# _inorganics_
## 3 Materials and Methods  
### General Methods  
All manipulations were performed under anaerobic conditions using standard Schlenk line and glovebox (MBraun, Germany) techniques, working under an atmosphere of dry argon or dinitrogen respectively. Solvents were distilled from appropriate drying agents and stored over either molecular sieves (4 A, for DCM and THF) or potassium mirrors. General reagents were obtained from Sigma-Aldrich (Gillingham, UK) or Fisher Scientific (Loughborough, UK) and purified by appropriate methods before use, precious metal salts were obtained from STREM (Cambridge, UK). [RuHCl(CO)(PPh\({}_{3}\))\({}_{3}\)] [51], RMe\({}_{2}\)SiCH\({}_{2}\)PCL\({}_{2}\) (R = Me, Ph [52], Tol [29], C\({}_{6}\)H\({}_{4}\)CF\({}_{3}\)[39]), RMe\({}_{2}\)SiC=P [29; 30; 40] and [Ru[P=CH(SiMe\({}_{2}\)R)]Cl(CO)(PPh\({}_{3}\))\({}_{2}\)] (R = Me [29; 30], Ph [29], Tol, C\({}_{6}\)H\({}_{4}\)CF\({}_{3}\)\(\cdot\)\(p\)[40]) were prepared as previously described. Unless otherwise stated, NMR spectra were recorded at 303 K on a Varian VNMRS 400 (\({}^{1}\)H 399.50 MHz, \({}^{13}\)C 100.46 MHz, \({}^{19}\)F 375.87, \({}^{31}\)P 161.71 MHz, \({}^{29}\)Si 79.37 MHz) spectrometer (Varian, Yarnton, UK). All spectra are referenced to external Me\({}_{4}\)Si, 85% H\({}_{3}\)PO\({}_{4}\) or CFCl\({}_{3}\) as appropriate. Carbon-13 spectra were assigned by recourse to the 2D (HSQC, HMBC) spectra; phosphaalkenic proton and silicon shifts were determined indirectly by \({}^{1}\)H-\({}^{31}\)P and \({}^{1}\)H-\({}^{29}\)Si correlation (HMBC). Elemental analyses were obtained by Mr. [PERSON] of the London Metropolitan University Elemental Analysis Service.  
\begin{table}
\begin{tabular}{c c c c c c} \hline \hline \multicolumn{1}{c}{**Compound**} & & \multicolumn{2}{c}{\(\delta\)**p\({}^{1}\)**} & \multicolumn{2}{c}{\(\delta\)**c\({}^{2}\)**} & \multicolumn{2}{c}{\(\delta\)**H\({}^{2}\)**} \\  & & **R** & **P=C** & **PPh\({}_{3}\)** & **P=C** & **P=CH(\({}^{1}\))/Hz\({}^{3}\)** \\ \hline
**2\({}^{4}\)** & **2a** & Me & 58.7 & 46.6, 42.0 & 45.1 & 1.59 (137) \\ (pz\({}^{\prime}\) = pz) & **2b** & Ph & 57.0 & 47.0, 41.7 & 42.6 & 1.72 (135) \\
**3** & **3a** & Me\({}^{4}\) & 32.9 & 46.6, 39.2 & 44.9 & 1.62 (123) \\ (pz\({}^{\prime}\) = pzMe2) & **3b** & Ph\({}^{4}\) & 32.3 & 47.0, 38.9 & 41.8 & 1.77 (128) \\  & **3c** & C\({}_{6}\)H\({}_{4}\)Me-\(p\)\({}^{5}\) & 32.6 & 46.7, 39.1 & 41.8 & 1.75 (136) \\  & **3d** & C\({}_{6}\)H\({}_{4}\)CF\({}_{3}\)-\(p\)\({}^{5}\) & 32.1 & 46.6, 38.6 & 39.8 & 1.66 (135) \\
**4\({}^{5}\)** & **4a** & Me & 76.6 & 47.7, 41.5 & 47.1 & 1.78 (136) \\ (pz\({}^{\prime}\) = pzC\({}^{\prime 33}\)) & **4b** & Ph & 74.9 & 48.0, 41.3 & 46.7 & 1.91 (136) \\  & **4c** & C\({}_{6}\)H\({}_{4}\)Me-\(p\) & 75.0 & 47.9, 41.3 & 45.4 & 1.90 (134) \\  & **4d** & C\({}_{6}\)H\({}_{4}\)CF\({}_{3}\)-\(p\) & 73.8 & 47.8, 40.9 & 43.8 & 1.82 (134) \\
**5\({}^{5}\)** & **5a** & Me & 64.6 & 46.9, 38.4 & 45.2 & 1.76 (129) \\ (pz\({}^{\prime}\) = pzMeC\({}^{\prime 33}\)) & **5b** & Ph & 62.7 & 47.2, 38.3 & 41.8 & 1.97 (131) \\  & **5c** & C\({}_{6}\)H\({}_{4}\)Me-\(p\) & 61.6 & 47.2, 38.4 & 42.1 & 1.97 (135) \\  & **5d** & C\({}_{6}\)H\({}_{4}\)CF\({}_{3}\)-\(p\) & 62.0 & 47.1, 37.8 & 40.7 & 1.85 (133) \\
**6\({}^{5}\)** & **6a** & Me & 64.4 & 47.4, 41.8 & 47.5 & 1.74 (137) \\ (pz\({}^{\prime}\) = pz\({}^{\prime 3}\)) & **6d** & C\({}_{6}\)H\({}_{4}\)CF\({}_{3}\)-\(p\) & 60.5 & 47.7, 41.3 & 43.7 & 1.78 (136) \\ \hline \hline \end{tabular} \({}^{1}\) Referenced to 85% H\({}_{3}\)PO\({}_{4}\); \({}^{2}\) Referenced to SiMe\({}_{2}\); \({}^{3}\) Measured from coupled \({}^{1}\)H–\({}^{13}\)C HSQC spectra; \({}^{4}\) Recorded as solutions in CDC\({}_{2}\)Cl\({}_{2}\); \({}^{5}\) Recorded as solutions in CDC\({}_{3}\).  
\end{table}
Table 1: NMR Spectroscopic data for [RuI\(\eta\)1–\(N\):\(\eta\)2–\(PC\)-P(pz\({}^{\prime}\))=CH(SiMe\({}_{2}\)R)Cl(CO)(PPh\({}_{3}\))\({}_{2}\)].