97932-51-9Relevant academic research and scientific papers
Photochemistry of Ru(etp)(CO)H2 (etp = PhP(CH2CH 2PPh2)2): Fast oxidative addition and coordination following exclusive dihydrogen loss
Montiel-Palma, Virginia,Pattison, David I.,Perutz, Robin N.,Turner, Claire
, p. 4034 - 4039 (2004)
The photochemistry of Ru(etp)(CO)H2 (1, etp = PhP(CH 2CH2PPh2)2) has been studied by UV/vis spectroscopy following nanosecond laser flash photolysis and by NMR and IR spectroscopy following steady-state irradiation. Steady-state irradiation under CO, C2H4, and Et3SiH yields Ru(etp)(CO)2 Ru(etp)(CO)(C2H4), and Ru(etp)(CO)(SiEt3)H, respectively. Laser flash photolysis (laser wavelength 308 nm) of 1 in cyclohexane generates the 16-electron transient Ru(etp)(CO). In the absence of additional ligands, Ru(etp)(CO) decays by reaction with photoejected dihydrogen, regenerating 1. When flash photolysis was performed in the presence of added ligands, the transient decays by pseudo-first-order kinetics with second-order rate constants on the order of 108 dm3 mol-1 s-1. However, the fastest reaction rate (H2) is only a factor of ca. 4 greater than the slowest (Et3SiH). Activation parameters for the reaction of 1 with Et3SiH were determined as ΔG298? = 25.7 ± 0.1 kJ mol-1, ΔH? = 11 ± 1 kJ mol -1, and ΔS? = -49 ± 4 J mol-1 K -1. The evidence from the UV/vis spectrum of the transient and from the structures of the stable photoproducts indicates that Ru(etp)(CO) adopts a nonplanar geometry.
