(P-Bis(pentafluorophenyl) substituted) PCP-pincer Ru(II) complexes: A theoretical study of the molecular structure and electronic properties

The differences between the molecular structures of the PCP-pincer complex [RuCl{C6H3(CH2P(C6H5)2)2-2,6}(PPh3)] ([RuCl(PCPH)(PPh3)], 1) and its tetrakis-pentafluorophenyl substituted analogue [RuCl{C6H3(CH2P(C6F5)2)2-2,6}(PPh3)] ([RuCl(PCPF20)(PPh3)], 2) have been rationalised by performing calculations on the cations [Ru(PCPH)(PPh3)]+ (1cat) and [Ru(PCPF20)(PPh3)]+ (2cat). The molecular interactions between the chloride ligand and the axial rings, as found in 1 and 2, respectively, have been studied computationally in the model systems [(C6X5PH2)2Cl−] (X = H, F). The calculations on 2cat show that in 2 it is most likely the attractive electrostatic interaction between the chloride ligand and the fluorinated phenyl rings that forces the Cipso atom to occupy an axial position rather than an equatorial one in the observed (X-ray of 2) square pyramidal arrangement. In 1, however, repulsive steric hindrance forces the PPh3 ligand to take the apical position. The applicability of the TD-DFT method for the calculation of the electronic spectra of the PCP-pincer compounds 1 and 2 has been tested. The results indicate that the excitation energies calculated for both complexes are in a reasonable agreement with the experimental absorption maxima. However, for 1, all the calculated transition energies are underestimated.

A theoretical study of the molecular structure of complex [RuCl{C6H3(CH2P(C6H5)2)2-2,6}(PPh3)] ([RuCl(PCPH)(PPh3)], 1) and its tetrakis-pentafluorophenyl substituted analogue [RuCl{C6H3(CH2P(C6F5)2)2-2,6}(PPh3)] ([RuCl(PCPF20)(PPh3)], 2) has been carried out to rationalise the observed structural changes observed in 2 compared to 1 upon replacement of C6H5- by C6F5-groups. The results of the calculations, performed on the models [(C6F5PH2)2Cl]− and [(C6H5PH2)2Cl]−, show that in complex 2 the chloride ligand interacts with the axial fluorinated phenyl rings. The spectroscopic features of both complexes have been interpreted with the TD-DFT method.Figure optionsDownload as PowerPoint slide