6. DISCUSIÓN DE RESULTADOS:
6.2. Contrastación de resultados con otros estudios similares:
General Methods. Racemic Br2BINOL,28 (COD)PtCl2,29 G1-CO2Me and G1t-
CO2Me19 were synthesized according to literature procedures. The platinum complexes
P2PtCl2, P2PtCO3, and P2Pt(BINOL) were synthesized by procedures similar to those
published for dppe analogs16,30 All chemicals were purchased from Aldrich except 1,2- bis(dichlorophosphino)ethane (Strem) and (S)-BINOL (Kankyo Kagaku Center Co., Ltd., Japan), and used as received. Before use, acetone was distilled from calcium sulfate. Tetrahydrofuran, dichloromethane and toluene were passed through a column of activated alumina. Chlorobenzene was distilled from P2O5 and freeze-pump-thaw degassed before use
in polymerizations, but was used as received for rebinding experiments. AIBN (2,2’- azobis(isobutyro)nitrile) was recrystallized from methanol, dried in vacuo, and stored under nitrogen at -35 °C. EDMA (ethylene glycol dimethacrylate) was washed twice with aqueous 1 M NaOH and once with brine to remove inhibitor, dried over MgSO4, filtered, distilled
(105 °C/1 mmHg), freeze-pump-thaw degassed, and stored under nitrogen at -35 °C. Polymerizations were performed in an MBraun LabMaster 100 glovebox. Reactions performed under nitrogen were carried out using standard Schlenk techniques.
NMR spectra were recorded on either a Bruker Avance 300 or a Bruker Avance 400 spectrometer. Chemical shifts are reported in ppm and are referenced to the residual solvent
28 Cram, D. J.; Sogah, G. D. Y. J. Am. Chem. Soc.1979, 101, 3035-3042.
29 McDermott, J. X.; White, J. F.; Whitesides, G. M. J. Am. Chem. Soc.1976, 98, 6521-6527.
30 (a) Gugger, P.; Limmer, S. O.; Watson, A. A.; Willis, A. C.; Wild, S. B. Inorg. Chem.1993, 32, 5692- 5696. (b) Brunkan, N. M.; White, P. S.; Gagné, M. R. Angew. Chem., Int. Ed.1998, 37, 1579-1582.
peaks (1H and 13C NMR) or to an external standard (85% H3PO4, 31P NMR). The dendritic
P2PtCl2 compounds were not soluble enough in chloroform to allow carbon spectra to be
recorded even overnight. Many of the carbon signals in G1t(2,3,4) and the Pt(BINOL)s
overlap, and therefore signals were not detected for all carbons in the compounds. Carbon spectra for phosphorus-containing compounds were recorded while decoupling both hydrogen and phosphorus nuclei. Microanalysis for dppe-OTBDMS and dppe-OH was not
obtained because these compounds did not combust completely for elemental analysis (∆%C was repeatedly >10%). Microanalysis of the P2Pt(BINOL) compounds was not obtained
because these compounds tend to retain traces of solvent.
HPLC analysis was performed on a Hewlett-Packard Series 1100 instrument, using a Daicel Chiralcel OD-H column (95% hexanes/5% ethanol, 0.8 mL/min flow rate). UV absorbance chromatograms were recorded at wavelengths of 220, 232, 254, 289 and 333 nm and compared to calibration curves to determine analyte concentration.
TBDMS 4-bromophenol. A solution of 4-bromophenol (10.0 g, 58 mmol) and
imidazole (5.9 g, 87 mmol) in 200 mL dimethylformamide was cooled to 0 °C, and tert- butyldimethylsilylchloride (TBDMS-Cl, 9.6 g, 64 mmol) was added. The solution was stirred for 12 hours and allowed to warm to room temperature. A saturated aqueous solution of ammonium chloride (100 mL) was added, and the mixture was extracted with 200 mL ethyl acetate. The ethyl acetate was washed with 100 mL 0.5 M NaOH and with 100 mL brine, dried over magnesium sulfate, and filtered. The solvent was removed in vacuo to give TBDMS 4-bromophenol (15.5 g, 93% yield). 1H NMR: (400 MHz, CDCl3, δ): 7.34 (d, J =
CDCl3, δ): 155.1, 132.6, 122.2, 113.9, 26.0, 18.5, -4.2. Anal. Calcd for C12H19BrOSi: C,
50.17; H, 6.67. Found: C, 50.02; H, 6.68.
dppe-OTBDMS. Magnesium turnings (2.0 g, 84 mmol) were flame dried inside a
100-mL Schlenk flask. The flask was cooled and 2.0 mL THF was added, followed by 0.25 mL (4.3 mmol) methyl iodide. The mixture was stirred for several minutes until cloudy. The liquid was removed by cannula and the magnesium was rinsed three times with 2 mL THF. A solution of 12.0 g (42 mmol) TBDMS 4-bromophenol in 40 mL THF was added to the magnesium and the mixture was refluxed for 3 hours. After cooling, the solution was filtered via cannula from the magnesium into a flame-dried 250-mL Schlenk flask. The solution was cooled to -50 °C and a solution of 1.3 mL (8.4 mmol) 1,2-bis(dichlorophosphino)ethane in 5.0 mL THF was added dropwise. The solution was stirred at -50 °C for 4 hours before quenching with 2.0 mL deoxygenated methanol. Borane-tetrahydrofuran complex (60 mL of a 1.0 M solution in tetrahydrofuran) was added and the solution was allowed to warm to room temperature overnight. The volume of the solution was reduced in vacuo until white solid appeared. Ethanol (25 mL) was added, and the mixture was stored at -26 °C overnight. The white solid was collected by vacuum filtration (5.1 g, 64% yield). 1H NMR: (400 MHz, CDCl3, δ): 7.45 (m, 8H), 6.84 (d, J = 8.4 Hz, 8H), 2.22 (br, 4H), 0.95 (s, 36H), 0.19 (s, 24H). 13C NMR: (75.5 MHz, CDCl
3, δ): 158.8, 133.9, 120.8, 120.1, 25.7, 20.3, -4.2. 31P NMR:
(161.3 MHz, CDCl3, δ): 15.5.
dppe-OH. dppe-OTBDMS (3.0 g, 3.2 mmol) was dissolved in 75 mL THF and
cooled to 0 °C. A solution of tetrabutylammonium fluoride (1.0 M in THF, 16 mL) was added dropwise. The solution was allowed to stir 16 h and warm to room temperature. A white precipitate formed. The volume of the solution was reduced in vacuo to 10 mL and 25
mL of ethanol was added to further precipitate the product. The white solid was collected by vacuum filtration and dried in vacuo. (1.5 g, 64% yield). 1H NMR: (400 MHz, DMSO-d6,
δ): 7.25 (m, 8H), 6.70 (d, J = 8.4 Hz, 8 H), 3.17 (m, 8H), 2.00 (br, 4H), 1.55 (m, 8H), 1.31 (q, J = 7.2 Hz, 8H), 0.94 (t, J = 7.2 Hz, 12H). 13C NMR: (75.5 MHz, DMSO-d6, δ): 164.9,
134.2, 117.8, 117.7, 114.5, 58.5, 24.0, 21.3, 20.1, 14.4. 31P NMR: (162.1 MHz, DMSO-d6,
δ): 13.1.
G0. (Method A): dppe-OH (0.25 g, 0.34 mmol), 4-vinylbenzoic acid (0.25 g, 1.7
mmol) and 4-(dimethylamino)pyridine (0.13 g, 1.0 mmol) were dissolved in 40 mL dichloromethane. 1,3-Dicyclohexylcarbodiimide (0.35 g, 1.7 mmol) was added and the mixture was stirred for 16 hours at room temperature under nitrogen. The reaction was then eluted through a pad of silica with 75 mL ethyl acetate. After removal of the solvent in vacuo, methanol was added to the resultant oil to precipitate a solid. The solid was collected by vacuum filtration and rinsed with methanol and hexanes. The solid was dissolved along with 1,4-diazabicyclo[2.2.2]octane (0.15 g, 1.4 mmol) in 30 mL toluene and the solution was stirred at 35 °C under nitrogen for 16 hours. The solution was reduced in volume to 5 mL and 25 mL of methanol was added to precipitate the product. A white solid was collected by vacuum filtration, rinsed with methanol, and dried in vacuo to give G0 (0.22 g, 65% yield).
1H NMR: (400 MHz, CDCl
3, δ): 8.12 (d, J = 8.4 Hz, 8H), 7.49 (d, J = 8.0 Hz, 8H), 7.42 (m,
8H), 7.19 (d, J = 8.4 Hz, 8H), 6.76 (dd, J = 17.6, 10.8 Hz, 4H), 5.89 (d, J = 17.6 Hz, 4H), 5.41 (d, J = 10.8 Hz, 4H), 2.12 (br, 4H). 13C NMR: (75.5 MHz, CDCl3, δ):165.0, 151.9,
143.0, 136.3, 135.5, 134.3, 130.9, 128.8, 126.6, 122.3, 117.3, 24.4. 31P NMR: (162.1 MHz, CDCl3, δ): -12.6. Anal. Calcd for C62H48O8P2: C, 75.76; H, 4.92. Found: C, 75.71; H, 4.95.
(G0)PtCl2. (Method B): A solution of G0 (0.20 g, 0.20 mmol) in 10 mL
dichloromethane was added to a solution of (COD)PtCl2 (0.075 g, 0.20 mmol) in 10 mL
dichloromethane. The solution was stirred for 1 hour before the solvent was removed in vacuo. Methanol (20 mL) was added and the white solid was collected by vacuum filtration, rinsed with methanol and dried in vacuo to give (G0)PtCl2 (0.21 g, 85% yield). 1H NMR:
(400 MHz, CDCl3, δ): 8.14 (d, J = 8.0 Hz, 8H), 7.97 (dd, J = 11.8, 8.4 Hz, 8H), 7.53 (d, J =
8.0 Hz, 8H), 7.38 (dd, J = 8.4, 2.0 Hz, 8H), 6.78 (dd, J = 17.6, 10.8 Hz, 4 H), 5.91 (d, J = 17.6 Hz, 4H), 5.43 (d, J = 10.8 Hz, 4H), 2.42 (m, 4H). 31P NMR: (162.1 MHz, CDCl
3, δ):
40.7 (JPt-P = 3592 Hz).
5. (Method C): To a solution of (G0)PtCl2 (0.12 g, 0.095 mmol) in 25 mL
dichloromethane was added silver carbonate (39 mg, 0.14 mmol) and 5 drops of distilled water. The mixture was stirred at room temperature, protected from light until all the PtCl2
was converted to PtCO3 as monitored by 31P NMR. The mixture was filtered through a pad
of Celite to remove the silver salts. (S)-BINOL (30 mg, 0.11 mmol) was added to a solution of the PtCO3 in 25 mL dichloromethane and the solution was stirred at room temperature
until 31P NMR showed complete conversion to the Pt(BINOL). The dichloromethane was removed in vacuo and 25 mL diethyl ether was added. The yellow solid was collected by vacuum filtration and rinsed with an additional 25 mL diethyl ether to remove excess BINOL. After drying overnight in vacuo 5, (G0)Pt((S)-BINOL) (0.12 g, 84% yield) was
obtained. 1H NMR: (400 MHz, CDCl3, δ): 8.19 (d, J = 8.4 Hz, 4H), 8.08 (m, 8H), 7.81 (m,
4H), 7.68 (d, J = 8.0 Hz, 2H), 7.54 (m, 6H), 7.47 (d, J = 8.4 Hz, 4H), 7.35 (d, J = 7.2 Hz, 4H), 7.26 (d, J = 7.6 Hz, 4H), 7.06 (m, 2H), 6.96 (m, 4H), 6.79 (dd, J = 17.6, 10.8 Hz, 2H), 6.74 (dd, J = 17.6, 10.8 Hz, 2H), 6.54 (d, J = 8.8 Hz, 2H), 5.93 (d, J = 17.6 Hz, 2H), 5.87 (d,
J = 17.6 Hz, 2H), 5.45 (d, J = 10.8 Hz, 2H), 5.40 (d, J = 10.8 Hz, 2H), 2.23 (m, 4H). 13C NMR: (75.5 MHz, CDCl3, δ): 164.8, 164.6, 161.6, 154.2, 154.1, 143.3, 143.2, 136.2, 136.0,
135.5, 135.1, 134.2, 131.1, 131.0, 129.1, 128.31, 128.27, 127.7, 126.73, 126.68, 126.2, 125.6, 124.9, 124.6, 123.7, 123.1, 122.9, 121.4, 117.6, 27.6. 31P NMR: (162.1 MHz, CDCl3, δ):
27.1 (JPt-P = 3621 Hz). Anal. Calcd for C82H60O10P2Pt: C, 67.35; H, 4.14. Found: C, 66.32;
H, 4.43.
G1-COOH. G1-CO2Me (3.0 g, 7.5 mmol) was suspended in 125 mL absolute
ethanol. Crushed potassium hydroxide pellets (1.1 g, 19 mmol) were added to the suspension and the mixture was refluxed for 16 hours. The ethanol was removed in vacuo, and the residue was taken up in 100 mL ethyl acetate and acidified with an equal volume of 1 M hydrochloric acid. The aqueous layer was removed, and the ethyl acetate was washed again with 100 mL 1 M hydrochloric acid, then with 100 mL distilled water, and finally with 100 mL brine. After drying over magnesium sulfate, the ethyl acetate was removed in vacuo. The resulting yellow solid was partially dissolved in dichloromethane and hexanes was added to induce precipitation. Upon collection by filtration, 2.3 g of a white solid was obtained (75% yield). 1H NMR: (400 MHz, CDCl3, δ): 7.42 (d, J = 8.0 Hz, 4H), 7.37 (d, J = 8.4 Hz,
4H), 7.34 (d, J = 2.4 Hz, 2H), 6.82 (t, J = 2.4 Hz, 1H), 6.71 (dd, J = 17.6 Hz, 10.8 Hz, 2H), 5.76 (dd, J = 17.6 Hz, 0.8 Hz, 2H), 5.25 (dd, J = 10.8 Hz, 0.8 Hz, 2H), 5.06 (s, 4H). 13C
NMR: (100.6 MHz, CDCl3, δ): 172.0, 160.1, 137.9, 136.7, 136.2, 131.4, 128.1, 126.8, 114.6,
109.3, 108.6, 70.4. Anal. Calcd for C25H22O4: C, 77.70; H, 5.74. Found: C, 77.73; H, 5.77. G1. Method A: G1-COOH (0.26 g, 1.7 mmol). Yield: 0.37 g, 56%. 1H NMR: (400
MHz, CDCl3, δ): 7.39 (m, 48H), 7.18 (d, J = 8.4 Hz, 8H), 6.82 (t, J = 2.0 Hz, 4H), 6.70 (dd, J
2.12 (br, 4H). 13C NMR: (75.5 MHz, CDCl3, δ): 164.9, 160.1, 151.9, 137.8, 136.7, 136.1,
135.6, 134.3, 131.5, 128.1, 126.8, 122.4, 122.3, 114.6, 109.2, 70.4, 24.6. 31P NMR: (162.1 MHz, CDCl3, δ): -13.7. Anal. Calcd for C126H104O16P2: C, 78.16; H, 5.41. Found: C, 77.99;
H, 5.29.
(G1)PtCl2. Method B: G1 (0.39 g, 0.20 mmol). Yield: 0.41 g, 92%. 1H NMR: (400
MHz, CDCl3, δ): 7.98 (m, 8H), 7.40 (m, 48H), 6.85 (s, 4H), 6.71 (dd, J = 17.6, 10.8 Hz, 8H),
5.75 (d, J = 17.6 Hz, 8H), 5.25 (d, J = 10.8 Hz, 8H), 5.06 (s, 16H), 2.45 (m, 4H). 31P NMR: (162.1 MHz, CDCl3, δ): 40.6 ppm (JPt-P = 3600 Hz).
6. Method C: (G1)PtCl2 (0.21 g, 0.095 mmol). Yield: 0.19 g, 81%. 1H NMR: (400
MHz, CDCl3, δ): 8.11 (m, 2H), 7.85 (m, 2H), 7.70 (d, J = 8.0 Hz, 2H), 7.55 (d, J = 8.8 Hz, 2H), 7.38 (m, 48H), 7.08 (m, 2H), 6.88 (m, 2H), 6.83 (m, 2H), 6.72 (m, 8H), 6.56 (d, J = 8.8 Hz, 2H), 5.77 (d, J = 17.6 Hz, 4H), 5.74 (d, J = 17.6 Hz, 4H), 5.26 (d, J = 10.8 Hz, 4H), 5.24 (d, J = 10.8 Hz, 4H), 4.99 (s, 8H), 4.93 (s, 8H), 2.25 (m, 4H). 13C NMR: (75.5 MHz, CDCl3, δ): 164.7, 164.5, 161.6, 160.3, 160.2, 154.2, 154.1, 137.9, 137.8, 136.7, 136.1, 136.0, 135.5, 135.2, 131.12, 131.08, 129.1, 128.2, 128.1, 127.7, 126.8, 126.3, 125.6, 125.0, 124.6, 123.9, 123.1, 122.9, 121.4, 117.6, 109.4, 109.4, 108.5, 70.5, 70.4, 27.6. 31P NMR: (162.1 MHz, CDCl3, δ): 27.0 (JPt-P = 3580 Hz).
G1(2,3)-COOH. Vinyl benzyl chloride (9.0 mL, 65 mmol) was added to a
suspension of 2,3-dihydroxybenzoic acid (1.0 g, 6.5 mmol), potassium carbonate (3.6 g, 26 mmol), 18-crown-6 (0.34 g, 1.3 mmol), and tetrabutylammonium iodide (0.12 g, 0.32 mmol) in 40 mL acetone. The mixture was heated to reflux for 16 hours under nitrogen until a TLC showed complete consumption of the benzoic acid. Insoluble salts were removed by vacuum filtration and the solvent was removed from the filtrate in vacuo. The residue was then
redissolved in 50 mL dichloromethane and washed 3 times with 50 mL distilled water then dried over magnesium sulfate. The dichloromethane was removed in vacuo to yield a yellow oil. Isopropanol (50 mL) and potassium hydroxide (1.8 g, 32 mmol) were added to the oil and, this mixture was heated to reflux for 16 hours, then an additional 1.8 g (32 mmol) potassium hydroxide was added and the reflux was continued for 24 hours until a TLC showed complete consumption of starting material. After the isopropanol was removed in vacuo, 50 mL of ethyl acetate and 50 mL 1M hydrochloric acid were added and the mixture was stirred for 30 minutes. The aqueous layer was removed and the ethyl acetate was washed again with 50 mL 1M hydrochloric acid, then twice with 50 mL distilled water, and finally with 50 mL brine. The ethyl acetate was dried over magnesium sulfate and filtered. After removing the ethyl acetate in vacuo, 10 mL of dichloromethane was added to dissolve the product followed by 20 mL hexanes, and the mixture was stored at -26 °C overnight to induce precipitation. Upon collection by filtration, 1.5 g of a yellow solid was obtained (58% yield). 1H NMR: (400 MHz, CDCl3, δ): 7.72 (dd, J = 8.0, 1.6 Hz, 1H), 7.45 (d, J = 8.0 Hz, 2H), 7.41 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 7.27 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 1.6 Hz, 1H), 7.17 (t, J = 8.0 Hz, 1H), 6.74 (dd, J = 17.6, 10.8 Hz, 1H), 6.67 (dd, J = 17.6, 10.8 Hz, 1H), 5.78 (d, J = 17.6 Hz, 1H), 5.74 (d, J = 17.6 Hz, 1H), 5.29 (d, J = 10.8 Hz, 1H), 5.27 (d, J = 10.8 Hz, 1H), 5.23 (s, 2H), 5.15 (s, 2H). 13C NMR: (100.6 MHz, CDCl3, δ): 165.5; 151.6; 147.4; 138.9; 138.3; 136.6; 136.5; 135.6; 134.4; 129.9; 128.4; 127.0; 125.4; 124.9; 123.4; 119.4; 115.3; 115.0; 71.7. Anal Calcd for C25H22O4: C, 77.70; H, 5.74. Found:
C, 77.72; H, 5.82.
G1(2,3). Method A: G1(2,3)-COOH (0.26 g, 1.7 mmol). Yield: 0.32 g, 47%. 1H
7.13 (m, 16H), 6.72 (dd, J = 17.6, 10.8 Hz, 4H), 6.63 (dd, J = 17.6, 10.8 Hz, 4H), 5.76 (d, J = 17.6 Hz, 4H), 5.66 (d, J = 17.6 Hz, 4H), 5.26 (d, J = 10.8 Hz, 4H), 5.17 (d, J = 10.8 Hz, 4H), 5.11 (s, 16H), 2.12 (br, 4H). 13C NMR: (75.5 MHz, CDCl3, δ): 164.5, 153.2, 151.8, 149.3,
137.8, 137.6, 137.1, 136.9, 136.7, 136.3, 135.5, 134.3, 129.2, 128.2, 126.8, 126.5, 126.2, 124.4, 123.7, 122.3, 119.0, 114.6, 114.2, 75.9, 71.5, 24.7. 31P NMR: (162.1 MHz, CDCl3, δ):
-13.3. Anal Calcd for C126H104O16P2: C, 78.16; H, 5.41. Found: C, 77.95; H, 5.36.
[G1(2,3)]PtCl2. Method B: G1(2,3) (0.39 g, 0.20 mmol). Yield: 0.41 g, 93%. 1H
NMR: (400 MHz, CDCl3, δ): 7.91 (dd, J = 11.8, 8,4 Hz, 8H), 7.54 (dd, J = 8.0, 1.6 Hz, 4H),
7.39 (m, 16H), 7.29 (m, 24H), 7.15 (m, 8H), 6.72 (dd, J = 17.6, 10.8 Hz, 4H), 6.65 (dd, J = 17.6, 10.8 Hz, 4H), 5.76 (d, J = 17.6 Hz, 4H), 5.68 (d, J = 17.6 Hz, 4H), 5.26 (d, J = 10.8 Hz, 4H), 5.17 (d, J = 10.8 Hz, 4H), 5.13 (s, 8H), 5.09 (s, 8H), 2.37 (m, 4H). 31P NMR: (162.1 MHz, CDCl3, δ): 40.7 ppm (JPt-P = 3596 Hz).
7. Method C: [G1(2,3)]PtCl2 (0.21 g, 0.095 mmol). Yield: 0.184 g, 80%. 1H NMR:
(400 MHz, CDCl3, δ): 8.07 (m, 4H), 7.81 (m, 4H), 7.66 (d, J = 8.0 Hz, 2H), 7.61 (dd, J = 7.6, 1.6 Hz, 2H), 7.52 (m, 4H), 7.35 (m, 34H), 7.10 (m, 20H), 6.74 (dd, J = 17.6, 10.8 Hz, 2H), 6.71 (dd, J = 17.6, 10.8 Hz, 2H), 6.62 (dd, J = 17.6, 10.8 Hz, 2H), 6.60 (dd, J = 17.6, 10.8 Hz, 2H), 6.53 (d, J = 8.8 Hz, 2H), 5.78 (d, J = 17.6 Hz, 2H), 5.76 (d, J = 17.6 Hz, 2H), 5.64 (d, J = 17.6 Hz, 2H), 5.63 (d, J = 17.6 Hz, 2H), 5.28 (d, J = 10.8 Hz, 2H), 5.26 (d, J = 10.8 Hz, 2H), 5.14 (m, 20H), 2.25 (m, 4H). 13C NMR: (75.5 MHz, CDCl3, δ): 154.1, 153.3, 153.2, 149.5, 149.4, 137.9, 137.8, 137.7, 137.6, 137.0, 136.7, 136.2, 136.0, 135.4, 135.1, 129.3, 129.2, 129.1, 128.2, 128.1, 127.8, 126.80, 126.77, 126.6, 126.5, 126.3, 126.2, 125.7, 125.6, 125.0, 124.53, 124.46, 123.7, 123.2, 123.0, 121.3, 119.3, 119.2, 114.6, 114.4, 114.3,
75.9, 75.8, 71.5, 27.6. 31P NMR: (162.1 MHz, CDCl3, δ): 27.2 (JPt-P = 3620 Hz). Anal Calcd
for C146H116O18P2Pt: C, 72.60; H, 4.84. Found: C, 72.09; H, 4.43.
G1(2,4)-CO2Me. Methyl 2,4-dihydroxy benzoate (1.0 g, 6.0 mmol), potassium
carbonate (2.1 g, 15 mmol), 18-crown-6 (0.31 g, 1.2 mmol), and tetrabutylammonium iodide (0.11 g, 0.30 mmol) were suspended in 30 mL acetone. Vinyl benzyl chloride (1.8 mL, 13 mmol) was then added and the mixture was refluxed under nitrogen for 16 hours. Insoluble salts were removed by vacuum filtration and the solvent was removed from the filtrate in vacuo. The residue was redissolved in 50 mL ether and washed 3 times with 50 mL distilled water. The ether layer was dried over magnesium sulfate, and evaporated to dryness in vacuo to give a pale yellow oil. Hexanes (1 mL) was added and the mixture was stored at - 26 °C for several days to give a white solid. The solid was dried in vacuo to give 2.0 g (85% yield). 1H NMR: (400 MHz, CDCl3, δ): 7.87 (d, J = 8.4 Hz, 1H), 7.38 (m, 8H), 6.71 (dd, J =
17.6, 10.8 Hz, 2H), 6.56 (m, 2H), 5.76 (d, J = 17.6 Hz, 1H), 5.75 (d, J = 17.6 Hz, 1H), 5.26 (d, J = 10.8 Hz, 1H), 5.24 (d, J = 10.8 Hz, 1H), 5.12 (s, 2H), 5.02 (s, 2H), 3.86 (s, 3H). 13C NMR: (100.6 MHz, CDCl3, δ): 166.4, 163.4, 160.4, 137.8, 137.3, 136.7, 136.6, 136.4, 135.9,
134.2, 128.0, 127.2, 126.7, 126.6, 114.6, 113.4, 106.3, 101.7, 70.6, 70.2, 51.9.
G1(2,4)-COOH. G1(2,4)-CO2Me (1.5 g, 3.8 mmol) was suspended in 75 mL
absolute ethanol. Crushed potassium hydroxide pellets (0.53 g, 9.4 mmol) were added to the suspension and the mixture was refluxed for 16 hours. The ethanol was removed in vacuo, and the residue was taken up in 50 mL ethyl acetate and acidified with an equal volume of 1 M hydrochloric acid. The aqueous layer was removed, and the ethyl acetate was washed again with 50 mL 1 M hydrochloric acid, then with 50 mL distilled water, and finally with 50 mL brine. After drying over magnesium sulfate, the ethyl acetate was removed in vacuo.
The resulting yellow solid was partially dissolved in dichloromethane and hexanes was added to induce precipitation. Upon collection by filtration, 1.0 g of a white solid was obtained (72% yield). 1H NMR: (400 MHz, CDCl3, δ): 8.13 (d, J = 8.8 Hz, 1H), 7.38 (m, 8H), 6.70
(m, 3H), 6.65 (d, J = 2 Hz, 1H), 5.78 (dd, J = 17.6, 10.8 Hz, 1H), 5.76 (dd, J = 17.6, 10.8 Hz, 1H), 5.30 (dd, J = 10.8 Hz, 0.4 Hz, 1H), 5.27 (dd, J = 10.8 Hz, 0.4 Hz, 1H), 5.20 (s, 2H), 5.08 (s, 2H). 13C NMR: (100.6 MHz, CDCl3, δ): 165.4; 164.3; 159.0; 138.9; 138.2; 136.6;
136.4; 136.0; 135.5; 133.8; 128.5; 128.1; 127.3; 126.9; 115.4; 114.9; 111.4; 108.2; 101.1; 72.3; 70.6. Anal. Calcd for C25H22O4: C, 77.70; H, 5.74. Found: C, 77.71; H, 5.69.
G1(2,4). Method A: G1(2,4)-COOH (0.26 g, 1.7 mmol). Yield: 0.34 g, 49%. 1H
NMR: (400 MHz, CDCl3, δ): 8.03 (d, J = 8.8 Hz, 4H), 7.38 (m, 42H), 7.15 (d, J = 8.4 Hz,
8H), 6.67 (m, 16H), 5.76 (d, J = 17.6 Hz, 4H), 5.68 (d, J = 17.6 Hz, 4H), 5.26 (d, J = 10.8 Hz, 4H), 5.18 (d, J = 10.8 Hz, 4H), 5.07 (s, 8H), 5.05 (s, 8H), 2.10 (br, 4H). 13C NMR: (75.5 MHz, CDCl3, δ): 164.1, 163.7, 161.3, 152.0, 138.0, 137.4, 136.8, 136.6, 136.2, 135.8, 135.1,
134.9, 134.2, 128.1, 127.4, 126.8, 126.7, 122.5, 114.7, 114.3, 112.4, 106.5, 101.6, 70.6, 70.3, 24.7. 31P NMR: (162.1 MHz, CDCl3, δ): -13.6. Anal. Calcd for C126H104O16P2: C, 78.16; H,
5.41. Found: C, 77.89; H, 5.35.
[G1(2,4)]PtCl2. Method B: G1(2,4) (0.39 g, 0.20 mmol). Yield: 0.40 g, 90%. 1H
NMR: (400 MHz, CDCl3, δ): 8.05 (d, J = 9.2 Hz, 4H), 7.91 (m, 8H), 7.39 (m, 42H), 6.67 (m,
16H), 5.76 (d, J = 17.6 Hz, 4H), 5.70 (d, J = 17.6 Hz, 4H), 5.26 (d, J = 10.8 Hz, 4H), 5.19 (d, J = 10.8 Hz, 4H), 5.13 (s, 8H), 5.08 (s, 8H). 31P NMR: (162.1 MHz, CDCl3, δ): 40.8 ppm
(JPt-P = 3608 Hz).
8. Method C: [G1(2,4)]PtCl2 (0.21 g, 0.095 mmol). Yield: 0.20 g, 85%. 1H NMR:
Hz, 2H), 7.52 (d, J = 8.8 Hz, 2H), 7.39 (m, 36H), 7.27 (d, J = 7.6 Hz, 4H), 7.00 (m, 6H), 6.67 (m, 16H), 6.54 (d, J = 8.4 Hz, 2H), 5.75 (m, 8H), 5.28 (m, 4H), 5.11 (m, 20H), 2.25 (m, 4H). 13C NMR: (75.5 MHz, CDCl 3, δ): 163.3, 163.25, 163.16, 161.8, 161.5, 161.4, 154.4, 154.3, 138.0, 137.9, 137.6, 137.4, 136.6, 136.1, 136.0, 135.7, 135.0, 129.1, 128.1, 128.1, 127.6, 127.4, 126.82, 126.79, 126.7, 126.3, 125.7, 124.9, 124.5, 123.3, 123.1, 121.2, 114.7, 114.4, 114.3, 111.7, 106.6, 101.7, 101.6, 70.6, 70.4, 27.6. 31P NMR: (162.1 MHz, CDCl3, δ): 27.3
(JPt-P = 3621 Hz). Anal. Calcd for C146H116O18P2Pt: C, 72.60; H, 4.84. Found: C, 71.20; H,
4.19.
G1t-COOH. G1t-CO2Me (1.5 g, 2.8 mmol) was suspended in 50 mL absolute
ethanol. Crushed potassium hydroxide pellets (0.40 g, 7.0 mmol) were added to the suspension and the mixture was refluxed for 16 hours. The ethanol was removed in vacuo and the residue was taken up in 50 mL ethyl acetate and acidified with an equal volume of 1 M hydrochloric acid. The aqueous layer was removed, and the ethyl acetate was washed again with 50 mL 1 M hydrochloric acid, then with 50 mL distilled water, and finally with 50 mL brine. After drying over magnesium sulfate, the ethyl acetate was removed in vacuo. The resulting yellow solid was partially dissolved in dichloromethane and hexanes was added to induce precipitation. Upon collection by filtration, 0.91 g of a white solid was obtained (63% yield). 1H NMR: (400 MHz, CDCl3, δ): 7.38 (m, 10H), 7.32 (d, J = 8.0 Hz, 2H), 7.27
(d, J = 8.4 Hz, 2H), 6.72 (dd, J = 17.6 Hz, 10.8 Hz, 2H), 6.86 (dd, J = 16.4 Hz, 10.8 Hz, 1H), 5.76 (d, J = 17.6 Hz, 2H), 5.72 (d, J = 16.4 Hz, 1H), 5.26 (d, J = 10.8 Hz, 2H), 5.23 (d, J = 10.8 Hz, 1H), 5.11 (s, 6H). 13C NMR: (100.6 MHz, CDCl3, δ): 171.5, 152.9, 143.4, 137.7,
137.6, 137.3, 136.9, 136.8, 136.4, 129.1, 128.1, 126.8, 126.4, 124.4, 114.5, 114.3, 110.0, 75.2, 71.3. Anal Calcd for C34H30O5: C, 78.74; H, 5.83. Found: C, 78.60; H, 5.84.
G1t. Method A: G1t-COOH (0.89 g, 1.7 mmol). Yield: 0.41 g, 47%. 1H NMR: (400 MHz, CDCl3, δ): 7.47 (s, 8H), 7.37 (m, 40H), (7.28 m, 16H), 7.16 (d, J = 8.4 Hz, 8 H), 6.69 (m, 12H), 5.74 (d, J = 17.6 Hz, 8H), 5.72 (d, J = 17.6 Hz, 4H), 5.24 (d, J = 10.8 Hz, 8H), 5.23 (d, J = 10.8 Hz, 4H), 5.10 (s, 24H), 2.12 (br, 4H). 13C NMR: (75.5 MHz, CDCl3, δ): 164.8, 152.9, 151.9, 143.3, 137.7, 137.6, 137.2, 136.9, 136.8, 136.3, 135.6, 134.4, 129.1, 128.1, 126.7, 126.4, 124.5, 122.3, 114.5, 114.2, 109.9, 75.2, 71.3, 24.7. 31P NMR: (162.1 MHz, CDCl3, δ): -13.5. Anal. Calcd for C162H136O20P2: C, 78.94; H, 5.56. Found: C, 78.69;
H, 5.43.
(G1t)PtCl2. Method B: G1t (0.49 g, 0.20 mmol). Yield: 0.51 g, 94%. 1H NMR:
(400 MHz, CDCl3, δ): 7.95 (m, 8H), 7.48 (s, 8H), 7.39 (m, 56H), 6.70 (m, 12H), 5.75 (d, J =
17.6 Hz, 8H), 5.73 (d, J = 17.6 Hz, 4H), 5.25 (d, J = 10.8 Hz, 8H), 5.24 (d, J = 10.8 Hz, 4H), 5.14 (s, 24H), 2.42 (m, 4H). 31P NMR: (162.1 MHz, CDCl3, δ): 40.9 (JPt-P = 3597 Hz).
9. Method C: (G1t)PtCl2 (0.26 g, 0.095 mmol). Yield: 0.24 g, 87%. 1H NMR: (400
MHz, CDCl3, δ): 8.10 (m, 4H), 7.87 (m, 4H), 7.70 (d, J = 8.4 Hz, 2H), 7.55 (m, 6H), 7.35 (m, 60H), 7.10 (m, 2H), 7.01 (m, 4H), 6.70 (m, 12H), 6.58 (d, J= 8.4 Hz, 2H), 5.74 (m, 12H), 5.25 (m, 12H), 5.18 (s, 8H), 5.17 (s, 4H), 5.12 (s, 4H), 5.11 (s, 8H), 2.27 (m, 4H). 13C NMR: (75.5 MHz, CDCl3, δ): 164.6, 164.4, 161.6, 154.2, 154.2, 153.0, 152.9, 143.5, 143.4, 137.8, 137.7, 137.6, 137.6, 137.1, 136.9, 136.7, 136.6, 136.2, 136.2, 136.0, 135.3, 129.11, 129.09, 128.14, 128.09, 126.7, 126.4, 125.0, 124.7, 124.0, 123.1, 122.9, 121.4, 114.5, 114.3, 110.0, 75.24, 75.21, 71.4, 71.3, 27.5. 31P NMR: (162.1 MHz, CDCl 3, δ): 27.0 (JPt-P = 3577 Hz).
Anal Calcd for C182H148O22P2Pt: C, 74.25; H, 5.07. Found: C, 73.29; H, 4.80.
G1t(2,3,4)-COOH. Vinyl benzyl chloride (8.4 mL, 59 mmol) was added to a
mmol), 18-crown-6 (0.31 g, 1.2 mmol), and tetrabutylammonium iodide (0.11 g, 0.29 mmol) in 60 mL acetone. The mixture was heated to reflux for 16 hours under nitrogen until a TLC showed complete consumption of the benzoic acid. Insoluble salts were removed by vacuum filtration and the solvent was removed from the filtrate in vacuo. The residue was then redissolved in 50 mL dichloromethane and washed 3 times with 50 mL distilled water then dried over magnesium sulfate. The dichloromethane was removed in vacuo to yield a yellow oil. Isopropanol (100 mL) and potassium hydroxide (1.7 g, 29 mmol) were added to the oil and, this mixture was heated to reflux for 16 hours, then an additional 1.7 g (29 mmol) potassium hydroxide was added and the reflux was continued for 24 hours until a TLC showed complete consumption of starting material. After the isopropanol was removed in vacuo, 100 mL of ethyl acetate and 100 mL 1M hydrochloric acid were added and the mixture was stirred for 30 minutes. The aqueous layer was removed and the ethyl acetate was washed again with 100 mL 1M hydrochloric acid, then twice with 100 mL distilled water, and finally with 100 mL brine. The ethyl acetate was dried over magnesium sulfate and filtered. After removing the ethyl acetate in vacuo, 10 mL of dichloromethane was added to dissolve the product followed by 20 mL hexanes, and the mixture was stored at -26 °C overnight to induce precipitation. Upon collection by filtration, 1.4 g of a yellow solid was obtained (46% yield). 1H NMR: (400 MHz, CDCl3, δ): 7.87 (d, J = 8.8 Hz, 1H); 7.35
(m, 12H); 6.87 (d, J = 8.8 Hz, 1H); 6.72 (m, 3H); 5.76 (m, 3H); 5.27 (m, 3H); 5.25 (s, 2H); 5.15 (s, 2H); 5.05 (s, 2H). 13C NMR: (100.6 MHz, CDCl3, δ): 165.4; 157.7; 152.2; 141.1;
138.9; 138.14; 138.10; 136.7; 136.6; 136.50; 136.47; 135.5; 134.3; 129.9; 129.3; 128.9; 128.2; 127.0; 126.9; 126.6; 115.7; 115.3; 114.9; 126.6; 115.7; 115.3; 114.9; 114.7; 110.0; 77.8, 76.0, 71.2. Anal. Calcd for C34H30O5: C, 78.74; H, 5.83. Found: C, 78.94; H, 5.84.
G1t(2,3,4). Method A: G1t(2,3,4)-COOH (0.89 g, 1.7 mmol). Yield: 0.43 g, 49%. 1H NMR: (400 MHz, CDCl 3, δ): 7.77 (d, J = 8.4 Hz, 4H), 7.32 (m, 56H), 7.13 (d, J = 8.4 Hz, 8H), 6.70 (m, 16H), 5.77 (d, J = 17.6 Hz, 4H), 5.73 (d, J = 17.6 Hz, 4H), 5.68 (d, J = 17.6 Hz, 4H), 5.27 (d, J = 10.8 Hz, 4H), 5.24 (d, J = 10.8 Hz, 4H), 5.18 (d, J = 10.8 Hz, 4H), 5.091 (s, 8H), 5.089 (s, 8H), 5.00 (s, 8H), 2.13 (br, 4H). 13C NMR: (75.5 MHz, CDCl3, δ): 163.7, 157.5, 154.8, 151.9, 143.0, 137.9, 137.69, 137.67, 137.0, 136.9, 136.7, 135.8, 135.3, 134.3, 129.4, 129.3, 128.0, 126.8, 126.5, 126.5, 122.4, 118.0, 114.7, 114.3, 109.0, 76.4, 75.7, 71.0, 24.7. 31P NMR: (162.1 MHz, CDCl3, δ): -13.0. Anal. Calcd for C162H136O20P2: C,
78.94; H, 5.56. Found: C, 78.76; H, 5.49.
[G1t(2,3,4)]PtCl2. Method B: G1t(2,3,4) (0.49 g, 0.20 mmol). Yield: 0.48 g, 88%. 1H NMR: (400 MHz, CDCl 3, δ): 7.93 (m, 8H), 7.80 (d, J = 8.8 Hz, 4H), 7.33 (m, 56H), 6.83 (d, J = 8.8 Hz, 4H), 6.71 (m, 12H), 5.78 (d, J = 17.6 Hz, 4H), 5.73 (d, J = 17.6 Hz, 4H), 5.71 (d, J = 17.6 Hz, 4H), 5.28 (d, J = 10.8 Hz, 4H), 5.24 (d, J = 10.8 Hz, 4H), 5.19 (d, J = 10.8 Hz, 4H), 5.15 (s, 8H), 5.14 (s, 8H), 5.02 (s, 8H), 2.40 (m, 4H). 31P NMR: (162.1 MHz, CDCl3, δ): 40.9 (JPt-P = 3596 Hz).
10. A solution of [G1t(2,3,4)]PtCl2 (0.26 g, 0.095 mmol) in 25 mL dichloromethane
was added silver carbonate (39 mg, 0.14 mmol) and 5 drops of distilled water. The mixture was stirred at room temperature, protected from light until all the PtCl2 was converted to
PtCO3 as monitored by 31P NMR. The mixture was filtered through a pad of Celite to
remove the silver salts. (S)-BINOL (30 mg, 0.11 mmol) was added to a solution of the PtCO3 in 25 mL dichloromethane and the solution was stirred at room temperature until 31P
NMR showed complete conversion to the Pt(BINOL). The dichloromethane was removed in vacuo and 25 mL diethyl ether was added. The ether was decanted from the yellow oil, and
this process was repeated 3 times. After drying overnight in vacuo 10 [G1t(2,3,4)]Pt((S)-
BINOL) (0.23 g, 84% yield) was obtained as a foamy solid from which complete solvent removal was impossible. 1H NMR: (400 MHz, CDCl3, δ): 8.08 (m, 4H), 7.87 (d, J = 8.8 Hz,
2H), 7.81 (m, 4H), 7.76 (d, J = 8.8 Hz, 2H), 7.54 (d, J = 8.8 Hz, 2H), 7.31 (m, 58H), 7.03 (m, 6H), 6.87 (d, J = 8.8 Hz, 2H), 6.70 (m, 12H), 6.54 (d, J = 8.8 Hz, 2H), 5.73 (m, 12H), 5.28 (m, 8H), 5.13 (m, 28H), 2.23 (m, 4H). 13C NMR: (75.5 MHz, CDCl3, δ):.155.0, 154.9, 154.3, 154.2, 153.2, 143.1, 143.0, 138.0, 137.9, 137.8, 137.71, 137.66, 137.0, 136.92, 136.85, 136.7, 136.0, 135.8, 135.5, 135.0, 134.0, 129.4, 129.3, 129.1, 128.08, 128.05, 126.8, 126.6, 126.51, 126.47, 125.0, 124.6, 123.2, 123.1, 121.3, 117.5, 117.4, 114.7, 114.3, 109.2, 76.4, 75.71, 75.66, 71.0. 31P NMR: (162.1 MHz, CDCl3, δ): 27.5 (JPt-P = 3630 Hz).
G1n(3,5)-COOH. Vinyl benzyl chloride (7.0 mL, 49 mmol) was added to a
suspension of 3,5-dihydroxy-2-naphthoic acid (1.0 g, 4.9 mmol), potassium carbonate (2.7 g, 20 mmol), 18-crown-6 (0.26 g, 0.98 mmol), and tetrabutylammonium iodide (91 mg, 0.25 mmol) in 30 mL acetone. The mixture was heated to reflux for 16 hours under nitrogen until a TLC showed complete consumption of the naphthoic acid. Insoluble salts were removed by vacuum filtration and the solvent was removed from the filtrate in vacuo. The residue was then redissolved in 50 mL dichloromethane and washed 3 times with 50 mL distilled water then dried over magnesium sulfate. The dichloromethane was removed in vacuo to yield a yellow oil. Isopropanol (50 mL) and potassium hydroxide (1.4 g, 25 mmol) was added to the oil and, this mixture was heated to reflux for 16 hours, then an additional 1.4 g (25 mmol) potassium hydroxide was added and the reflux was continued for 24 hours until a TLC showed complete consumption of starting material. After the isopropanol was removed in vacuo, 50 mL of ethyl acetate and 50 mL 1M hydrochloric acid were added and the
mixture was stirred for 30 minutes. The aqueous layer was removed and the ethyl acetate was washed again with 50 mL 1M hydrochloric acid, then twice with 50 mL distilled water, and finally with 50 mL brine. The ethyl acetate was dried over magnesium sulfate and filtered. After removing the ethyl acetate in vacuo, 10 mL of dichloromethane was added to dissolve the product followed by 20 mL hexanes, and the mixture was stored at -26 °C overnight to induce precipitation. Upon collection by filtration, 0.87 g of a yellow solid was obtained (41% yield). 1H NMR: (400 MHz, CDCl3, δ): 8.74 (s, 1H), 7.81 (s, 1H); 7.45 (m,
9H), 7.32 (t, J = 8.0 Hz, 1H), 6.96 (d, J = 8.0 Hz, 1H), 6.72 (m, 2H), 5.79 (d, J = 17.6 Hz, 1H), 5.77 (d, J = 17.6 Hz, 1H), 5.34 (s, 2H), 5.30 (d, J = 10.8 Hz, 1H), 5.29 (d, J = 10.8 Hz, 1H), 5.22 (s, 2H). 13C NMR: (100.6 MHz, CDCl3, δ): 165.8; 153.6; 153.5; 138.7; 137.9;
136.6; 136.5; 136.4; 136.1; 134.2; 129.8; 129.1; 128.7; 128.1; 127.2; 126.8; 125.7; 122.1; 118.9; 115.3; 114.8; 108.8; 104.0; 72.4; 70.6. Anal. Calcd for C29H24O4: C, 79.80; H, 5.54.
Found: C, 79.51; H, 5.54.
G1n(3,5). Method A: G1n(3,5)-COOH (0.75 g, 1.7 mmol). Yield: 0.41 g, 53%. 1H
NMR: (400 MHz, CDCl3, δ): 8.46 (s, 4H), 7.72 (s, 4H), 7.32 (m, 56H), 6.91 (d, J = 7.6 Hz,
4H), 6.75 (dd, J = 17.6, 10.8 Hz, 4H), 6.66 (dd, J = 17.6, 10.8 Hz, 4H), 5.79 (d, J = 17.6 Hz, 4 H), 5.69 (d, J = 17.6 Hz, 4H), 5.22 (m, 24H), 2.17 (br, 4H). 13C NMR: (75.5 MHz, CDCl3,
δ): 164.6, 155.0, 153.4, 152.0, 137.7, 137.4, 136.8, 136.7, 136.5, 135.5, 134.3, 133.6, 133.5, 128.9, 127.9, 127.7, 126.8, 126.7, 124.7, 122.4, 121.7, 121.6, 114.6, 114.2, 108.2, 103.8, 103.7, 70.6, 70.4, 25.3. 31P NMR: (162.1 MHz, CDCl3, δ): -12.9. Anal. Calcd for
C142H112O16P2: C, 79.68; H, 5.25. Found: C, 79.72; H, 5.26.
[G1n(3,5)]PtCl2. Method B: G1n(3,5) (0.49 g, 0.20 mmol). Yield: 0.42 g, 88%. 1H
J = 7.6 Hz, 4H), 6.72 (m, 8H), 5.79 (d, J = 17.6 Hz, 4H), 5.71 (d, J = 17.6 Hz, 4H), 5.25 (m, 24H), 2.43 (m, 4H). 31P NMR: (162.1 MHz, CDCl3, δ): 40.9 (JPt-P = 3601 Hz).
11. Method C: [G1n(3,5)]PtCl2 (0.23 g, 0.095 mmol). Yield: 0.17 g, 69%. 1H NMR:
(400 MHz, CDCl3, δ): 8.58 (s, 2H), 8.46 (s, 2H), 8.12 (m, 4H), 7.87 (m, 4H), 7.80 (s, 2H), 7.73 (s, 2H), 7.68 (d, J = 8.0Hz, 2H), 7.56 (d, J = 8.8 Hz, 2H), 7.42 (m, 48H), 7.02 (m, 8H), 6.92 (d, J = 7.6 Hz, 2H), 6.76 (dd, J = 17.6, 10.8 Hz, 2H), 6.74 (dd, J = 17.6, 10.8 Hz, 2H), 6.64 (dd, J = 17.6, 10.8 Hz, 2H), 6.62 (dd, J = 17.6, 10.8 Hz, 2H), 6.58 (d, J = 8.4 Hz, 2H), 5.80 (d, J = 17.6 Hz, 2H), 5.78 (d, J = 17.6 Hz, 2H), 5.66 (d, J = 17.6 Hz, 2H), 5.65 (d, J = 17.6 Hz, 2H), 5.25 (m, 24H), 2.29 (m, 4H). 13C NMR: (75.5 MHz, CDCl3, δ): 154.4, 154.3, 153.5, 153.4, 153.3, 137.7, 137.5, 137.4, 136.7, 136.5, 136.0, 135.5, 135.1, 134.0, 133.9, 130.9, 129.4, 129.2, 129.1, 128.93, 128.86, 128.0, 127.8, 126.8, 126.7, 126.3, 125.5, 125.0, 124.9, 124.6, 123.6, 123.3, 123.1, 121.7, 121.4, 121.1, 118.4, 112.6, 114.3, 112.4, 108.4, 104.0, 103.9, 70.7, 70.4, 27.7. 31P NMR: (162.1 MHz, CDCl3, δ): 28.2 (JPt-P = 3645 Hz).
Anal. Calcd for C162H124O18P2Pt: C, 74.39; H, 4.78. Found: C, 71.75; H, 4.03.
dppe-OCO-Ph. To a suspension of dppe-OH (0.25 g, 0.34 mmol) in 20 mL
dichloromethane was added benzoyl chloride (0.20 mL, 1.7 mmol), followed by triethylamine (0.25 mL, 1.7 mmol). The suspension was stirred for 1 hour under nitrogen