# _inorganics_
## 3 Materials and Methods
### Syntheses and Characterisation  
[Ru[n\({}^{1}\)-\(N\):\(\pi^{2}\)-\(P\),C-P(pz\({}^{\rm Me2}\))=CH(SiMe\({}_{2}\)Tol)](CO)(PPh\({}_{3}\))\({}_{2}\)] (**3c**): In a representative procedure, following literature precedent for compounds **3a** and **3b**[29; 30], HpzMe2 (12.7 mg, 0.13 mmol) as solution in THF was treated, at ambient temperature, with a single equivalence of \({}^{n}\)BuLi (0.06 cm\({}^{3}\), 2.5 M in hexanes) and the mixture stirred for 5 min. The resulting solution was added directly to a solution of [Ru[P=CH(SiMe\({}_{2}\)Tol)]Cl(CO)(PPh\({}_{3}\))\({}_{2}\)] (**1c**, 67 mg, 0.08 mmol) at ambient temperature and the mixture stirred for 1h. Volatiles were removed under reduced pressure, then the residue extracted with CH\({}_{2}\)Cl\({}_{2}\) and the resulting solution filtered; the solvent was removed under reduced pressure and the resulting solid dried in vacuo, before being redissolved in CDCl\({}_{3}\) for spectroscopic analysis. \({}^{1}\)H NMR (CDCl\({}_{3}\)): \(\delta_{\rm H}\) 0.06 (s, 3H, SiMe\({}_{2}\)), 0.15 (s, 3H, SiMe\({}_{2}\)), 0.42 (s, 3H, Pz*-Me), 1.75 (m, 1H, CHSi (\({}^{1}\)J\({}_{\rm C-H}\) = 135.31 Hz), 1.95 (s, 3H, Pz*-Me), 2.34 (s, 3H, CH\({}_{3}\)), 5.04 (s, 1H, Pz*-H4), 7.08-7.42 (m, 35H, Ar-H). \({}^{13}\)C\({}^{[1}\)H NMR (CDCl\({}_{3}\)): \(\delta_{\rm C}\) \(-\) 0.9 (d, \({}^{3}\)J\({}_{\rm C-P}\) = 7.6 Hz, SiCH\({}_{3}\)), 0.16 (d, \({}^{3}\)J\({}_{\rm C-P}\) = 8.5 Hz, SiCH\({}_{3}\)), 9.6 (d, \({}^{3}\)J\({}_{\rm C-P}\) = 5.3 Hz, Pz-CH\({}_{3}\)), 11.9 (s, Pz-CH\({}_{3}\)), 21.6 (s, CH\({}_{3}\)), 41.8 (ddd, \(J\)\({}_{\rm C-P}\) = 4.5, 31.3, 78.6 Hz, CHSi (\({}^{1}\)J\({}_{\rm C-H}\) = 136.3 Hz)), 105.0 (d, \(J\)\({}_{\rm C-P}\) = 2.7 Hz, Pz*-C4), 127.6 (d, \(J\)\({}_{\rm C-P}\) = 8.87 Ha, Ar-C), 127.8 (d, \(J\)\({}_{\rm C-P}\) = 8.87 Hz, ArC), 128.2 (s, ArC), 128.6 (m, ArC), 128.9 (d, \(J\)\({}_{\rm C-P}\) = 6.7 Hz, ArC), 130.4 (d, \(J\)\({}_{\rm C-P}\) = 13.0 Hz, ArC), 133.6-134.4 (m, ArC), 137.4 (s, ArC), 138.2 (d, \(J\)\({}_{\rm C-P}\) = 30.7 Hz, ArC), 138.4 (d, \(J\)\({}_{\rm C-P}\) = 31.8 Hz, ArC), 145.2 (s, Pz*-C5), 152.4 (s, Pz*-C3), 209.5 (br, CO). \({}^{31}\)P[\({}^{1}\)H] NMR (CDCl\({}_{3}\)): \(\delta_{\rm P}\) 46.7 (d, \(J\)\({}_{\rm P-P}\) = 16.9 Hz), 39.1 (dd, \(J\)\({}_{\rm P-P}\) = 50.1, 16.7 Hz), 32.6 (d, \(J\)\({}_{\rm P-P}\) = 50.4 Hz, P=C). \({}^{29}\)Si[\({}^{1}\)H] NMR (CDCl\({}_{3}\)): \(\delta_{\rm Si}\) - 5.3. [Ru[n\({}^{1}\)-\(N\):\(\pi^{2}\)-\(P\),C-P(pz\({}^{\rm Me2}\))=CH(SiMe\({}_{2}\)C\({}_{6}\)H\({}_{4}\)CF\({}_{3}\)-\(p\))](CO)(PPh\({}_{3}\))\({}_{2}\)] (**3d**): In comparable fashion to **3c**, from the respective phosphaalkenyl **(**1d**). \({}^{1}\)H NMR (CDCl\({}_{3}\)): \(\delta_{\rm H}\) \(-\)0.02 (s, 3H, SiCH\({}_{3}\)), 0.18 (s, 3H, SiCH\({}_{3}\)), 0.42 (s, 3H, Pz*-Me), 1.66 (m, 1H, CHSi (\({}^{1}\)J\({}_{\rm C-H}\) = 135.3 Hz), 1.95 (s, 3H, Pz*-Me), 5.07 (s, 1H, Pz*-H4), 7.09-7.34 (m, 35H, Ar-H), 7.45-7.56 (m, 4H, C\({}_{6}\)H\({}_{4}\)CF\({}_{3}\)). \({}^{19}\)F NMR (CDCl\({}_{3}\)): \(\delta_{\rm F}\) \(-\)63.06 (s). \({}^{13}\)C[\({}^{1}\)H] NMR (CDCl\({}_{3}\)): \(\delta_{\rm C}\) \(-\) 1.3 (d, \({}^{3}\)J\({}_{\rm C-P}\) = 8 Hz, SiCH\({}_{3}\)), 0.3 (d, \({}^{3}\)J\({}_{\rm C-P}\) = 8 Hz, SiCH\({}_{3}\)), 9.6 (d, \({}^{3}\)J\({}_{\rm C-P}\) = 5.3 Hz, Pz-CH\({}_{3}\)), 11.9 (s, Pz-CH\({}_{3}\)), 39.8 (br. (\({}^{1}\)J\({}_{\rm C-H}\) = 135.3 Hz) CHSi), 105.2 (d, \(J\)\({}_{\rm C-P}\) = 2.9 Hz, Pz*C4), 123.8 (q, \({}^{2}\)J\({}_{\rm C-F}\) = 3.9 Hz, CCF\({}_{3}\)), 130.9 (q, \({}^{1}\)J\({}_{\rm C-F}\) = 240.0 Hz, CF\({}_{3}\)), 127.6-129.1, 134.1-135.5, 137.2-138.1 (3 \(\times\) m, PPh\({}_{3}\), C\({}_{6}\)H\({}_{4}\)), 145.3 (d, \({}^{2}\)J\({}_{\rm C-P}\) = 1.5 Hz, Pz*-C5), 152.7 (s, Pz*-C3), 209.7 (br, CO). \({}^{31}\)P[\({}^{1}\)H] NMR (CDCl\({}_{3}\)): \(\delta_{\rm P}\) 46.6 (d, \({}^{2}\)J\({}_{\rm P-P}\) = 16.2 Hz, PPh\({}_{3}\)), 38.6 (dd, \({}^{2}\)J\({}_{\rm P-P}\) = 54.4, 16.2 Hz, PPh\({}_{3}\)), 32.1 (d, \({}^{2}\)J\({}_{\rm P-P}\) = 51.4 Hz, P=C).