumor cell proliferation Murine adenocarcinoma TS/A cells, sown 24 h before, were treated with the compounds at 1/100 M concentrations for 24, 48 or 72 h in complete medium supplemented with 5% fetal calf serum. Cell viability was evaluated at the end of each treatment by the MTT assay. The reported data were the mean of three different experiments and each value was expressed as percentage of optical density of treated cells vs. controls (%T/C) ± S.E. calculated on the average of four separate wells per experiment. Statistical analysis: ANOVA and Dunnett post-test. ∗P < 0.05. ∗∗P < 0.01, vs. controls. J. Cluster Sci.2000, 11, 95

  10. Results and Discussion

  11. Scheme 1 PTA =

  12. Scheme 2 PTA =

  13. 31P{1H} (Pink) and 1H(3.5-5.2 ppm) (Green) NMR spectra in CD2Cl2of the reaction of Compound 2 with (a) 0, (b) 1.0, (c) 1.5, (d) 2.0, and (e) 2.5 equiv of HOTf. Compound 2 HOTf = CF3SO3H

  14. Scheme 2 PTA =

  15. Scheme 3 PTA =

  16. Scheme 4 PTA =

  17. Scheme 5 γ- attack γ- phosphonioalkynyl α- attack α isomerization γ α- phosphonioallenyl

  18. Scheme 6 PTA =

  19. Thermodynamic Parameters for the Formation of Complexes 8 (MeOD) and 9 (CD2Cl2) Plots of ln Keq vs 1000/T (K-1) for the equilibrium reactions of compound 5 with PPh2Me (left) and with PTA (right).

  20. Scheme 7 PTA =

  21. Conclusions

  22. Different reaction pathways were followed in polar • (MeOH) and apolar (toluene) solvents. • The reactivity of these species with selected electrophiles and nucleophiles was then investigated with the aim of shedding light on the possible different reactivities exhibited by related neutral versus cationic pair of unsaturated carbenes. • The solid-state structure of compound 9 confirmed the presence of the P-alkylated water-soluble PTA phosphine as the pendant group of the phosphonioallenyl moiety.

  23. You Make Me Completed

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