Appendix A: Molecular Modelling
Table A.1 Crystallographic and theoretic values of essential bond lengths and angles of the Grubbs-type catalysts systems
Bond lengths (Å) Bond Angles (°)
Catalyst Ru=C Ru-Clave Ru-Pave Cl-Ru-Cl P(1)-Ru-P(2) Ru=C-R
Grubbs 126 (A1) 1.838 2.390 2.416 168.21 161.90 136.70 Grubbs 115 (A1) 1.878 2.452 2.490 160.97 163.35 136.04 Grubbs 1a (A1) 1.878 2.456 2.485 163.95 163.02 136.43 Grubbs 227 (A2) 1.835 2.395 2.425b 1.67.71 163.73 137.00 Grubbs 227 (A2) 2.085NHC Grubbs 215 (A2) 1.879 2.461 2.525b 169.97 165.34 136.81 Grubbs 215 (A2) 2.121NHC Grubbs 2a (A2) 1.876 2.458 2.528b 169.83 166.00 136.75 Grubbs 2a (A2) 2.124NHC Phobcat28 (A3) - - 2.445 - 159.60 - Phobcata (A3) 1.880 2.453 2.441 167.39 159.50 136.87 Phobcata (A9) 1.880 2.456 2.458 170.53 159.51 137.30 CyMea (A14) 1.881 2.453 2.473 170.16 163.11 137.42 CyMea (A4) 1.877 2.433 2.464 166.87 159.96 135.60 CyMea (A10) 1.880 2.451 2.484 167.78 166.99 136.77 CyMea (A15) 1.880 2.446 2.460 167.22 159.63 136.48 PhMea (A16) 1.885 2.446 2.434 167.28 171.89 136.13 PhMea (A6) 1.881 2.455 2.398 167.79 153.22 136.04 PhMea (A12) 1.885 2.443 2.437 166.94 172.12 135.86 PhMea (A17) 1.882 2.454 2.397 167.65 153.07 135.81 CyiPa (A18) 1.878 2.446 2.468 169.06 163.94 136.63 CyiPa (A5) 1.878 2.447 2.458 167.21 158.90 136.24 CyiPa (A11) 1.880 2.433 2.482 164.09 166.20 134.35 CyiPa (A19) 1.878 2.448 2.459 167.95 157.32 136.84 PhiPa (A20) 1.886 2.428 2.444 162.77 169.06 133.68 PhiPa (A7) 1.881 2.456 2.395 167.94 153.65 136.12 PhiPa (A13) 1.885 2.445 2.431 168.55 171.49 136.19 PhiPa (A21) 1.881 2.456 2.395 168.02 152.96 135.98 CytBa (A26) 1.875 2.432 2.547 161.98 166.92 132.95 CytBa (A25) 1.877 2.442 2.506 165.89 160.01 136.20 CytBa (A28) 1.875 2.432 2.546 162.07 166.49 133.00 CytBa (A27) 1.876 2.442 2.503 165.74 159.57 135.94 PhtBa (A22) 1.888 2.454 2.484 172.45 172.78 136.84 PhtBa (A8) 1.879 2.453 2.435 167.82 154.69 136.15 PhtBa (A24) 1.889 2.458 2.466 172.29 171.93 137.74 PhtBa (A23) 1.880 2.454 2.434 167.33 154.04 136.00
a DMol3 GGA/PW91/DNP – full DFT-calculation of geometries.
b The single phosphine bond length of Grubbs 2 is indicated. NHC
Appendix A: Molecular Modelling
118
Figure A.1 The dissociation and activation steps during the productive metathesis of 1-octene with A1, A2 and A3 benzylidene and methylidene precatalysts to yield the catalytically active heptylidene (F).
Appendix A: Molecular Modelling
Figure A.2 The dissociation and activation steps during the productive metathesis of 1-octene with a selection of the new tt-precatalysts to yield the catalytically active heptylidene (F).
Appendix A: Molecular Modelling
120
Figure A.3 The dissociation and activation steps during the productive metathesis of 1-octene with a selection of the new cc-precatalysts to yield the catalytically active heptylidene (F).
Appendix A: Molecular Modelling
Figure A.4 A comparison between the steps of the catalytic cycle of a selection of the new tt-precatalysts.
Appendix A: Molecular Modelling
122
Figure A.5 A comparison between the steps of the catalytic cycle of a selection of the new cc-precatalysts.
Appendix A: Molecular Modelling
Figure A.6 A comparison between the cis- and trans-7-tetradecene formation catalytic cycle steps of a selection of the new tt-precatalysts.
Appendix A: Molecular Modelling
124
Figure A.7 A comparison between the cis- and trans-7-tetradecene formation catalytic cycle steps of a selection of the new cc-precatalysts.
Appendix A: Molecular Modelling
Table A.2 The calculated metallacyclobutane ring D bond lengths of A4 to A28 Step Bond-1 (Å) Bond-2 (Å) Bond-3 (Å) Bond-4 (Å) Bond-5 (Å)
D4 2.048 2.018 1.580 1.587 2.270 D5 2.048 2.016 1.581 1.587 2.273 D6 2.040 2.016 1.586 1.585 2.271 D7 2.042 2.018 1.582 1.586 2.271 D8 2.050 2.019 1.581 1.582 2.274 D9 2.036 2.025 1.587 1.581 2.271 D10 2.040 2.022 1.581 1.586 2.268 D11 2.042 2.016 1.589 1.583 2.272 D12 2.041 2.019 1.580 1.589 2.273 D13 2.053 2.014 1.584 1.587 2.275 D14 2.038 2.021 1.585 1.584 2.269 D15 2.042 2.019 1.583 1.586 2.268 D16 2.039 2.017 1.580 1.592 2.271 D17 2.040 2.005 1.582 1.592 2.271 D18 2.042 2.032 1.585 1.579 2.267 D19 2.047 2.018 1.586 1.584 2.271 D20 2.036 2.024 1.585 1.585 2.269 D21 2.051 2.010 1.580 1.590 2.270 D22 2.036 2.032 1.589 1.578 2.266 D23 2.043 2.014 1.592 1.582 2.269 D24 2.047 2.018 1.582 1.585 2.274 D25 2.065 2.018 1.580 1.583 2.271 D26 2.037 2.039 1.590 1.572 2.263 D27 2.048 2.021 1.589 1.578 2.266 D28 2.056 2.008 1.580 1.590 2.272
Appendix A: Molecular Modelling
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Table A.3 The calculated metallacyclobutane ring tH bond lengths of A4 to A28 Step Bond-1 (Å) Bond-2 (Å) Bond-3 (Å) Bond-4 (Å) Bond-5 (Å)
tH4 2.015 1.995 1.553 1.624 2.296 tH5 2.012 2.000 1.554 1.621 2.297 tH6 2.014 1.995 1.557 1.620 2.300 tH7 2.014 1.997 1.558 1.617 2.302 tH8 2.013 1.998 1.555 1.620 2.302 tH9 2.001 2.010 1.569 1.603 2.303 tH10 2.009 2.002 1.560 1.613 2.297 tH11 2.017 1.991 1.556 1.625 2.302 tH12 2.009 1.999 1.557 1.620 2.302 tH13 2.017 1.989 1.553 1.632 2.301 tH14 2.009 2.009 1.558 1.613 2.301 tH15 2.010 2.003 1.559 1.616 2.302 tH16 2.008 2.003 1.559 1.616 2.303 tH17 2.012 2.001 1.561 1.613 2.304 tH18 2.009 2.008 1.561 1.610 2.304 tH19 2.015 2.018 1.560 1.601 2.306 tH20 2.007 2.006 1.558 1.616 2.305 tH21 2.007 2.004 1.571 1.603 2.310 tH22 2.009 2.008 1.555 1.619 2.309 tH23 2.007 2.013 1.561 1.609 2.312 tH24 2.005 2.001 1.582 1.607 2.310 tH25 2.023 1.990 1.551 1.634 2.305 tH26 1.996 2.033 1.571 1.593 2.313 tH27 2.003 2.027 1.556 1.606 2.304 tH28 2.006 2.008 1.561 1.613 2.300
Appendix A: Molecular Modelling
Table A.4 The calculated metallacyclobutane ring cH bond lengths of A1 to A28, A105 and A106
Step Bond-1 (Å) Bond-2 (Å) Bond-3 (Å) Bond-4 (Å) Bond-5 (Å)
cH1 1.997 2.009 1.576 1.621 2.305 cH2 1.981 2.023 1.587 1.613 2.313 cH3 1.989 2.043 1.593 1.601 2.312 cH4 1.997 2.021 1.568 1.637 2.305 cH5 1.996 2.019 1.577 1.619 2.310 cH6 1.995 2.009 1.583 1.616 2.305 cH7 1.996 2.006 1.583 1.615 2.306 cH8 1.990 2.010 1.584 1.612 2.307 cH9 2.009 2.010 1.566 1.638 2.307 cH10 1.999 2.011 1.578 1.619 2.304 cH11 1.993 2.023 1.571 1.633 2.301 cH12 1.996 2.011 1.567 1.637 2.305 cH13 1.995 2.012 1.578 1.621 2.306 cH14 2.007 2.012 1.574 1.622 2.310 cH15 2.007 2.002 1.571 1.631 2.307 cH16 2.005 2.005 1.567 1.635 2.307 cH17 1.995 2.019 1.575 1.625 2.307 cH18 2.002 2.016 1.578 1.618 2.311 cH19 2.011 2.016 1.563 1.635 2.312 cH20 2.009 2.012 1.568 1.628 2.310 cH21 2.006 1.995 1.578 1.625 2.306 cH22 1.998 2.014 1.569 1.630 2.312 cH23 1.982 2.037 1.590 1.606 2.316 cH24 2.008 1.987 1.567 1.635 2.297 cH25 1.994 2.009 1.575 1.620 2.301 cH26 2.008 2.028 1.568 1.625 2.312 cH27 2.003 2.006 1.572 1.625 2.308 cH28 1.980 2.058 1.595 1.585 2.312 cH105 2.002 2.006 1.567 1.636 2.305 cH106 2.006 2.009 1.577 1.625 2.306
Appendix A: Molecular Modelling
128
Table A.5 The calculated metallacyclobutane ring M bond lengths of A4 to A28 Step Bond-1 (Å) Bond-2 (Å) Bond-3 (Å) Bond-4 (Å) Bond-5 (Å)
M4 2.006 2.006 1.564 1.602 2.262 M5 2.005 2.002 1.569 1.599 2.263 M6 2.002 2.006 1.573 1595 2.265 M7 2.003 2.005 1.571 1.596 2.266 M8 2.001 2.007 1.570 1.596 2.267 M9 2.004 2.015 1.566 1.594 2.261 M10 2.000 2.013 1.569 1.595 2.261 M11 1.998 2.012 1.575 1.591 2.263 M12 2.000 2.008 1.565 1.602 2.264 M13 2.003 2.001 1.569 1.600 2.264 M14 2.000 2.021 1.568 1.593 2.266 M15 2.007 2.005 1.567 1.600 2.265 M16 2.002 2.011 1.563 1.603 2.268 M17 2.003 2.005 1.573 1.595 2.267 M18 2.000 2.022 1.575 1.588 2.268 M19 2.009 2.006 1.565 1.599 2.265 M20 2.001 2.016 1.567 1.601 2.270 M21 2.005 2.006 1.571 1.596 2.267 M22 2.005 2.026 1.556 1.602 2.269 M23 2.003 2.010 1.569 1.594 2.269 M24 2.003 1.999 1.566 1.606 2.268 M25 2.006 2.002 1.563 1.605 2.263 M26 1.986 2.038 1.589 1.578 2.263 M27 2.005 2.015 1.560 1.599 2.266 M28 2.002 2.006 1.568 1.597 2.262
Appendix A: Molecular Modelling
Table A.6 A comparison between the molecular modelling G(complex) and G(Ru1) values of Grubbs1, Grubbs 2 and Phobcat precatalysts
Step Grubbs 1 (%) Grubbs 2 (%) ttPhobcat (%) ccPhobcat (%)
A 94.31 75.71 95.12 74.87 94.29 77.26 93.03 76.62 B 78.87 66.77 80.22 65.42 77.00 67.12 76.67 67.18 C 91.68 76.25 93.27 75.67 91.25 77.14 91.37 77.39 C-D 90.92 75.29 93.48 75.00 91.96 75.98 91.04 75.84 D 89.31 73.97 93.30 74.49 90.96 74.96 91.05 74.97 D-E 91.21 75.54 93.28 75.87 92.56 76.48 92.64 76.69 E 92.32 78.01 93.40 76.93 92.35 78.65 91.21 78.41 F 76.73 67.19 78.93 66.88 75.20 67.46 74.72 67.69 G_tC14 91.43 78.56 91.99 77.17 88.60 78.73 89.91 78.93 G-H_tC14 90.33 76.72 93.18 76.77 89.18 77.36 90.60 77.73 H_tC14 88.91 75.36 92.70 75.61 89.19 75.93 90.40 76.17 H-I_tC14 90.94 76.81 94.29 76.77 91.60 77.82 90.85 77.74 I_tC14 90.78 74.05 93.88 77.69 91.22 78.50 91.06 79.08 J 77.16 68.26 79.31 67.72 75.03 68.83 75.15 68.22 K 91.17 73.89 92.42 76.50 90.96 77.82 91.19 77.76 K-M 91.80 77.30 92.68 76.41 91.05 77.89 91.12 77.89 M 88.99 75.42 93.32 75.64 90.08 75.92 90.35 75.92 M-N 90.20 77.03 92.65 76.53 88.25 77.70 89.54 77.88 N 89.82 79.06 91.57 75.70 87.95 77.86 89.01 78.48 G_cC14 89.88 74.57 93.95 78.05 87.62 76.99 90.30 78.69 G-H_cC14 90.23 76.58 93.46 76.72 90.62 76.63 91.78 76.78 H_cC14 88.94 75.42 93.50 75.70 90.79 75.24 91.61 75.52 H-I_cC14 90.96 76.89 94.39 76.73 92.95 77.04 91.97 77.07 I_cC14 90.38 77.16 92.12 76.72 92.63 78.38 92.04 77.98
Appendix A: Molecular Modelling
130
Table A.7 A comparison between the molecular modelling G(complex) and G(Ru1) values of CyMe precatalysts
Step ttCyMe_a (%) ccCyMe_a (%) ttCyMe_b (%) ccCyMe_b (%)
A 94.33 77.03 92.59 76.03 93.86 76.94 92.91 75.58 B 75.04 67.38 78.09 67.02 77.76 67.17 75.75 66.86 C 91.48 78.69 91.12 78.15 90.15 77.01 90.57 77.42 C-D 91.13 76.28 89.88 76.12 90.46 76.22 90.52 76.26 D 90.80 74.90 90.41 75.30 90.56 75.24 90.92 75.24 D-E 91.89 76.72 92.87 76.90 91.69 76.57 92.48 76.90 E 90.88 77.02 93.24 79.11 92.54 78.20 93.41 79.22 F 79.06 68.19 77.56 68.58 76.48 67.80 76.54 68.49 G_tC14 89.66 78.61 90.04 79.09 89.77 78.17 89.98 78.64 G-H_tC14 90.31 77.58 90.77 77.59 90.14 77.52 90.51 77.80 H_tC14 90.60 76.62 89.94 76.09 90.60 76.39 90.40 76.45 H-I_tC14 90.95 77.76 90.41 77.56 91.43 77.85 91.44 77.77 I_tC14 91.65 79.45 91.02 78.61 91.04 78.45 91.30 78.24 J 75.79 68.96 76.44 68.36 75.74 68.97 76.46 68.36 K 89.05 78.98 90.06 77.98 91.21 79.33 90.43 78.22 K-M 90.23 78.23 90.08 77.93 91.63 78.39 90.52 78.14 M 90.83 76.65 90.04 76.10 90.87 76.45 90.57 76.55 M-N 89.17 77.82 89.50 78.35 89.03 78.03 89.32 78.04 N 89.12 77.91 89.14 79.91 88.58 78.83 89.30 78.26 G_cC14 89.46 74.77 90.02 75.41 90.50 74.97 90.01 78.25 G-H_cC14 90.57 77.25 91.00 77.19 90.53 77.18 90.66 77.41 H_cC14 90.17 75.85 90.15 75.52 90.87 76.04 90.47 76.00 H-I_cC14 90.91 77.71 90.66 77.51 91.51 77.81 91.23 77.71 I_cC14 91.41 78.50 90.74 77.80 90.70 78.24 91.61 78.09
Appendix A: Molecular Modelling
Table A.8 A comparison between the molecular modelling G(complex) and G(Ru1) values of CyiP precatalysts
Step ttCyiP_a (%) ccCyiP_a (%) ttCyiP_b (%) ccCyiP_b (%)
A 94.93 76.99 94.01 76.42 95.25 76.96 94.22 76.31 B 75.94 67.11 80.09 66.81 77.84 67.10 78.83 76.31 C 92.55 78.69 91.75 76.95 91.59 77.77 92.42 76.72 C-D 92.09 76.31 91.75 75.98 91.50 76.28 92.53 76.08 D 92.21 75.00 91.80 74.82 91.93 75.16 92.23 75.28 D-E 92.52 76.69 93.21 76.91 92.73 76.54 92.56 76.08 E 92.99 78.19 93.06 78.85 92.79 77.63 92.41 77.01 F 78.78 67.54 77.05 68.48 75.21 66.71 77.75 68.52 G_tC14 92.02 78.19 90.92 78.18 92.42 78.28 90.84 79.27 G-H_tC14 92.54 77.42 91.43 77.56 92.71 77.15 90.96 77.83 H_tC14 91.63 76.54 91.65 76.07 91.64 75.43 91.58 76.62 H-I_tC14 91.52 77.64 92.44 77.55 92.25 78.00 93.25 77.55 I_tC14 90.36 77.84 92.47 77.72 91.55 78.49 93.22 78.11 J 76.20 68.99 78.14 68.22 76.70 68.68 78.11 68.25 K 90.84 78.99 92.13 78.02 90.92 78.51 92.19 77.97 K-M 91.52 78.43 91.99 77.91 91.06 78.53 92.35 77.94 M 92.38 76.73 92.14 76.08 92.43 76.35 92.30 76.57 M-N 91.81 82.39 90.03 78.47 91.76 77.48 89.74 79.52 N 91.47 82.59 89.06 79.55 91.69 78.88 89.29 79.65 G_cC14 91.88 77.91 90.58 75.36 90.09 74.03 91.46 78.71 G-H_cC14 92.58 77.21 91.67 77.16 93.83 76.63 91.43 77.52 H_cC14 90.59 75.90 91.64 75.54 94.07 75.53 91.83 76.09 H-I_cC14 92.44 77.82 92.82 77.41 93.66 77.19 93.23 77.60 I_cC14 92.80 78.89 92.42 77.37 91.13 78.02 93.45 78.22
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Table A.9 A comparison between the molecular modelling G(complex) and G(Ru1) values of CytB precatalysts
Step ttCytB_a (%) ccCytB_a (%) ttCytB_b (%) ccCytB_b (%)
A 95.64 75.74 95.33 74.49 95.53 75.97 95.52 74.60 B 76.34 67.02 80.68 66.06 78.30 66.69 77.82 66.64 C 92.67 77.47 92.20 75.36 91.79 76.54 92.83 75.53 C-D 92.29 75.31 91.75 75.17 92.04 75.89 92.43 75.16 D 91.75 74.17 91.70 74.51 92.44 74.85 92.41 74.93 D-E 92.12 79.74 92.93 76.04 92.75 75.55 92.69 76.40 E 92.22 75.26 92.88 77.67 93.04 76.57 93.24 77.67 F 79.71 66.56 78.56 68.26 79.89 66.46 79.21 68.36 G_tC14 91.98 76.76 91.52 79.04 92.25 76.92 91.50 77.96 G-H_tC14 91.98 76.47 91.95 76.88 92.34 76.25 91.92 77.31 H_tC14 91.83 75.91 91.74 75.23 91.76 75.38 92.21 76.20 H-I_tC14 92.17 77.09 92.18 76.16 92.56 78.17 92.98 76.40 I_tC14 92.22 77.98 92.24 76.12 91.94 78.13 93.00 76.37 J 77.99 68.68 79.14 67.33 77.88 68.77 79.09 67.36 K 91.75 78.28 92.49 76.52 91.63 78.30 91.97 80.73 K-M 91.62 77.76 91.62 75.36 92.00 77.29 91.85 75.77 M 92.17 76.16 90.81 75.12 91.98 75.87 92.10 76.18 M-N 91.52 76.62 91.15 77.49 91.96 76.59 90.93 77.62 N 91.24 76.89 90.50 79.30 91.86 76.65 91.05 77.67 G_cC14 92.02 76.73 91.49 78.40 92.80 77.43 91.84 78.31 G-H_cC14 92.17 76.57 92.34 76.34 92.70 76.48 92.56 77.31 H_cC14 92.24 75.99 92.10 74.68 92.72 75.77 92.78 75.37 H-I_cC14 92.50 77.14 92.46 76.20 92.80 77.26 93.81 76.05 I_cC14 92.49 78.00 92.96 76.29 91.37 78.15 93.91 76.43
Appendix A: Molecular Modelling
Table A.10 A comparison between the molecular modelling G(complex) and G(Ru1) values of PhMe precatalysts
Step ttPhMe_a (%) ccPhMe_a (%) ttPhMe_b (%) ccPhMe_b (%)
A 91.89 78.83 91.80 76.40 91.89 78.84 91.82 76.40 B 73.68 67.60 76.19 67.21 75.16 67.72 75.85 67.61 C 89.89 79.27 89.52 77.98 89.08 78.24 90.43 77.96 C-D 88.75 76.74 88.34 76.51 88.63 76.89 88.97 76.65 D 87.85 75.61 88.43 75.64 88.14 76.04 88.31 75.71 D-E 90.56 77.27 91.05 77.49 89.74 76.90 90.58 77.59 E 91.79 78.62 91.48 79.77 90.60 78.04 91.69 79.80 F 75.63 67.87 74.51 68.80 75.05 67.86 74.61 68.85 G_tC14 87.51 73.81 89.08 79.87 88.40 78.43 88.75 80.44 G-H_tC14 88.51 78.17 88.61 78.29 88.51 78.05 88.13 78.32 H_tC14 87.83 77.08 87.63 76.79 87.71 76.88 87.61 76.95 H-I_tC14 90.33 78.55 89.12 77.91 90.58 78.60 89.88 77.91 I_tC14 90.84 80.49 88.36 76.99 89.26 79.33 89.66 74.70 J 73.29 69.16 74.69 68.24 73.42 69.17 74.76 68.29 K 89.84 80.34 87.72 78.29 88.90 80.35 85.64 78.07 K-M 89.69 78.87 88.78 78.23 90.13 78.90 89.10 78.22 M 88.19 77.13 87.70 76.84 88.41 77.20 87.64 77.03 M-N 87.61 78.13 87.96 78.67 87.56 78.10 87.48 78.65 N 88.37 79.04 87.34 80.70 87.83 78.37 87.42 80.00 G_cC14 88.32 74.72 88.58 80.06 88.34 78.23 87.52 75.84 G-H_cC14 88.41 78.02 88.61 77.96 88.73 77.94 89.84 80.28 H_cC14 88.33 76.73 87.01 76.22 88.62 76.40 88.79 76.68 H-I_cC14 90.61 78.48 89.40 77.98 91.08 77.99 91.08 77.84 I_cC14 91.18 79.89 88.25 77.68 90.26 79.12 91.30 78.00
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Table A.11 A comparison between the molecular modelling G(complex) and G(Ru1) values of PhiP precatalysts
Step ttPhiP_a (%) ccPhiP_a (%) ttPhiP_b (%) ccPhiP_b (%)
A 92.77 78.91 93.49 76.45 92.98 78.91 93.36 76.28 B 74.25 67.68 78.38 67.09 75.27 67.72 77.58 67.34 C 90.35 79.32 91.71 77.92 88.38 78.13 90.96 78.21 C-D 89.97 76.74 90.51 76.37 89.05 76.82 91.08 76.54 D 89.64 75.43 89.99 75.43 89.93 75.29 88.59 75.28 D-E 91.45 77.08 91.57 77.44 91.60 76.82 91.19 77.69 E 92.20 78.55 92.08 79.77 92.11 78.59 89.46 79.05 F 76.87 67.67 75.24 68.85 77.00 67.73 76.52 69.02 G_tC14 92.14 78.69 89.56 79.83 91.86 78.48 89.61 80.16 G-H_tC14 90.78 78.09 89.23 78.24 90.91 77.93 89.24 78.23 H_tC14 88.60 77.01 89.21 76.78 90.10 76.95 89.26 77.13 H-I_tC14 91.06 78.63 91.65 77.67 91.14 78.63 91.99 77.84 I_tC14 90.76 80.28 89.16 77.52 91.37 79.64 90.44 77.25 J 74.07 69.14 76.30 68.23 74.17 69.16 76.29 68.21 K 88.17 79.81 89.61 78.39 88.03 79.70 89.92 79.02 K-M 90.25 78.87 91.26 77.96 90.69 78.94 91.37 78.06 M 89.29 77.29 89.26 76.79 89.95 77.14 89.26 77.13 M-N 90.21 78.06 87.73 79.48 90.52 77.95 88.43 78.76 N 90.58 83.23 87.80 80.74 90.54 83.10 88.54 79.92 G_cC14 90.92 78.11 87.44 75.67 91.62 78.29 89.07 79.76 G-H_cC14 90.72 77.78 89.42 77.79 91.05 77.96 89.17 78.09 H_cC14 89.84 76.80 87.06 75.68 90.44 77.04 89.57 76.39 H-I_cC14 91.09 78.46 91.81 77.92 91.64 78.00 92.08 77.85 I_cC14 91.73 79.66 91.13 74.18 91.77 79.47 90.91 78.23
Appendix A: Molecular Modelling
Table A.12 A comparison between the molecular modelling G(complex) and G(Ru1) values of PhtB precatalysts
Step ttPhtB_a (%) ccPhtB_a (%) ttPhtB_b (%) ccPhtB_b (%)
A 93.50 77.69 94.02 74.48 93.46 77.79 94.08 74.66 B 77.57 65.36 79.79 66.41 76.38 67.09 78.91 66.10 C 92.07 79.03 91.44 75.65 91.91 78.60 92.30 75.75 C-D 91.19 76.36 91.36 75.84 91.08 76.75 92.09 75.90 D 91.17 75.14 91.32 75.21 91.10 75.56 91.12 75.43 D-E 92.31 75.96 92.14 77.12 92.21 75.83 91.66 77.28 E 92.18 76.05 92.39 79.51 92.54 76.17 92.41 79.12 F 79.20 67.30 75.99 68.62 78.48 66.67 75.71 67.59 G_tC14 92.17 77.30 90.87 79.42 92.05 77.54 90.78 79.49 G-H_tC14 92.05 77.45 91.60 78.00 91.91 77.12 91.15 78.14 H_tC14 91.58 76.82 91.16 76.39 91.30 76.40 90.54 76.57 H-I_tC14 91.74 78.26 91.76 76.80 92.11 77.83 92.18 76.79 I_tC14 91.91 79.77 91.80 76.49 92.06 78.78 92.14 77.19 J 75.55 69.09 78.48 67.82 75.43 69.04 78.45 67.83 K 88.84 79.14 91.37 77.62 91.12 80.00 91.55 77.60 K-M 91.20 78.97 91.75 76.69 91.77 78.81 92.24 76.90 M 91.21 77.03 91.28 75.97 91.71 76.80 90.96 77.11 M-N 90.91 77.36 91.26 78.21 91.43 77.28 90.01 78.63 N 90.87 77.93 91.16 78.54 91.13 77.38 90.12 78.93 G_cC14 91.43 73.72 92.10 78.35 91.78 74.15 89.05 78.73 G-H_cC14 92.04 77.39 91.92 77.74 92.05 76.98 91.00 78.14 H_cC14 91.76 76.74 91.28 76.20 91.56 76.06 90.55 77.04 H-I_cC14 91.79 78.20 92.09 77.00 92.59 77.78 93.16 76.75 I_cC14 92.41 79.25 92.11 76.79 92.79 79.29 93.62 76.48
Appendix A: Molecular Modelling
136
Table A.13 A comparison between the molecular modelling G(complex) values of Grubbs1, Grubbs 2 and the average calculated for Phobcat and the new Cy-R and Ph-R precatalysts
Step A1
(%)
A2 (%)
Phobcatave CyMe (%) CyiP ave (%) CytB ave (%) PhMe ave (%) PhiP ave (%) PhtB ave (%) ave (%) A 94.31 95.12 93.66 93.42 94.60 95.51 91.85 93.15 93.77 B 78.87 80.22 76.84 76.66 78.18 78.29 75.22 76.37 78.16 C 91.68 93.27 91.31 90.83 92.08 92.37 89.73 90.35 91.93 C-D 90.92 93.48 91.50 90.50 91.97 92.13 88.67 90.15 91.43 D 89.31 93.30 91.01 90.67 92.04 92.08 88.18 89.54 91.18 D-E 91.21 93.28 92.60 92.23 92.76 92.62 90.48 91.45 92.08 E 92.32 93.40 91.78 92.52 92.81 92.85 91.39 91.46 92.38 F 76.73 78.93 74.96 77.41 77.20 79.34 74.95 76.41 77.35 G_tC14 91.43 91.99 89.26 89.86 91.55 91.81 88.44 90.79 91.47 G-H_tC14 90.33 93.18 89.89 90.43 91.91 92.05 88.44 90.04 91.68 H_tC14 88.91 92.70 89.80 90.39 91.63 91.89 87.70 89.29 91.15 H-I_tC14 90.94 94.29 91.23 91.06 92.37 92.47 89.98 91.46 91.95 I_tC14 90.78 93.88 91.14 91.25 91.90 92.35 89.53 90.43 91.98 J 77.16 79.31 75.09 76.11 77.29 78.53 74.04 75.21 76.98 K 91.17 92.42 91.08 90.19 91.52 91.96 88.03 88.93 90.72 K-M 91.80 92.68 91.09 90.62 91.73 91.77 89.43 90.89 91.74 M 88.99 93.32 90.22 90.58 92.31 91.77 87.99 89.44 91.29 M-N 90.20 92.65 88.90 89.26 90.84 91.39 87.65 89.22 90.90 N 89.82 91.57 88.48 89.04 90.38 91.16 87.74 89.37 90.82 G_cC14 89.88 93.95 88.96 90.00 91.00 92.04 88.19 89.76 91.09 G-H_cC14 90.23 93.46 91.20 90.69 92.38 92.44 88.90 90.09 91.75 H_cC14 88.94 93.50 91.20 90.42 92.03 92.46 88.19 89.23 91.29 H-I_cC14 90.96 94.39 92.46 91.08 93.04 92.89 90.54 91.66 92.41 I_cC14 90.38 92.12 92.34 91.12 92.45 92.68 90.25 91.39 92.73
Appendix A: Molecular Modelling
Table A.14 A comparison between the molecular modelling G(Ru1) values of Grubbs1, Grubbs 2 and the average calculated for Phobcat and the new Cy-R and Ph-R precatalysts
Step A1
(%)
A2 (%)
Phobcatave CyMe (%) CyiP ave (%) CytB ave (%) PhMe ave (%) PhiP ave (%) PhtB ave (%) ave (%) A 75.71 74.87 76.94 76.40 76.67 75.20 77.62 77.64 76.16 B 66.77 65.42 67.15 67.11 69.33 66.60 67.54 67.46 66.24 C 76.25 75.67 77.27 77.82 77.53 76.23 78.36 78.40 77.26 C-D 75.29 75.00 75.91 76.22 76.16 75.38 76.70 76.62 76.21 D 73.97 74.49 74.97 75.17 75.07 74.62 75.75 75.36 75.34 D-E 75.54 75.87 76.59 76.77 76.56 76.93 77.31 77.26 76.55 E 78.01 76.93 78.53 78.39 77.92 76.79 79.06 78.99 77.71 F 67.19 66.88 67.58 68.27 67.81 67.41 68.35 68.32 67.55 G_tC14 78.56 77.17 78.83 78.63 78.48 77.67 78.14 79.29 78.44 G-H_tC14 76.72 76.77 77.55 77.62 77.49 76.73 78.21 78.12 77.68 H_tC14 75.36 75.61 76.05 76.39 76.17 75.68 76.93 76.97 76.55 H-I_tC14 76.81 76.77 77.78 77.74 77.69 76.96 78.24 78.19 77.42 I_tC14 74.05 77.69 78.79 78.69 78.04 77.15 77.88 78.67 78.06 J 68.26 67.72 68.53 68.66 68.54 68.04 68.72 68.69 68.45 K 73.89 76.50 77.79 78.63 78.37 78.46 79.26 79.23 78.59 K-M 77.30 76.41 77.89 78.17 78.20 76.55 78.56 78.46 77.84 M 75.42 75.64 75.92 76.44 76.43 75.83 77.05 77.09 76.73 M-N 77.03 76.53 77.79 78.06 79.47 77.08 78.39 78.56 77.87 N 79.06 75.70 78.17 78.73 80.17 77.63 79.53 81.75 78.20 G_cC14 74.57 78.05 77.84 75.85 76.50 77.72 77.21 77.96 76.24 G-H_cC14 76.58 76.72 76.71 77.26 77.13 76.68 78.55 77.91 77.56 H_cC14 75.42 75.70 75.38 75.85 75.77 75.45 76.51 76.48 76.51 H-I_cC14 76.89 76.73 77.06 77.69 77.51 76.66 78.07 78.06 77.43 I_cC14 77.16 76.72 78.18 78.16 78.13 77.22 78.67 77.89 77.95
Appendix B: Spectra
B.1 Infrared spectra
Appendix B: Spectra
140 Figure B.2 Infrared spectrum of 111.
Appendix B: Spectra
Appendix B: Spectra
142 Figure B.4 Infrared spectrum of 112.
Appendix B: Spectra
Appendix B: Spectra
144 Figure B.6 Infrared spectrum of 119.
Appendix B: Spectra
Appendix B: Spectra
146
B.2 Mass spectra
Appendix B: Spectra
Appendix B: Spectra
148 Figure B.10 GC-MS-EI-spectrum of 127: m/z 110 [M+].
Appendix B: Spectra
Appendix B: Spectra
150 Figure B.12 GC-MS-EI-spectrum of 109: m/z 164 [M+].
Appendix B: Spectra
Appendix B: Spectra
152 Figure B.14 GC-MS-EI-spectrum of 116: m/z 190 [M+].
Appendix B: Spectra
Appendix B: Spectra
154 Figure B.16 GC-MS-EI-spectrum of 129: m/z 194 [M+].
Appendix B: Spectra
Appendix B: Spectra
156 Figure B.18 GC-MS-EI-spectrum of 111: m/z 200 [M+].
Appendix B: Spectra
Appendix B: Spectra
158
Appendix B: Spectra
Appendix B: Spectra
160
Appendix B: Spectra
Appendix B: Spectra
162 Figure B.24 GC-MS-EI-spectrum of 124: m/z 110 [M+].
Appendix B: Spectra
Appendix B: Spectra
164
B.3 Nuclear Magnetic Resonance Spectra
Appendix B: Spectra
Appendix B: Spectra
166 Figure B.28 DEPT 135 (CDCl3) spectrum of 110.
Appendix B: Spectra
Appendix B: Spectra
168 Figure B.30 HSQC (CDCl3) spectrum of 110.
Appendix B: Spectra
Appendix B: Spectra
170
Appendix B: Spectra
Appendix B: Spectra
172 Figure B.34 COSY (CDCl3) spectrum of 111.
Appendix B: Spectra
Appendix B: Spectra
174
Appendix B: Spectra
Appendix B: Spectra
176 Figure B.38 DEPT 135 (CDCl3) spectrum of 118.
Appendix B: Spectra
Appendix B: Spectra
178 Figure B.40 HSQC (CDCl3) spectrum of 118.
Appendix B: Spectra
Appendix B: Spectra
180
Appendix B: Spectra
Appendix B: Spectra
182 Figure B.44 COSY (CDCl3) spectrum of 112.
Appendix B: Spectra
Appendix B: Spectra
184
Appendix B: Spectra
Appendix B: Spectra
186 Figure B.48 DEPT 135 (CDCl3) spectrum of 113.
Appendix B: Spectra
Appendix B: Spectra
188 Figure B.50 HSQC (CDCl3) spectrum of 113.
Appendix B: Spectra
Appendix B: Spectra
190
Appendix B: Spectra
Appendix B: Spectra
192 Figure B.54 COSY (CDCl3) spectrum of 119.
Appendix B: Spectra
Appendix B: Spectra
194
Appendix B: Spectra
Appendix B: Spectra
196 Figure B.58 DEPT 135 (CDCl3) spectrum of 121.
Appendix B: Spectra
Appendix B: Spectra
198 Figure B.60 COSY (CDCl3) spectrum of 121.
Appendix B: Spectra
