Theoretical study of the influence of solvent polarity on the 31P and 13C NMR parameters of the Ru(PH3)4(η2-benzyne) complex

Abstract

In this study, using the wB97XD method, quantum chemical calculations were used to analyze the effect of solvent on 31P and 13C NMR parameters of the Ru(PH3)4(η2-benzyne) complex. The solvent effects were examined using the self-consistent reaction field theory (SCRF) based on the Polarizable Continuum Model (PCM). The stability of this complex was studied in the singlet and triplet states. The 31P and 13C NMR chemical shifts of the complex were calculated for both gas and solution phases. One-bond nuclear spin–spin coupling constants of RhC and RuP bonds as well as two-bond nuclear spin–spin coupling constants of P⋯P were estimated. The correlations of these parameters and solvent polarity functions including both the dielectric constant (ε) and refractive index (nD) of the liquid medium were explored further. In addition, the most significant Ramsey terms involved significantly in 1J(RuP), 1J(RuC) and 2J(P⋯P) values were determined. Finally, the correlations between 1J(RuP), 1J(RuC) and the APT net charge on the Ru atom were studied.