P-CH3-RU HEAT ABSOBTION
The decomposition of P (CH3) absorbed on RU can be seen X-ray using synchrotron radiation (Wang et al. 2015). Using the chemical shifts in the P 2p core levels, we get phosphorus containing surface reactions. On RU P (CH3)3 breaks to P (CH3)2 then P (CH3) then P when heated
PCL3 also undergoes the same reaction that is PCL3 then PCL2 then PCL then P.
These decompositions are estimated using the bond order conversion Morse potential (BOCMP)
From the experimental data, we see that they agree.
P (CH3)3 decomposes at around 79K- 450K while PH3 is at 190K-700K. PCL3 is around 300K.
EXPERIMENT NMR RESULT
1H NMR (400 MHz, CDCl3) (d ppm): 3.25 (s, 3H, CH3 ), 3.66 (s, 3H, CH3 ), 3.95 (s, 3H, CH3), 4.61 (t, 2H,CH2, J =5.5Hz), 4.94 (t, 2H,CH2, J =5.5Hz), 6.97-7.16 (m, 2H, PH), 7.36-7.65 (m, 3H, PH), 7.67 (m, 2H, PH), 10.07 ( s, 1H, P).
13C NMR (400 MHz, CDCl3) (d ppm): 10.0, 14.4, 22.3, 24.2, 30.9 ,34.6. 42.7, 50.1, 76.8, 77.1, 77.4, 81.5., 97.3., 120.8, 121.9.0, 126,3, 129.0 129.5, 132.2140.5 , 143.2, 153.6,.
P(CH3)3 undergoes a series of demethylation steps as it decomposes to form P. Using the BOCMP tables we can estimate the heat absorption. Binding energy of phosphorus is estimated using the Born –Haber cycle. From the tables the estimated heat of molecular absorption for P(CH3)3 is 166 KJ/ mol. This implies that P(CH3)3 will dissociate upon absorption on Ru if the activation barriers for decomposition are small.
Applying SXPS using synchrotron radiation to study P(CH3)3 has played a major role in understanding its chemistry. The chemical shifts have been analyzed in the P 2p core levels for easy analyzing.
Wang, L., Zhang, T., Li, P., Huang, W., Tang, J., Wang, P., & Zhang, K. (2015). Use of synchrotron radiation-analytical techniques to reveal chemical origin of silver-nanoparticle cytotoxicity. ACS nano, 9(6), 6532-6547.
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