Supporting Information Wiley-VCH 2007 69451 Weinheim, Germany
Carbene Activation of P 4 and Subsequent Derivatization Jason D. Masuda, Wolfgang W. Schoeller, Bruno Donnadieu, and Guy Bertrand * [*] Dr. J. D. Masuda, Prof. W. W. Schoeller, B. Donnadieu, Prof. G. Bertrand UCR-CNRS Joint Research Chemistry Laboratory (UMI 2957) Department of Chemistry University of California Riverside, CA 92521-0403 (USA) Fax: (+1) 951-827-2725 E-mail: gbertran@mail.ucr.edu Contents 1. Synthesis and characterization compounds 2a, 3 and 6 2. Crystal Structure Determination of compounds 2a, 3 and 6 1. Synthesis and characterization General All manipulations were performed under an inert atmosphere of dry argon by using standard Schlenk techniques or in an mbraun glovebox. Dry, oxygen-free solvents were employed. 1 H, 13 C, and 31 P NMR spectra were recorded on Bruker Avance 300 or Varian Inova 400 and 500 spectrometers. 1 H and 13 C NMR chemical shifts are reported relative to SiMe 4. 31 P NMR chemical shifts are reported relative to 85% H 3 PO 4. Synthesis of 2 CAAC 1 [1] (200 mg, 0.524 mmol) was added to a rapidly stirred suspension of P 4 (32.5 mg, 0.262 mmol) in 10 ml hexanes. Immediately upon addition a blue colored solution formed. The mixture was stirred for two hours at room temperature and the solution was filtered through a glass filter paper. Upon concentration of the solution under vacuum, a dark blue crystalline material precipitated and was isolated by filtration. Slow evaporation of a hexanes solution of this material gave 2a as single crystals suitable for an X-ray diffraction study; 65% yield; m.p. 184-185 C. 31 P{ 1 H} NMR (300 MHz, [D 8 ]benzene, 25 C): δ= 2a trans (major) 568.2 and 120.8 ppm (AA XX spin system, J AA = -679.4, J AX = -248.7, J AX = -70.7, J XX = -13.7), 2b cis (minor), 452.0 and 115.3 ppm (AA XX spin system, J AA = -511.2, J AX = -424.7, J AX = -10.8, J XX = - 319.1) (Fig. 1). [2] Due to the presence of cis and trans isomers and the highly complex nature of the CAAC ligands, meaningful interpretation of the 13 C{ 1 H} and 1 H NMR spectra was not possible.
Figure 1. 31 P{ 1 H} NMR spectrum (121.5 MHz) for 2 Synthesis of 3 CAAC 1 (500 mg, 1.31 mmol) and P 4 (81.1 mg, 0.66 mmol) were combined in 20 ml hexanes and stirred overnight. To the resulting blue solution was added 200 µl of 2,3-dimethylbutadiene and upon stirring overnight, a yellow solution remained. Analysis by 31 P NMR showed nearly quantitative conversion of 3. The solution was then filtered through a glass fiber plug and all volatiles were removed under vacuum. Adduct 3 was recrystallized by diffusion of a diethyl ether solution (15 ml) into 20 ml of acetonitrile; 35% yield; m.p. 130 C dec; 31 P{ 1 H} NMR (121.5 MHz, [D 6 ]benzene, 25 C): δ= 55.8 and -35.8 ppm, J AA = -240.8, J AB = -203.1, J AB = 237.4, J BB = -7.6. Due to the highly complex nature of the CAAC ligands, only partial assignments are made: δ=7.27-7.39 (m, 1H, Ar), 7.05-7.14 (m, 2H, Ar), 3.25 (sept, 2H, 3 J(H,H)=7 Hz, ipr-h), 3.10 (sept, 2H, 3 J(H,H)=7 Hz, ipr-h), 2.99 (m, 2H, ipr-h), 2.56 (m, 2H), 2.41 (m, 3H), 2.12 (m, 2H), 1.87 (m, 6H), 1.73 (m, 6H), 1.73 (d, 3H, 3 J(H,H)=7 Hz, ipr-ch 3 ), 1.43 (d, 6H, 3 J(H,H)=7 Hz, ipr-ch 3 ), 1.42 (s, 6H, CH 3 ), 1.33 (d, 3H, 3 J(H,H)=7 Hz, ipr-ch 3 ), 1.28 (d, 3H, 3 J(H,H)=7 Hz, ipr-ch 3 ), 1.18 (d, 3H, 3 J(H,H)=7 Hz, ipr-ch 3 ), 1.14 (d, 3H, 3 J(H,H)=7 Hz, ipr-ch 3 ), 1.03 (d, 3H, 3 J(H,H)=7 Hz, ipr-ch 3 ), 0.87 (s, 6H, CH 3 ), 0.66 (s, 6H, CH 3 ); 13 C{ 1 H} NMR (125.75 MHz, [D 6 ]benzene, 25 C): δ= 199.8 (d of m, 1 J(P,C)=126 Hz, PCN), 150.5 (Ar), 148.2 (Ar), 138.6 (Ar), 129.4 (Ar-H), 126.1 (Ar-H), 126.2 (Ar-H), 116.3 (br, C=C), 68.4, 59.6, 59.5, 56.5 (CH 2 ), 53.9 (CH 2 ), 51.7 (C-H), 36.4 (CH 2 ), 33.9 (br m, CH 2 ), 32.3 (CH 3 ), 30.2 (CH), 29.6 (CH), 29.4 (CH), 28.9 (CH3), 28.6 (CH), 28.3 (CH), 28.0 (CH 3 ), 27.6 (CH 3 ), 27.1 (CH), 27.0 (CH), 25.6 (CH 3 ), 25.5 (CH 2 ), 25.4 (CH 2 ), 24.4 (CH 3 ), 21.9 (m, CH 3 ). Synthesis of 6 CAAC 1 (150 mg, 0.393 mmol) was added to a rapidly stirred mixture of P 4 (45.8 mg, 0.393 mmol) and 2,3-dimethylbutadiene (2 ml) in hexanes (3 ml). Immediately upon addition a faint blue colored solution formed, which then turned yellow over 1 hour. The solution was stirred overnight and the solvents removed under vacuum. Analysis of the crude material by 31 P spectroscopy showed exclusive formation of 6. The yellow residue was then dissolved in hexanes and filtered through a glass wool plug. Concentration of the solution by evaporation under vacuum gave 117 mg of yellow crystals. Yield: 52%; m.p. 206-210 C; 31 P{ 1 H} NMR (121.5 MHz, [D 6 ]benzene, 25 C): δ= 17.6, -171.6 and -200.8 ppm, J AM = -212.1, J AX = 154.9, J MX = -202.6, J AX = 143.6, J MX = -133.6, J XX = -149.8. [19] (Fig. 2); 1 H NMR (500 MHz,
[D 6 ]benzene, 25 C): δ=7.20-7.23 (m, 1H, Ar), 7.11-7.15 (m, 2H, Ar), 3.29 (sept, 1H, 3 J(H,H)=7 Hz, ipr-h), 3.28 (sept, 1H, 3 J(H,H)=7 Hz, ipr-h), 2.82 (m, 1H, ipr-h), 2.51 (m, 1H), 2.39 (d, 1H, J(H,H)=13 Hz, CH 2 ), 2.25 (d, 1H, J(H,H)=13 Hz, CH 2 ), 2.09 (m, 3H), 1.74 (d, 3H, 3 J(H,H)=7 Hz, ipr-ch 3 ), 1.73 (d, 3H, 3 J(H,H)=7 Hz, ipr-ch 3 ), 1.60 (d, 1H, J(H,H)=13 Hz, CH 2 ), 1.50 (d, 6H, 4 J(P,H)=8 Hz, C=CCH 3 ), 1.42 (d, 3H, 3 J(H,H)=7 Hz, ipr-ch 3 ), 1.30 (d, 6H, 3 J(H,H)=7 Hz, ipr-ch 3 ), 1.27 (s, 3H, CH 3 ), 1.07-1.12 (m, 8H), 0.91 (d, J(H,H)=13 Hz, CH 2 ), 0.87 (d, 3 J(H,H)=7 Hz, ipr-ch 3 ), 0.78 ppm (m, 1H); 13 C{ 1 H} NMR (125.75 MHz, [D 6 ]benzene, 25 C): δ= 199.2 (d of m, 1 J(P,C)=128 Hz, PCN), 150.0 (Ar), 135.9 (Ar), 130.1 (Ar-H), 126.8 (Ar-H), 126.4 (Ar-H), 121.3 (br m, C=C), 68.9, 59.9 (NCCH 3 ), 59.7 (NCCH 3 ), 55.2 (CH 2 ), 54.2 (CH 2 ), 51.2 (CH), 31.0 (CH 3 ), 30.2 (CH 3 ), 30.1 (CH), 29.4 (CH), 29.3 (CH), 27.7 (CH), 27.6 (CH), 27.5 (CH 3 ), 27.1 (CH 3 ), 26.8 (br, PCH 2 ), 25.9 (CH 3 ), 25.1 (CH 3 ), 25.0 (CH 2 ), 24.9 (CH 2 ), 23.6 (CH 3 ), 21.4 (CH 3 ), 21.4 (CH 3 ), 20.7 (dd, 2 J(P,C)=23 Hz, 3 J(P,C)=4 Hz, C=CCH 3 ). Figure 2. 31 P{1H} NMR spectrum (121.5 MHz) of 6. Full spectrum (bottom) and expansions (inset) showing the experimental (upright) and simulated[3] (inverted) spectra. 2. Crystal Structure Determination of compound 2a, 3 and 6 The Bruker X8-APEX [4] X-ray diffraction instrument with Mo-radiation was used for data collection. All data frames were collected at low temperature (T = 100 K) using an ω, φ-scan mode (0.3 o ω-scan width, hemisphere of reflections) and integrated using a Bruker SAINTPLUS software package. [5] The intensity data were corrected for Lorentzian polarization. Absorption corrections were performed using the SADABS program. [6] The SIR92 [7] was used for direct methods of phase determination, and Bruker SHELXTL software package [8] for structure refinement and difference Fourier maps. Atomic coordinates, isotropic and anisotropic displacement parameters of all the non-hydrogen atoms of compounds were refined by means of a full matrix least-squares procedure on F 2. All H-atoms were included in the refinement in calculated positions riding on the C atoms. Molecular drawings were made using ORTEP3. [9] (2a) Crystal and structure parameters: size 0.37 x 0.27 x 0.15 mm 3, monoclinic, space group P2(1), a = 16.388(10) Å, b = 19.127(12) Å, c = 19.070(12) Å, α = 90.0 o β = 112.178(7) o, γ = 90.0 o, V = 5535(6) Å 3, ρ calcd = 1.065 g/cm 3, Mo-radiation (λ = 0.71073 Å), T = 100(2) K, reflections collected = 28961, independent reflections = 15288 (R int = 0.1250), absorption coefficient µ = 0.170 mm -1 ; max/min
transmission = 0.9429 and 0.9749, 1117 parameters were refined and converged at R1 = 0.0876, wr2 = 0.1867, with intensity I>2σ(I), structure_flack parameter = 0.07(16). (3) Crystal and structure parameters: size 0.32 x 0.15 x 0.13 mm 3, orthorhombic, space group P2(1)2(1)2(1), a = 16.9587(17) Å, b = 17.0358(17) Å, c = 42.574(4) Å, α = 90.0 o β = 90.0 o, γ = 90.0 o, V = 12300(2) Å 3, ρ calcd = 1.113 g/cm 3, Mo-radiation (λ = 0.71073 Å), T = 100(2) K, reflections collected = 77652, independent reflections = 20906 (R int = 0.0715), absorption coefficient µ = 0.162 mm -1 ; max/min transmission = 0.9792 and 0.9499, 1313 parameters were refined and converged at R1 = 0.1023, wr2 = 0.2366, with intensity I>2σ(I). (6) Crystal and structure parameters: size 0.20 x 0.15 x 0.10 mm 3, monoclinic, space group P2(1), a = 8.959(2) Å, b = 17.088(4) Å, c = 12.003(3) Å, α = 90.0 o β = 111.195(3) o, γ = 90.0 o, V = 1713.2(7) Å 3, ρ calcd = 1.139 g/cm 3, Mo-radiation (λ = 0.71073 Å), T = 100(2) K, reflections collected = 18602, independent reflections = 4329 (R int = 0.0605), absorption coefficient µ = 0.242 mm -1 ; max/min transmission = 0.9532 and 0.9762, 355 parameters were refined and converged at R1 = 0.0430, wr2 = 0.0943, with intensity I>2σ(I), structure_flack parameter = 0.07(11). [1] V. Lavallo, Y. Canac, C. Präsang, B. Donnadieu, G. Bertrand, Angew. Chem. 2005, 117, 5851-5855; Angew. Chem. Int. Ed. 2005, 44, 5705-5709. [2] Coupling constants for the AA XX spin system were calculated mathematically using equations provided in: F.A. Bovey, in Nuclear Magnetic Resonance Spectroscopy, 2 nd edition, Academic Press, 1988. The calculated parameters were shown to reproduce the experimental spectra in gnmr. [3] Spectral parameters were determined iteratively using full lineshape analysis using the computer program gnmr: P.H.M. Budzelaar, gnmr, Version 5.0.6.0, 2006. [4] APEX 2 version 2.0-2. Bruker AXS Inc., Madison, Wisconsin, USA, 2005. [5] SAINT version V7.21A. Bruker AXS Inc., Madison, Wisconsin, USA, 2005. [6] SADABS version 2004/1. Bruker Analytical X-Ray System, Inc., Madison, Wisconsin, USA, 2004. [7] SIR92 - A program for crystal structure solution. A. Altomare, G. Cascarano, C. Giacovazzo and A. Guagliardi, J. Appl. Crystallogr. 1993, 26, 343-350. [8] SHELXTL Software Version 6.14, Dec, Bruker Analytical X-Ray System, Inc.,Madison, Wisconsin, USA, 2003. [9] ORTEP3 for Windows - L. J. Farrugia, J. Appl. Crystallogr. 1997, 30, 565.