Supporting Information for Angew. Chem. Int. Ed. Z19280 Wiley-VCH 2002 69451 Weinheim, Germany
A New Method for Determining the Difference in Relative Apicophilicity of Carbon Substituents of 10-P-5 Phosphoranes: Disclosure of Solvent Effect on Apicophilicity and Novel Cocrystallization of Two Pseudorotamers in a Single Crystal** Shiro Matsukawa, Kazumasa Kajiyama, Satoshi Kojima, Shin-ya Furuta, Yohsuke Yamamoto, and Kin-ya Akiba* [*] Prof. Dr. K.-y. Akiba Advanced Research Center for Science and Engineering Waseda University 3-4-1 Ohkubo, Shinjuku-ku, Tokyo 169-8555, Japan Tel & Fax : (+81)3-5286-3165 E-mail : akibaky@waseda.jp S. Matsukawa, Dr. S. Kojima, S.-y. Furuta, Prof. Dr.Y. Yamamoto Department of Chemistry, Graduate School of Science Hiroshima University 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8526, Japan Dr. K. Kajiyama Department of Chemistry, School of Science Kitasato University 1-15-1 Kitasato, Sagamihara 228-8555, Japan
Supporting Information NMR measurements 1 H NMR (400 MHz), 19 F NMR (376 MHz), and 31 P NMR (162 MHz) spectra were recorded on a JEOL EX-400 spectrometer. 1 H NMR chemical shifts (δ) are given in ppm downfield shift from Me4Si, determined by residual chloroform (δ = 7.26). 19 F NMR chemical shifts (δ) are given in ppm downfield shift from external CFCl3. 31 P NMR chemical shifts (δ) are given in ppm downfield shift from external 85% H3PO4. 1a 1 H NMR (CDCl 3, δ) 9.45 (br s, 1H), 8.16-8.11 (m, 1H), 7.81-7.75 (m, 4H), 7.38-7.33 (m, 1H), 7.27-7.12 (m, 3H), 2.57 (d, 3H, 2 JP-H = 13.7 Hz), 1.46 (d, 3H, 2 JP-H = 5.9 Hz); 19 F NMR (CDCl3, δ) -72.8 (q, 3F, 4 JF-F = 8.5 Hz), -76.3 (q, 3F, 4 JF-F = 9.7 Hz), -76.7 (q, 3F, 4 JF-F = 9.7 Hz), -77.0 (q, 3F, 4 JF-F = 8.5 Hz); 31 P NMR (CDCl3, δ) -34.8. 1b 1 H NMR (CDCl 3, δ) 9.99 (1bB, br s, 1H), 9.61 (1bA, br s, 1H), 8.21-8.16 (1bB, m, 1H), 8.08-8.02 (1bA, m, 1H), 7.83-7.71 (m, 4.0H), 7.40-7.32 (m, 1.0H), 7.26-7.19 (m, 1.2H), 7.12 (1bA, ddd, 1H, J = 9.7, 8.0, 1.5 Hz), 3.26-3.12 (1bA, m, 1H), 2.91-2.79 (1bA, m, 1H), 2.59 (1bB, d, 3H, 2 JP-H = 13.3 Hz), 2.53-2.06 (1bB, m, 1H), 1.97-1.90 (1bB, m, 1H), 1.47 (1bA, d, 3H, 2 JP-H = 5.8 Hz), 1.03 (1bA, dt, 3H, 3 JP-H = 27.0 Hz, 3 JH-H = 7.7 Hz), 0.84 (1bB, dt, 3H, 3 JP-H = 14.8 Hz, 3 JH-H = 6.8 Hz); 19 F NMR (CDCl3, δ) -72.8 (1bA, m, 3F), -73.0 (1bB, m, 3F), -75.9 (1bB, q, 3F, 4 JF-F = 9.8 Hz), -76.1 (1bB, q, 3F, 4 JF-F = 9.8 Hz), -76.3 (1bA, q, 3F, 4 JF-F = 8.5 Hz), -76.6 (1bA, m, 6F), -77.0 (1bB, m, 3F); 31 P NMR (CDCl3, δ) -21.9 (1bA), -25.3 (1bB). 1c 1 H NMR (CDCl 3, δ) 10.01 (1cB, br s, 1H), 9.67 (1cA, br s, 1H), 8.20-8.14 (1cB, m, 1H), 8.07-8.01 (1cA, m, 1H), 7.85-7.72 (m, 4.0H), 7.40-7.19 (m, 2.2H), 7.11 (1cA, dd, 1H, J = 20.6, 8.2 Hz), 3.16-3.05 (1cA, m, 1H), 2.83-2.73 (1cA, m, 1H), 2.60 (1cB, d, 3H, 2 JP-H = 13.3 Hz), 2.07-1.98 (1cB, m, 1H), 1.91-1.82 (1cB, m, 1H), 1.52-1.39 (m, 1.0H), 1.48 (1cA, d, 3H, 2 JP-H = 6.0 Hz), 1.23-1.10 (m, 1
1.0H), 0.98 (1cA, td, 3H, 3 JH-H = 7.0 Hz, 4 JP-H = 2.9 Hz), 0.92 (1cB, t, 3H, 3 JH-H = 6.8 Hz); 19 F NMR (CDCl 3, δ) -72.7 (1cA, q, 3F, 4 JF-F = 8.5 Hz), -72.9 (1cB, m, 3F), -75.9 (1cB, q, 3F, 4 J F-F = 9.8 Hz), -76.1 (1cB, q, 3F, 4 JF-F = 9.8 Hz), -76.4 (1cA, q, 3F, 4 JF-F = 8.5 Hz), -76.6 (1cA, m, 6F), -77.0 (1cB, m, 3F); 31 P NMR (CDCl3, δ) -24.5 (1cA), -26.5 (1cB). 1d 1 H NMR (CDCl 3, δ) 10.00 (1dB, br, 1H), 9.67 (1dA, br s, 1H), 8.19-8.13 (1dB, m, 1H), 8.07-8.02 (1dA, m, 1H), 7.82-7.80 (m, 5.0H), 7.38-7.29 (m, 1.0H), 7.14-7.07 (m, 1.0H), 3.14-3.06 (1dA, m, 1H), 2.83-2.74 (1dA, m, 1H), 2.60 (1dB, d, 3H, 2 JP-H = 13.7 Hz), 2.08-1.99 (1dB, m, 1H), 1.91-1.83 (1dB, m, 1H), 1.48 (1dA, d, 3H, 2 JP-H = 5.9 Hz), 1.38-0.86 (m, 4.0H), 0.85-0.78 (m, 3.0H); 19 F NMR (CDCl 3, δ) -72.7 (1dA, q, 3F, 4 JF-F = 8.6 Hz), -73.0 (1dB, m, 3F), -75.8 (1dB, q, 3F, 4 J F-F = 8.6 Hz), -76.1 (1dB, q, 3F, 4 JF-F = 8.6 Hz), -76.4 (1dA, q, 3F, 4 JF-F = 8.6 Hz), -76.6 (1dA, m, 6F), -77.0 (1dB, m, 3F); 31 P NMR (CDCl3, δ) -24.2 (1dA), -26.2 (1dB). 1e 1 H NMR (CDCl 3, δ) 8.91 (1eB, br s, 1H), 8.27-8.22 (1eB, m, 1H), 8.13-8.12 (1eA, m, 1H), 7.85-7.74 (m, 4H), 7.41-7.37 (m, 1H), 7.26-7.12 (m, 2H), 5.19 (1eA, dd, 1H, 2 JP-H = 3.9 Hz, 2 JH-H = 12.6 Hz), 4.63 (1eA, d, 1H, 2 JH-H = 12.6 Hz), 3.97 (1eB, dd, 1H, 2 JP-H = 3.1 Hz, 2 JH-H = 12.6 Hz), 3.39 (1eB, s, 3H), 3.27 (1eA, s, 3H), 2.93 (1eB, d, 1H, 2 JH-H = 12.6 Hz), 2.64 (1eB, d, 3H, 2 J P-H = 14.5 Hz), 1.60 (1eA, d, 3H, 2 JP-H = 7.0 Hz); 19 F NMR (CDCl3, δ) -72.8 (1eA, br s, 3F), -73.0 (1eB, m, 3F), -75.8 (1eA, q, 3F, 4 JF-F = 9.8 Hz), -76.2 (1eB, q, 3F, 4 JF-F = 8.5 Hz), -76.4 (1eB, q, 3F, 4 JF-F = 8.5 Hz), -76.5 (1eA, q, 3F, 4 JF-F = 9.8 Hz), -76.8 (1eA, m, 3F), -76.8 (1eB, q, 3F, 4 JF-F = 8.5 Hz), 31 P NMR (CDCl3, δ) -25.7 (1eA), -35.5 (1eB). 1f 1 H NMR (CDCl 3, δ) 7.99-7.19 (m, 14H), 2.75 (d, 3H, 2 JP-H = 13.7 Hz); 19 F NMR (CDCl3, δ) - 72.6 (br s, 3F), -76.0 (q, 6F, 4 JF-F = 8.6 Hz), -77.1 (br s, 3F); 31 P NMR (CDCl3, δ) -22.5. 1g 2
1 H NMR (CDCl 3, δ) 9.91 (1gA, br s, 1H), 9.56 (1gB, br s, 1H), 8.38-8.33 (1gB, m, 1H), 7.92-7.76 (m, 3.2H), 7.63-7.56 (m, 1.5H), 7.52-7.33 (m, 1.5H), 7.23-7.18 (m, 0.8H), 7.09 (1gA, dd, 1H, J = 20.3, 8.1 Hz), 6.93 (1gA, d, 2H, J = 7.3 Hz), 6.82 (1gB, d, 2H, J = 7.8 Hz), 6.61 (1gA, dd, 2H, J = 8.1, 3.2 Hz), 6.15 (1gB, d, 2H, J = 6.8 Hz), 4.81 (1gA, dd, 1H, 2 JP-H = 19.8 Hz, 2 JH-H = 14.9 Hz), 4.43 (1gA, dd, 1H, 2 JP-H = 22.5 Hz, 2 JH-H = 14.9 Hz), 3.59 (1gB, dd, 1H, 2 JP-H = 9.8 Hz, 2 JH-H = 12.7 Hz), 3.19 (1gB, dd, 1H, 2 JP-H = 5.1 Hz, 2 JH-H = 12.7 Hz), 2.63 (1gB, d, 3H, 2 JP-H = 13.4 Hz), 2.27 (1gA, d, 3H, 7 JP-H = 3.4 Hz), 2.23 (1gB, s, 3H), 1.17 (1gA, d, 3H, 2 JP-H = 6.3 Hz); 19 F NMR (CDCl3, δ) -72.6 (1gA, m, 3F;), -73.2 (1gB, qq, 3F, 4 JF-F = 8.5 Hz, 9 JF-F = 4.3 Hz), -75.4 (1gA, q, 3F, 4 JF-F = 9.2 Hz), -76.1 (1gB, q, 3F, 4 JF-F = 8.5 Hz), -76.2 (1gA, q, 3F, 4 JF-F = 8.5 Hz) -76.6 (1gA, m, 3F), -76.8 (1gB, qq, 3F, 4 JF-F = 8.5 Hz, 9 JF-F = 4.3 Hz), -77.4 (1gB, q, 3F, 4 JF-F = 8.5 Hz); 31 P NMR (CDCl3, δ) -25.2 (1gA), -34.2 (1gB). 1h 1 H NMR (CDCl 3, δ) 9.86 (1hA, br s, 1H), 9.48 (1hB, br s, 1H), 8.40-8.35 (1hB, m, 1H), 7.90 (1hA br s, 1H), 7.84-7.62 (m, 2.0H), 7.61-7.34 (m, 3.0H), 7.25-6.90 (m, 5.0H), 6.74 (1hA, d, 2H, JH-H = 7.0 Hz), 6.27 (1hB, d, 2H, JH-H = 7.0 Hz), 4.85 (1hA, dd, 1H, 2 JP-H = 19.8 Hz, 2 JH-H = 14.9 Hz), 4.47 (1hA, dd, 1H, 2 JP-H = 22.2 Hz, 2 JH-H = 14.9 Hz), 3.64 (1hB, dd, 1H, 2 JP-H = 9.5 Hz, 2 JH- H = 12.8 Hz), 3.22 (1hB, dd, 1H, 2 JP-H = 5.5 Hz, 2 JH-H = 12.8 Hz), 2.64 (1hB, d, 3H, 2 JP-H = 13.7 Hz), 1.17 (1hA, d, 3H, 2 JP-H = 6.4 Hz); 19 F NMR (CDCl3, δ) -72.7 (1hA, m, 3F), -73.2 (1hB m, 3F), -75.4 (1hA, q, 3F, 4 JF-F = 9.7 Hz), -76.1 (1hB, q, 3F, 4 JF-F = 9.7 Hz), -76.2 (1hA, q, 3F, 4 J F-F = 8.6 Hz), -76.6 (1hA, m, 3F), -76.8 (1hB, m, 3F), -77.4 (1hB, q, 3F, 4 JF-F = 8.6 Hz); 31 P NMR (CDCl3, δ) -25.7 (1hA), -35.2 (1hB). 1i 1 H NMR (CDCl 3, δ) 9.77 (1iA, br s, 1H), 9.39 (1iB, br s, 1H), 8.36-8.31 (1iB, m, 1H), 7.91-7.73 (m, 3.6H), 7.66-7.56 (m, 1.5H), 7.52-7.32 (m, 1.8H), 7.24-7.20 (m, 0.7H), 7.09 (1iA, dd, 1H, J = 20.3, 7.3 Hz), 6.83 (1iA, m, 2H), 6.74-6.69 (m, 2.0H), 4.82 (1iA, dd, 1H, 2 JP-H = 19.8 Hz, 2 JH-H = 15.1 Hz), 4.42 (1iA, dd, 1H, 2 JP-H = 22.2 Hz, 2 JH-H = 15.1 Hz), 3.61 (1iB, dd, 1H, 2 JP-H = 10.3 Hz, 2 JH-H = 12.7 Hz), 3.18 (1iB, dd, 1H, 2 JP-H = 4.9 Hz, 2 JH-H = 12.7 Hz), 2.63 (1iB, d, 3H 3
2 J P-H = 13.4 Hz), 1.18 (1iA, d, 3H, 2 JP-H = 8.3 Hz); 19 F NMR (CDCl3, δ) -72.7 (1iA, q, 3F, 4 JF- F = 8.5 Hz), -73.3 (1iB, m, 3F), -75.4 (1iA, q, 3F, 4 JF-F = 8.5 Hz), -76.1 (1iB, q, 3F, 4 JF-F = 8.5 Hz), -76.2 (1iA, q, 3F, 4 JF-F = 8.5 Hz), -76.6 (1iA, q, 3F, 4 JF-F = 8.5 Hz), -76.7 (1iB, m, 3F), -77.4 (1iB, q, 3F, 4 JF-F = 8.5 Hz), -114.8 (1iA, br s, 1F), -117.3 (1iB, br s, 1F); 31 P NMR (CDCl3, δ) - 26.7 (1iA, br s), -34.2 (1iB, 6 JP-F = 3.7 Hz). F 3 C CF 3HO CF 3 O CF3 P R Me A F 3 C CF 3HO CF 3 O CF3 P Me B R Chemical shifts (δ, ppm : upper values) and coupling constants ( 2 J P-H, ppm : lower values in parentheses) of the methyl groups in 1 H NMR. R CDCl 3 A B C 6 D 6 A B THF-d 8 A B Acetone-d 6 A B CD 3 CN A B 1a 1b 1c 1d 1e 1f 1g 1h 1i Me Et n-pr n-bu CH 2 OMe Ph CH 2 C 6 H 4 (p-me) CH 2 Ph CH 2 C 6 H 4 (p-f) 1.46 (5.9) 1.47 (5.8) 1.48 (6.0) 1.48 (5.9) 1.60 (7.0) ( ) 1.17 (6.3) 1.17 (6.4) 1.18 (8.3) 2.57 (13.7) 2.59 (13.3) 2.60 (13.3) 2.60 (13.7) 2.64 (14.5) 2.75 (13.7) 2.63 (13.4) 2.64 (13.7) 2.63 (13.4) 0.88 (6.3) 0.92 (5.8) 0.99 (5.8) 1.05 (7.5) 1.33 (7.0) ( ) 0.98 (6.5) 0.94 (6.3) 0.86 (6.3) 2.24 (13.7) 2.30 (13.1) 2.33 (13.1) 2.35 (13.1) 2.62 (14.3) 2.60 (13.8) 2.42 (13.3) 2.40 (13.5) 2.32 (13.3) 1.50 (6.6) 1.51 (5.8) 1.52 (6.3) 1.52 (6.3) 1.61 (5.8) ( ) 1.22 (6.3) 1.23 (6.0) 1.25 (8.2) 2.53 (14.0) 2.55 (13.5) 2.56 (13.5) 2.57 (13.3) 2.52 (14.5) 2.72 (11.8) 2.62 (13.8) 2.64 (14.0) 2.63 (13.8) 1.60 (6.8) 1.60 (6.5) 1.61 (6.5) 1.62 (6.5) 1.66 (7.3) ( ) 1.29 (6.8) 1.29 (7.0) 1.32 (6.8) 2.57 (14.0) 2.60 (13.5) 2.61 (13.5) 2.61 (13.6) 2.56 (14.5) 2.74 (14.7) 2.66 (14.0) 2.68 (13.8) 2.67 (13.8) 1.50 (6.8) 1.51 (5.8) 1.55 (5.8) 1.52 (6.8) 1.59 (7.3) ( ) 1.25 (6.3) 1.22 (7.0) 1.22 (6.3) 2.50 (13.8) 2.54 (13.3) 2.56 (13.3) 2.53 (13.5) 2.53 (14.5) 2.69 (13.8) 2.61 (12.9) 2.60 (13.5) 2.58 (12.7) 4
F 3 C CF 3HO CF 3 O CF3 P R Me A F 3 C CF 3HO CF 3 O CF3 P Me R B Chemical shifts (δ, ppm) of 31 P NMR in various solvents. 1a 1b 1c 1d 1e 1f 1g 1h 1i R Me Et n-pr n-bu CH 2 OMe Ph CH 2 C 6 H 4 (p-me) CH 2 Ph CH 2 C 6 H 4 (p-f) CDCl 3 C 6 D 6 THF-d 8 Acetone-d 6 CD 3 CN A B A B A B A B A B -34.8-34.5-29.7-28.0-26.6-21.9-24.5-24.2-25.7-25.2-25.7-26.7-25.3-26.5-26.2-35.5-22.5-34.2-35.2-36.8-21.4-24.5-24.2-25.4-25.4-25.9-26.5-24.8-26.6-26.3-35.1-21.9-33.5-34.5-35.9-17.0-20.1-19.7-22.6-20.6-20.6-21.6-20.4-21.7-21.4-33.6-21.1-27.9-28.8-30.0-15.3-18.3-17.9-21.5-19.6-20.2-20.5-18.3-19.8-19.4-32.9-19.5-26.8-27.8-28.9-13.6-16.7-16.6-18.1-16.3-17.9-20.4-32.2-17.9-18.2-26.0-18.7-27.0-18.9-28.1 5
X-ray structural determinations of 1a - 1i. Crystals suitable for X-ray structural determination were mounted on a Mac Science DIP2030 imaging plate diffractometer and irradiated with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) for data collection. Unit cell parameters were determined by autoindexing several images in each data set separately with the DENZO program (Mac Science). For each data set, rotation images were collected in 3 increments with a total rotation of 180 about the φ axis. Data were processed by using SCALEPACK. The structure was solved by a direct method with the SIR-92 program. Refinement of F was carried out by full-matrix least-squares. All non-hydrogen atoms were refined with anisotropic thermal parameters. The hydrogen atoms were included in the refinement with isotropic thermal parameters. The crystallographic data were summarized in Table S1. 6
Table S1. Crystallographic data Compound 1a 1b 1c Formula C20H15F12O2P C21H17F12O2P C22H19F12O2P Mot wt 546.29 560.32 574.35 Cryst syst Orthorhombic Monoclinic Monoclinic Space group Pna21 P21/n P21/n Color colorless colorless colorless Habit prism plate prism Cryst dimens, mm 0.30 x 0.25 x 0.20 0.65 x 0.35 x 0.05 0.20 x 0.20 x 0.10 a, Å 17.9640(6) 10.4300(2) 10.5720(3) b, Å 10.1010(3) 18.0140(4) 18.0290(5) c, Å 11.9380(4) 12.4740(3) 12.8920(3) α, deg 90 90 90 β, deg 90 102.795(1) 100.561(1) γ, deg 90 90 90 V, Å 3 2166.2(2) 2285.49(9) 2415.6(1) Z 4 4 4 Dcalc, g cm -3 1.675 1.628 1.579 Abs coeff, mm -1 0.246 0.235 0.225 F(000) 1096 1128 1160 Radiation; λ, Å Mo Kα; 0.71073 Mo Kα; 0.71073 Mo Kα; 0.71073 Temp, K 298 298 298 Data collcd +h, +k, +l +h, +k, ±l +h, +k, ±l Total data collcd, 2951 5670 6006 unique, 2951 5487 5812 obsd 2430 (I > 3σ(I)) 4749 (I > 3σ(I)) 4809 (I > 3σ(I)) Rint 0.000 0.000 0.000 No of params refined 316 325 334 R 0.0576 0.0650 0.0848 Rw 0.0798 0.1453 0.2044 GOF 1.016 1.362 1.979 Max shift in final cycle 0.0073 0.0001 0.0002 Final diff map, max, e/å 0.30 0.17 0.32 Solv for crystallization CH3CN CH3CN CH3CN Function minimized was sum [w( Fo 2 Fc 2 ) 2 ] where w = 1.0/[(sigma Fo 2 + 0.0007 Fo 2 ]. R = sum[ Fo Fc )/sum Fo. Rw = [sumw( Fo Fc ) 2 /sum Fo 2 ] 1/2. 7
Table S1 (continued). Compound 1d 1e 1f Formula C23H21F12O2P C21H17F12O2P C25H17F12O2P Mot wt 588.37 640.38 608.36 Cryst syst Monoclinic Monoclinic Orthorhombic Space group P21/n P21 P212121 Color colorless colorless colorless Habit plate prism plate Cryst dimens, mm 0.50 x 0.40 x 0.05 0.65 x 0.35 x 0.15 0.85 x 0.40 x 0.15 a, Å 10.6230(6) 9.0890(1) 9.8750(3) b, Å 17.804(1) 25.8410(5) 14.5480(2) c, Å 13.4070(5) 10.9370(2) 17.6650(5) α, deg 90 90 90 β, deg 98.981(2) 113.921(1) 90 γ, deg 90 90 90 V, Å 3 2504.6(2) 2348.12(7) 2537.78(9) Z 4 4 4 Dcalc, g cm -3 1.560 1.630 1.592 Abs coeff, mm -1 0.219 0.234 0.219 F(000) 1192 1160 1224 Radiation; λ, Å Mo Kα; 0.71073 Mo Kα; 0.71073 Mo Kα; 0.71073 Temp, K 298 298 298 Data collcd +h, +k, ±l +h, +k, ±l +h, +k, +l Total data collcd, 5655 5185 3236 unique, 5655 5169 3236 obsd 3316 (I > 3σ(I)) 4935 (I > 3σ(I)) 3132 (I > 3σ(I)) Rint 0.000 0.000 0.000 No of params refined 344 667 361 R 0.0752 0.0539 0.0623 Rw 0.1283 0.0843 0.0876 GOF 1.291 1.058 1.108 Max shift in final cycle 0.0018 0.0076 0.0201 Final diff map, max, e/å 0.40 0.15 0.26 Solv for crystallization CH3CN CH3CN CH3CN 8
Table S1 (continued). Compound 1g 1h 1i Formula C27H21F12O2P C26H19F12O2P C26H18F13O2P Mot wt 636.42 622.39 640.38 Cryst syst Triclinic Triclinic Monoclinic Space group P-1 P-1 P21/c Color colorless colorless colorless Habit prism plate plate Cryst dimens, mm 0.40 x 0.30 x 0.20 0.40 x 0.40x 0.20 0.20 x 0.20 x 0.05 a, Å 9.4340(5) 11.7550(4) 16.611(1) b, Å 10.8630(5) 12.5610(8) 10.6280(7) c, Å 14.4460(6) 18.904(1) 17.0740(7) α, deg 88.814(3) 93.532(2) 90 β, deg 86.530(3) 102.047(3) 119.205(3) γ, deg 67.657(2) 100.279(4) 90 V, Å 3 1366.8(1) 2671.8(2) 2631.1(3) Z 2 4 4 Dcalc, g cm -3 1.546 1.547 1.617 Abs coeff, mm -1 0.207 0.210 0.221 F(000) 644 1256 1228 Radiation; λ, Å Mo Kα; 0.71073 Mo Kα; 0.71073 Mo Kα; 0.71073 Temp, K 298 298 298 Data collcd +h, ±k, ±l +h, ±k, ±l +h, +k, ±l Total data collcd, 5775 11220 5841 unique, 5775 11220 5841 obsd 4403 (I > 3σ(I)) 7190 (I > 3σ(I)) 3385 (I > 3σ(I)) Rint 0.000 0.000 0.000 No of params refined 379 740 379 R 0.0591 0.0658 0.0696 Rw 0.1119 0.1320 0.1316 GOF 1.126 1.767 1.632 Max shift in final cycle 0.0010 0.0020 0.0000 Final diff map, max, e/å 0.21 0.43 0.31 Solv for crystallization CH3CN CH3CN CH3CN 9
Figure S1. ORTEP drawing of 1a (30% thermal ellipsoids). O(1) O(2) C(1) P(1) C(10) C(20) C(19) Selected bond distances (Å) and angles (deg) for 1a; P(1) O(1), 2.030(2); P(1) C(1), 1.832(4); P(1) C(10), 1.853(4); P(1) C(19), 1.856(4); P(1) C(20), 1.818(5); O(1) P(1) C(1), 81.8(1); O(1) P(1) C(10), 82.6(1); O(1) P(1) C(19), 176.6(2); O(1) P(1) C(20), 86.7(2); C(1) P(1) C(10), 113.9(2); C(1) P(1) C(19), 101.2(2); C(1) P(1) C(20), 113.4(2); C(10) P(1) C(19), 94.6(2); C(10) P(1) C(20), 129.1(2); C(19) P(1) C(20), 93.7(3). 10
Figure S2. ORTEP drawing of 1b (30% thermal ellipsoids). O(1) O(2) C(1) P(1) C(10) C(20) C(19) Selected bond distances (Å) and angles (deg) for 1b; P(1) O(1), 2.120(2); P(1) C(1), 1.824(3); P(1) C(10), 1.849(3); P(1) C(19), 1.855(3); P(1) C(20), 1.838(3); O(1) P(1) C(1), 80.5(1); O(1) P(1) C(10), 80.20(10); O(1) P(1) C(19), 175.2(1); O(1) P(1) C(20), 86.1(1); C(1) P(1) C(10), 112.5(1); C(1) P(1) C(19), 102.8(2); C(1) P(1) C(20), 112.9(1); C(10) P(1) C(19), 95.3(1); C(10) P(1) C(20), 129.3(1); C(19) P(1) C(20), 95.8(1). 11
Figure S3. ORTEP drawing of 1c (30% thermal ellipsoids). O(1) C(1) O(2) C(20) P(1) C(10) C(19) Selected bond distances (Å) and angles (deg) for 1c; P(1) O(1), 2.104(3); P(1) C(1), 1.820(5); P(1) C(10), 1.850(4); P(1) C(19), 1.857(5); P(1) C(20), 1.829(5); O(1) P(1) C(1), 80.5(2); O(1) P(1) C(10), 81.7(2); O(1) P(1) C(19), 175.3(2); O(1) P(1) C(20), 86.7(2); C(1) P(1) C(10), 113.7(2); C(1) P(1) C(19), 103.0(3); C(1) P(1) C(20), 113.7(2); C(10) P(1) C(19), 93.9(3); C(10) P(1) C(20), 128.3(2); C(19) P(1) C(20), 94.7(3). 12
Figure S4. ORTEP drawing of 1d (30% thermal ellipsoids). O(1) C(1) O(2) P(1) C(10) C(20) C(19) Selected bond distances (Å) and angles (deg) for 1d; P(1) O(1), 2.069(3); P(1) C(1), 1.824(5); P(1) C(10), 1.847(4); P(1) C(19), 1.861(6); P(1) C(20), 1.838(5); O(1) P(1) C(1), 80.6(2); O(1) P(1) C(10), 82.9(1); O(1) P(1) C(19), 176.7(2); O(1) P(1) C(20), 86.0(2); C(1) P(1) C(10), 113.0(2); C(1) P(1) C(19), 102.0(3); C(1) P(1) C(20), 114.8(2); C(10) P(1) C(19), 94.2(2); C(10) P(1) C(20), 128.1(2); C(19) P(10) C(20), 94.6(3). 13
Figure S5. ORTEP drawings of 1e (30% thermal ellipsoids). O(1) O(2) C(1) C(10) C(20) P(1) C(19) O(3) Selected bond distances (Å) and angles (deg) for the 1st molecule of 1e; P(1) O(1), 1.976(3); P(1) C(1), 1.830(4); P(1) C(10), 1.858(3); P(1) C(19), 1.885(5); P(1) C(20), 1.820(4); O(1) P(1) C(1), 83.0(2); O(1) P(1) C(10), 84.2(1); O(1) P(1) C(19), 174.9(2); O(1) P(1) C(20), 87.4(2); C(1) P(1) C(10), 113.8(2); C(1) P(1) C(19), 101.2(2); C(1) P(1) C(20), 114.9(2); C(10) P(1) C(19), 91.5(2); C(10) P(1) C(20), 129.0(2); C(19) P(1) C(20), 93.3(2). 14
O(5) O(4) C(31) C(22) P(2) C(42) C(40) O(6) Selected bond distances (Å) and angles (deg) for the 2nd molecule of 1e; P(2) O(4), 1.990(3); P(2) C(22), 1.830(4); P(2) C(31), 1.854(4); P(2) C(40), 1.889(4); P(2) C(42), 1.811(4); O(4) P(2) C(22), 82.6(2); O(4) P(2) C(31), 83.5(1); O(4) P(2) C(40), 173.5(2); O(4) P(2) C(42), 88.2(2); C(22) P(2) C(31), 114.6(2); C(22) P(2) C(40), 102.1(2); C(22) P(2) C(42), 113.7(2); C(31) P(2) C(40), 90.4(2); C(31) P(2) C(42), 129.3(2); C(40) P(2) C(42), 93.9(2). 15
Figure S6. ORTEP drawing of 1f (30% thermal ellipsoids). O(1) O(2) C(1) C(25) P(1) C(10) C(19) Selected bond distances (Å) and angles (deg) for 1f; P(1) O(1), 2.042(2); P(1) C(1), 1.837(3); P(1) C(10), 1.855(3); P(1) C(19), 1.870(3); P(1) C(25), 1.826(3); O(1) P(1) C(1), 81.2(1); O(1) P(1) C(10), 81.08(10); O(1) P(1) C(19), 178.1(1); O(1) P(1) C(25), 84.9(1); C(1) P(1) C(10), 112.2(1); C(1) P(1) C(19), 100.7(1); C(1) P(1) C(25), 114.1(1); C(10) P(1) C(19), 98.2(1); C(10) P(1) C(25), 128.5(1); C(19) P(10) C(25), 94.3(1). 16
Figure S7. ORTEP drawing of 1g (30% thermal ellipsoids). O(1) O(2) C(1) C(20) P(1) C(10) C(19) Me Selected bond distances (Å) and angles (deg) for 1g; P(1) O(1), 2.124(2); P(1) C(1), 1.824(3); P(1) C(10), 1.861(3); P(1) C(19), 1.849(3); P(1) C(20), 1.844(3); O(1) P(1) C(1), 80.5(1); O(1) P(1) C(10), 81.28(9); O(1) P(1) C(19), 175.9(1); O(1) P(1) C(20), 84.2(1); C(1) P(1) C(10), 111.0(1); C(1) P(1) C(19), 102.6(1); C(1) P(1) C(20), 114.7(1); C(10) P(1) C(19), 95.0(1); C(10) P(1) C(20), 128.7(1); C(19) P(10) C(20), 96.9(1). 17
Figure S8. ORTEP drawings of 1h (30% thermal ellipsoids). O(1) O(2) C(1) C(20) P(1) C(10) C(19) Selected bond distances (Å) and angles (deg) for the 1st molecule of 1h (1hA); P(1) O(1), 2.078(3); P(1) C(1), 1.809(5); P(1) C(10), 1.850(4); P(1) C(19), 1.853(5); P(1) C(20), 1.865(4); O(1) P(1) C(1), 81.1(2); O(1) P(1) C(10), 80.9(1); O(1) P(1) C(19), 174.3(2); O(1) P(1) C(20), 85.9(2); C(1) P(1) C(10), 114.1(2); C(1) P(1) C(19), 102.9(2); C(1) P(1) C(20), 112.5(2); C(10) P(1) C(19), 93.6(2); C(10) P(1) C(20), 128.5(2); C(19) P(1) C(20), 96.3(2). 18
O(3) O(4) C(27) P(2) C(36) C(52) C(45) Selected bond distances (Å) and angles (deg) for the 2nd molecule of 1h (1hB); P(2) O(3), 2.043(3); P(2) C(27), 1.844(5); P(2) C(36), 1.858(4); P(2) C(45), 1.892(5); P(2) C(52), 1.819(5); O(3) P(2) C(27), 81.3(2); O(3) P(2) C(36), 83.8(2); O(3) P(2) C(45), 179.5(2); O(3) P(2) C(52), 85.7(2); C(27) P(2) C(36), 111.6(2); C(27) P(2) C(45), 98.2(2); C(27) P(2) C(52), 117.7(2); C(36) P(2) C(45), 96.2(2); C(36) P(2) C(52), 127.0(2); C(45) P(2) C(52), 94.7(2). 19
Figure S9. ORTEP drawing of 1i (30% thermal ellipsoids). O(1) O(2) C(1) P(1) C(10) C(26) C(19) F Selected bond distances (Å) and angles (deg) for 1i; P(1) O(1), 2.060(4); P(1) C(1), 1.832(5); P(1) C(10), 1.854(5); P(1) C(19), 1.916(6); P(1) C(26), 1.800(6); O(1) P(1) C(1), 80.9(2); O(1) P(1) C(10), 83.0(2); O(1) P(1) C(19), 178.4(2); O(1) P(1) C(26), 85.6(2); C(1) P(1) C(10), 112.6(2); C(1) P(1) C(19), 99.5(2); C(1) P(1) C(26), 115.5(2); C(10) P(1) C(19), 95.4(2); C(10) P(1) C(26), 127.8(2); C(19) P(10) C(26), 95.6(3). 20