Métodos de determinación del radio de invasión y skin

Addition of KOtBu/MeOH to 34, synthesising compound G

To a stirring solution of 34 (0.151 g, 0.121 mmol) in DCM (5 cm3) was added KOtBu (0.058 g, 0.485 mmol) in MeOH (10 cm3) and the mixture stirred at ambient temperature for 1 h. Gradual formation of a bronze-coloured precipitate was observed. The mixture was filtered and the precipitate dried under reduced pressure. 1H NMR δH: 8.51 (dqnt, JHP = 20.8, 6.8 Hz).

13 C{1H} NMR (CD2Cl2) δC: 175.1. 31 P{1H} NMR (CD2Cl2) δP: 298.3 (qnt, JPP = 7.9 Hz), 52.1 (d, JPP = 7.9 Hz). Addition of [RuHCl(CO)(PPh3)3] to 40

[RuHCl(CO)(PPh3)3] (0.052 g, 0.055 mmol) and 40 (0.056 g, 0.055 mmol) were suspended in

THF (5 cm3) at ambient temperature and the mixture allowed to stir for 1 h. A gradual increase in solubility was observed over time. Solvent was removed under reduced pressure. No reaction was observed by 31P{1H} and 1H NMR spectroscopy, with only the presence of starting materials observed.

Addition of [Pd(PPh3)4] to 41

[Pd(PPh3)4] (0.112 g, 0.106 mmol) and 41 (0.110 g, 0.106 mmol) were suspended in THF (5

cm3) at ambient temperature and the mixture allowed to stir for 1.5 h. Solvent was removed under reduced pressure. No reaction was observed by 31P{1H} and 1H NMR spectroscopy, with only the presence of starting materials observed.

Addition of [Pt(PPh3)2(C2H4)] to 40

[Pt(PPh3)2(C2H4)] (0.036 g, 0.049 mmol) and 40 (0.050 g, 0.049 mmol) were suspended in THF

(5 cm3) at ambient temperature and the mixture allowed to stir for 1 h. Solvent was removed under reduced pressure. No reaction was observed by 31P{1H} and 1H NMR spectroscopy, with only the presence of starting materials observed.

Addition of [PdCl(C3H5)]2 to 40

[Pt(PPh3)2(C2H4)] (0.021 g, 0.057 mmol) and 40 (0.058 g, 0.057 mmol) were suspended in THF

(5 cm3) at ambient temperature and the mixture allowed to stir for 1 h. Solvent was removed under reduced pressure. An intractable mixture of products was observed by 31P{1H} and 1H NMR spectroscopy.

Addition of [AuCl(tht)] to 40

[AuCl(tht)] (0.010 g, 0.030 mmol) and 40 (0.030 g, 0.030 mmol) were suspended in toluene (5 cm3) at ambient temperature and the mixture allowed to stir for 20 h. Solvent was removed under reduced pressure. No reaction was observed by 31P{1H} and 1H NMR spectroscopy, with only the presence of starting materials observed.

Addition of [AuCl(PPh3)] to 41

Method A: [AuCl(PPh3)] (0.032 g, 0.065 mmol) and AgBF4 (0.013 g, 0.065 mmol) were

dissolved in THF (5 cm3) at ambient temperature and the solution stirred for 5 min. A solution of 41 (0.067 g, 0.065 mmol) in THF (5 cm3) was added and a gradual colour change to yellow/green then orange was observed over time. The mixture was stirred for 1 h and subsequently filtered. Solvent was removed under reduced pressure. An intractable mixture of products was observed by 31P{1H} and 1H NMR spectroscopy.

Method B: [AuCl(PPh3)] (0.039 g, 0.078 mmol) and AgBF4 (0.015 g, 0.078 mmol) were

dissolved in THF (5 cm3) at ambient temperature and the solution stirred for 5 min. The solution was cooled to −78 °C before addition of 41 (0.080 g, 0.078 mmol) in THF (5 cm3

) and a gradual colour change to orange/brown was observed over time, with formation of a white precipitate.

The mixture was allowed to warm to ambient temperature over 1 h. The mixture was filtered and solvent was removed under reduced pressure. An intractable mixture of products was observed by 31P{1H} and 1H NMR spectroscopy.

Addition of BF3·Et2O to 41

Method A: BF3·Et2O (0.013 cm 3

, 0.106 mmol) was added drop-wise to a stirring solution of 41 (0.110 g, 0.106 mml) in THF (5 cm3) at ambient temperature and the solution stirred for 1 h. A gradual colour change to dark orange was observed. Solvent was removed under reduced pressure. 31P{1H} NMR (CD2Cl2) δP: 212.6 (qnt, JPP = 10.2 Hz), 239.6 (qnt, JPP = 10.0 Hz), 52.1 (d, JPP = 10.0 Hz), 45.5 (d, JPP = 10.2 Hz). 11 B{1H} NMR (CD2Cl2) δB: 19.1, −1.1. 19 F NMR (CD2Cl2) δF: −76.6 (s), −76.5 (s). Method B: BF3·Et2O (0.008 cm 3

, 0.068 mmol) was added drop-wise to a stirring solution of 41 (0.070 g, 0.068 mmol) in THF (5 cm3) at −78 °C. The solution was allowed to warm to ambient temperature over 2 h with continual stirring. Solvent was removed under reduced pressure. Identical spectra were observed to that found for Method A.

Addition of BF3·Et2O to 45 BF3·Et2O (0.009 cm

3

, 0.075 mmol) was added drop-wise to a stirring solution of 45 (0.080 g, 0.075 mmol) in THF (5 cm3) at ambient temperature. The solution was stirred for 1 h with a colour change to dark red, then brown, observed over time. Solvent was removed under reduced pressure. An intractable mixture of products was observed by 31P{1H} and 1H NMR spectroscopy.

Addition of BCl3 to 41 BCl3 (0.12 cm

3

, 0.118 mmol) was added drop-wise to a stirring solution of 41 (0.122 g, 0.118 mmol) in THF (5 cm3) at ambient temperature and the solution stirred for 1 h. Solvent was removed under reduced pressure. An intractable mixture of products was observed by 31P{1H} and 1H NMR spectroscopy.

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