Synthesis, characterization and molecular recognition of bis-platinum terpyridine dimer. Supporting information

Transcription

1 This journal is (c) The Royal Society of Chemistry 008 Synthesis, characterization and molecular recognition of bis-platinum terpyridine dimer Robert Trokowski, Shigehisa Akine, Tatsuya abeshima Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai -- Tsukuba, Ibaraki 0-87, Japan Supporting information Experimental General Procedures. H MR spectra were recorded on a Bruker ARX00 (00 MHz), Bruker AVACE AV00 (00 MHz) or a Bruker AVACE AV00 (00 MHz) spectrometer. C MR spectra were recorded on a Bruker ARX00 (00 MHz) spectrometer. Chemical shifts (δ) are given in ppm relative to internal tetramethylsilane and coupling constants are reported in Hertz (Hz). ominal mass spectra (m/z) under the conditions of electrospray ionization were recorded on an Applied Biosystems Qstar/Pulsar i. Elemental analyses were performed at Chemical Analysis Center, University of Tsukuba. Melting points were obtained using a Yanaco melting point apparatus and are uncorrected. Materials. All reagents, obtained from WAKO Pure Chemical Industries, Ltd., TCI Tokyo Chemical Industry Co., Ltd., acalai Tesque, Inc. suppliers were used directly as supplied. -(-bromophenyl)pyridine Br -(,,,-Tetramethyl-,,-dioxaborolan--yl)pyridine (9. g,.0 mmol),,- dibromobenzene (. g,.0 eq) and tetrakis(triphenylphosphine)palladium (. g, 0.0 eq) were placed in 00 ml flask. Dioxane (0 ml) degassed via three freezepump-thaw cycles and potassium carbonate (.70 g,. eq) were added, and the resulting mixture was then stirred at 80 o C for days. The mixture was poured into water and extracted with chloroform (x0 ml). The combined organic layers were

2 This journal is (c) The Royal Society of Chemistry 008 dried with anhydrous MgSO. Solvents were removed and the reaction was purified by column chromatography (CHCl :MeOH :0.0) on silica gel to afford as colorless oil (.97 g, %). Found: C,.; H,.;,.0. Calc. for C H 8 Br: C., H.,,98%; δ H (00 MHz, CDCl ) (H, m), (H, m), (H, t, J.8 Hz), (H, dt, J., 8. Hz), (H, dd, J.8,. Hz), 8.79 (H, d, J. Hz); δ C (00 MHz, CDCl ).,.8,.7, 0., 0.,.0,.9,., 9.8, 8., 9.0; m/z (ESI-MS+).97 [M + H] +. -[-(,,,-tetramethyl-,,-dioxaborolan--yl)phenyl]pyridine O B O -(-Bromophenyl)pyridine (.97 g,.0 mmol),,,,,,,, -octamethyl-, - bi-,,-dioxaborolane (.0 g, eq), [,'- bis(diphenylphosphino)ferrocene]dichloropalladium(ii) Pd(dppf)Cl (0. g, 0.0 eq) and,'-bis(diphenylphosphino)ferrocene (0. g, 0.0 eq) were placed in 00 ml flask. Dioxane (80 ml) degassed via three freeze-pump-thaw cycles and potassium acetate (7.0 g, eq) were added, and the resulting mixture was then stirred at 80 o C for days. The mixture was poured into water and extracted with chloroform (x0 ml). The combined organic layers were dried with anhydrous MgSO. Solvents were removed and the reaction was purified by column chromatography (CHCl ) on silica gel to afford as colorless solid (.7 g, 9%). M.p o C. Found: C, 7.0; H, 7.;,.8. Calc. for C 7 H 0 BO /H O: C, 7.70; H, 7.;,.9%; δ H (00 MHz, CDCl ). (H, s), (H, dd, J.9, 7. Hz), (H, t, J 7. Hz), (H, dt, J., 7. Hz), (H, m), 7.99 (H, s), (H, dd, J.,.8 Hz), 8.8 (H, d, J. Hz); δ C (00 MHz, CDCl ).8, 8.99,., 8., 9.89,.8,.7,.8,.7, 7., 8.; m/z (ESI-MS+) 8. [M + H] +, 0. [M + a] +.

3 This journal is (c) The Royal Society of Chemistry 008 -[,-bis(pyridin--yl)pyridin--yl]phenyl trifluoromethanesulfonate OTf To a pyridine solution (0 ml) of -(-hydroxyphenyl)-, :, -terpyridine (.78 g, 8. mmol) was slowly added trifluoromethanesulfonic anhydride (.89 g,. eq) at 0 o C. The resulting mixture was stirred at 0 o C for min and warmed to room temperature with stirring for h. The resulting mixture was poured into water and extracted with dichloromethane (x0 ml). The dichloromethane extract was washed with brine (x0 ml) and dried over MgSO. Solvents were removed and the reaction was purified by column chromatography (CHCl ) on alumina to afford as colorless solid (.7 g, 70%). M.p. 7-9 o C. Found: C, 7.; H,.;, 9.. Calc. for C H F O S: C, 7.77; H,.08;, 9.9%; δ H (00 MHz, CDCl ) (H, m), (H, t, J 8. Hz), (H, t, J. Hz), (H, m), (H, dd, J 0.8, 8.0 Hz), 8.7 (H, s), (H, dt, J.,. Hz); δ C (00 MHz, CDCl ) 8.7, 0.,.,.7,.0, 7., 0.7,.89,., 8.0, 9., 0.0,.7,.. m/z (ESI-MS+) 8.07 [M + H] +.,-bis(pyridin--yl)--{-[-(pyridin--yl)phenyl]phenyl}pyridine A C B D A E -[,-Bis(pyridin--yl)pyridin--yl]phenyl trifluoromethanesulfonate (.7 g,.87 mmol), -[-(,,,-tetramethyl-,,-dioxaborolan--yl)phenyl]pyridine (.00 g,. eq), [,'-bis(diphenylphosphino)ferrocene]dichloropalladium(ii) Pd(dppf)Cl (0. g, 0.0 eq) and,'-bis(diphenylphosphino)ferrocene dppf (0.0 g, 0.0 eq) were

4 This journal is (c) The Royal Society of Chemistry 008 placed in 00 ml flask. Dioxane (0 ml) degassed via three freeze-pump-thaw cycles and potassium carbonate (.0 g,. eq) were added, and the resulting mixture was then stirred at 80 o C for days. The mixture was poured into water and extracted with chloroform (x0 ml). The combined organic layers were dried with anhydrous MgSO. Solvents were removed and the reaction was purified by column chromatography (CHCl :MeOH:Et :0.:0.) on silica gel to afford as white solid (0.9 g, %). Mp o C. Found: C, 8.0; H,.08;,.98. Calc. for C H : C, 8.09; H,.79;,.%; δ H (00 MHz; DMSO-d ) (H, m, H A, E ), 7.7 (H, t, J 7.7, H D ), 7.7 (H, t, J 7.7, H C ), 7.79 (H, d, J 7.8, H D ), 7.88 (H, d, J 7.8, H D ), 7.9 (H, m, H C, C ), 8.0 (H, td, J 7.8,.7, H A ), 8. (H, s, H D ), 8. (H, dt, J 8.0,.0, H E ), 8. (H, s, H C ), 8. (H, dd, J.8,., H E ), 8.9 (H, d, J 7.8, H A ), 8.77 (H, d, J., H A ), 8.79 (H, s, H B, B ), 9.0 (H, d, J., H E ); δ C (00 MHz, CDCl ) 9.9,.8,.00,.,.8,.7,.80, 7., 7.7, 8., 9.9, 0.0,.0,.99, 7., 8.9, 9.78,.0,.9, 8.89, 9.08, 9.7, 0.70,.,.0; m/z (ESI- MS+).7 [M + H] +, 8. [M + a] +, 97. [M + a] +. {[Pt()][BF ] } A C B Pt D A E Pt + BF - To a suspension of diiodo(cycloocta-,-diene)platinum (0. g, 0. mmol) in acetone ( ml) was added silver tetrafluoroborate (0. g,. eq). The resulting mixture was stirred at room temperature until a colorless solution was obtained (~0 min). The AgI precipitate was then removed by filtration. The solution was added to a,-bis(pyridin--yl)--{-[-(pyridin--yl)phenyl]phenyl}pyridine (8.0 mg, 0. mmol) in acetonitrile (70 ml) and chloroform ( ml). The reaction mixture was stirred at room temperature for 7 days. The solution was concentrated to small volume,

5 This journal is (c) The Royal Society of Chemistry 008 acetone (0 ml) was added and the resulting yellow precipitate was filtered off, washed with acetone and vacuum dried to afford bis-platinum complex (8.00 mg, 99%) as yellow microcrystalline yellow solid. M.p. above 00 o C. Found: C,.9; H,.09;,.8. Calc. for C H B F 8 Pt (8H O): C,.; H,.;,.0%; δ H (00 MHz, DMSO-d ) (8H, m, H A, C, D ), 8.0 (H, d, J 8.0, H D ), 8.07 (H, d, J 7.8, H C ), (8H, m, H A, D, E ), (H, m, H C, D ), (H, m, H A, C ), 8.7 (H, d, J 8., H A ), 8.8 (H, d, J 8., H E ), 8.9 (H, s, H B, B ), 9. (H, d, J., H E ), 9.9 (H, s, H E ); δ C (00 MHz, DMSO-d ) 0.99,.0,.,.89,.,.70, 7.0, 8., 8.80, 9.8, 9.,.70,.98, 8.00, 8.9, 8.97, 9.88,.89, 9.79, 0., 0.7,.,.79,.7; m/z (ESI-MS+) 8. [M BF ] +, 9.0 [/(M BF ) + CH C] +, 7.09 [M BF ] +, 9.08 [/(M BF ) + Cl] +. Figure S. H COSY spectrum of (DMSO-d, C, [] = mm, 00 MHz).

6 This journal is (c) The Royal Society of Chemistry 008 Figure S. H OESY spectrum of (DMSO-d, C, [] = mm, 00 MHz). Figure S. H COSY spectrum of (DMSO-d, C, [] = mm, 00 MHz).

7 This journal is (c) The Royal Society of Chemistry 008 Figure S. H OESY spectrum of (DMSO-d, C, [] = mm, 00 MHz). HO H C H H B H H A OH Pt Figure S. Illustration of the intermolecular OE cross peaks observed in the adduct formed by the dimer and naphthalene-,-diol. 7

8 This journal is (c) The Royal Society of Chemistry 008 Figure S. Partial H OESY spectrum of a : solution of and naphthalene-,- diol (DMSO-d, C, [] = mm, 00 MHz). Figure S7. ESI-MS spectrum (positive mode) of in MeOH/CHCl. Inset shows isotopic distribution and the calculated isotopic distribution for the [ - BF ] + ion. 8

9 This journal is (c) The Royal Society of Chemistry 008 Figure S8. Representative H MR spectra of the MR titration experiment performed by titrating with naphthalene-,-diol at C, A) [] = mm, B) [naphthalene-,-diol] = mm; all spectra recorded in DMSO-d, black squares represent H c proton (see assignment in Scheme ). Figure S9. Binding isotherm observed upon titration of with naphthalene-,-diol. 9

10 This journal is (c) The Royal Society of Chemistry 008 Figure S0. The electronic absorption spectra of by the addition of naphthalene-,-diol (DMSO, C, [] = 0. mm). Figure S. Job s plot of and naphthalene-,-diol indicating a : stoichiometry (DMSO, C, [] + [G] = mm). References. W. Li, D. P. elson, M. S. Jensen, R. S. Hoerrner, D. Cai, R. D. Larsen and P. J. Reider, J. Org. Chem., 00, 7, 9.. K. Hanabusa, M. Matsumoto, M. Kimura, A. Kakehi and H. Shirai, J. Colloid Interface Sci., 000,,. 0