DICHLORO(O-ISOPROPOXYPHENYLMETHYLENE)(TRICYCLOHEXYLPHOSPHINE)RUTHENIUM(II)

PIB-supported Grubbs-Hoveyda 2nd generation catalyst (molecule 8): A mixture of 1.14 g (0.48 mmol) of 1, 3-bis(2, 6-dimethyl-4-(polyisobutyl)phenyl)-4, 5-dihydro-imidazolium tetrafluoroborate, 0.15 g (0.75 mmol) of KHMDS, 0.05 g (0.5 mmol) of CuCl and 0.36 g (0.57 mmol) of 1st generation Hoveyda-Grubbs catalyst was prepared was dissolved in 5 mL of toluene. The solution was heated to 100 C. for 3 hours. Solvent was removed under reduced pressure and purified by column chromatography (dichloromethane) resulting in a dark green viscous residue. The yield was 60% (0.75 g). 1H-NMR (500 MHz, CDCl3), delta: 0.8-1.6 (m, 280H), 1.87 (s, 2H), 2.41 (b, 6H), 2.62 (b, 6H) 4.15 (s, 4H), 4.90 (m, 1H) 6.8 (m, 2H), 6.98 (m, 1H), 7.22 (b, 4H), 7.47 (m, 1H), and 16.67 (s, 1H). 13C NMR (125 MHz, CDCl3), delta: 21.62, multiple peaks between 30-40 and 58-60, 113.10, 122.42, 123.09, 126.53, 127.01, 129.69, 137.30, 139.21, 145.41, 145.44, 152.16, 152.43, 152.45, 211.19, and 297.23 (m).A dry, 1000-mL, one-necked, round-bottomed flask is equipped with a magnetic stirring bar, rubber septum and an argon inlet. The flask is charged under an argon atmosphere with a solid SIMES x HBF4 2 (35.28 mmol, 13.9 g) and dry n-hexane (400 ml_). A solution of potassium tert-amylate (21.6 ml_, 36.75 mmol) is added from a syringe and the resulting mixture is stirred under argon at room temperature for 1 h. To the resulted solution a solid Hoveyda-Grubbs 1st generation catalyst 1 (29.4 mmol, 17.6 g) is added in one portion. The flask is equipped with a reflux condenser with an argon inlet at the top and the reaction mixture is refluxed for 2 h. The contents of the flask are cooled to room temperature and solid CuCI (51.45 mmol, 5.1 g) is added slowly in three portions and the resulting mixture is refluxed for 2 h. From this point forth, all manipulations are carried out in air.; 1.11. Isolation of the product by crystallization; The reaction mixture is evaporated to dryness and re-dissolved in ethyl acetate (200 ml_). The solution is filtrated through a Buchner funnel with glass frit filled with Celite and then concentrated in vacuo. The residue is dissolved in ambient temp. 1 :10 v/v mixture of CH2CI2 and methanol (220 ml_). After concentration to ca. % of the initial volume using a rotary evaporator (room temperature) crystals are precipitated. These crystals are filtered- off on a Buchner funnel with glass frit. The crystals are washed twice with small portions of CH3OH (-20 ml_), and dried in vacuo to give pure Hoveyda 2nd catalysts 3 (25.3 mmol, 15.81 g). The filtrate after crystallization is evaporated to dryness and crystallized for the second time from CH2CI2 and methanol using the same protocol giving an additional crop of pure Hoveyda 2nd generation catalyst (1.7 mmol, 1.08 g). The total yield of pure Hoveyda-Grubbs 2nd generation catalyst 3 is 92% (27.0 mmol, 16.9 g).Metathesis by Ethenolysis of Methyl Oleate Catalyzed by a Type 3 Complex (FIG. 1) in an Ionic Liquid; 1 ml of 3-butyl-1, 2-dimethylimidazolium bis-triflylamide with formula [BMMI]+[N(CF3SO2)2]- pre-dried overnight at 80° C., 148 mg of methyl oleate (source: Fluka, with a purity higher than 98percent) and 15 mg of the complex with formula Cl2Ru(CH-o-O-iPrC6H4)PCy3 (synthesized by reacting the 1st generation Grubbs complex with formula Cl2Ru(CHC6H5)(PCy3)2 with 1-isopropoxy-2-vinylbenzene in the presence of CuCl), this corresponding to 5percent molar of catalyst with respect to methyl oleate, were introduced, in an inert atmosphere of argon, into an autoclave reactor provided with an agitation system and a pressure sensor. The autoclave was then placed under vacuum and pressurized to obtain a pressure of 10 bars (1 MPa) of ethylene (origin: Alphagas, quality N25). The temperature was kept constant at 20° C. The medium was stirred at ambient temperature for 2 hours, then the excess ethylene was slowly purged by returning to atmosphere pressure at a temperature not exceeding 20° C. and the autoclave was again placed under an atmosphere of argon. The products were separated from the ionic liquid by adding 2 to 3 ml of heptane distilled over CaH2 and degassed. An aliquot (100 mul) of the extracted solution was passed through a short silica column (2 cm) eluted with diethyl ether. It was analyzed by gas phase chromatography (ZB-1 column, 100percent dimethylpolysiloxane, 30 metres, helium vector gas 2 ml/min, temperature programming: 60° C. then 5° C./min to 220° C.) coupled to a mass spectrometer. The methyl oleate conversion was 95percent. It was calculated using decane as an internal reference. The reaction products were composed of 1-decene (fraction A) and methyl decenoate (fraction B). The presence of 1-decene isomers was not detected. Homo-metathesis products were present in trace amounts and could not be quantified.In a glove box, NHC ligand precursor 23 (63 mg, .13, mmol), ruthenium precursor 11 (78 mg, .13 mmol) and KOMJu(Fe) (29 mg, .13 mmol) were combined in toluene. The flask was sealed, removed from the glove box and stirred at 60 0C for 18 hours. The reaction was concentrated and purified by flash column chromatography (5% --> 20% Et2O/Pent). There were 3 bands that could be isolated from this column, first 2 brown bands and then one green band. The second brown band was the desired product; however, it was not completely pure after one column. Recolumning in 10% Et2O/Pentane gave a brown oil product completely pure by 1H NMR (9 mg, 9%) and another fraction still slightly impure (18 mg, 18%). The products were lyophilized from benzene to give solids. 1H NMR (300 MHz, CDCl3) delta 16.78 (s, IH), 8.13 (br, 2H), 7.74-7.62 (m, 4H), 7.07-7.04 (m, IH), 6.97 (dd, J = 3, 1.5 Hz, IH), 6.66 (t, J = 7.5 Hz, 3H), 6.34 (d, J = 8.4 Hz, IH), 4.49 (sept, J = 6 Hz, IH), 1..44 (d, J = 6 Hz, 6H), 1.44 (br, 18H), 1.18 (br, 18H); 13C (75 MHz, CDCl3) delta; HRMS (EI+) calc for C4IH56Cl2N2ORu, 764.2814. Found 764.2842.NHC ligand precursor 21 (9 mg, .03 mmol), KOz-Bu(F6) (6 mg, .03 mmol), and ruthenium complex 911 (13 mg, .02 mmol) were all combined in CgDbeta in a screw cap NMR tube in a glove box. The NMR tube was removed and heated at 600C for 2.5 hour in a fume hood. Conversion to catalyst 22 was determined to be 14% by proton NMR. 1H NMR (300 MHz, CDCl3) delta 17.19 (IH, s).NHC ligand precursor 10 (156 mg, .3 mmol), KOz-Bu(F g) (66 mg, .3 mmol), and ruthenium complex 11 (132 mg, .22 mmol) were all combined in toluene in a glove box. The flask was removed and stirred at 60 0C for 18 hours in a fume hood. The reaction mixture was then directly purified by flash column chromatography (5% Et2theta/Hexanes, run 2 times) to yield catalyst 12 (34 mg, 20%) as a green oil. The catalyst was then lyophilized from benzene to give a pale green solid. It should be noted that by 1H NMR the conversion to 12 is 50%. 1H NMR (300 MHz, CDCl3) delta 16.91 (IH, s), 8.14-8.13 (2H, m), 7.73 (2H, m), 7.64 (IH, m), 7.52 (IH, m), 7.06-6.92 (2H, m), 6.62 (IH, t, J = 7.5 Hz), 6.31 (IH, d, J - 8.4 Hz), 4.47 (IH, quint, J = 6 Hz), 3.51 (4H, s), 1.51 (18H, s), 1.35 (6H, d, J = 6 Hz), 1.24 (18H, s); HRMS (EI+) calc for C4IH58N2OCl2Ru 766.2970. Found 766.3007. Fig. 4 depicts the single crystal X-ray structure was obtained for catalyst 12.

Molecular Weight:600.6
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:6
Exact Mass:600.162849
Monoisotopic Mass:600.162849
Topological Polar Surface Area:9.2
Heavy Atom Count:33
Complexity:404
Covalently-Bonded Unit Count:2
Compound Is Canonicalized:Yes