31 P Chemical Shifts in Ru(II) Phosphine Complexes. A Computational Study of the Influence of the Coordination Sphere

Christophe Raynaud (1) , Eliott Norbert-Agaisse (1) , Brian R James (2) , Odile Eisenstein (1, 3)

1 ICGM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier
2 UBC Chemistry - Department of Chemistry [Vancouver]
3 Hylleraas - Hylleraas Centre for Quantum Molecular Sciences

NMR chemical shift has been the most versatile marker of chemical structures, by reflecting global and local electronic structures, and is very sensitive to any change within the chemical species. In this work, a set of Ru(II) complexes with the same five ligands and a variable 6 th ligand L (none, H2O, H2S, CH3SH, H2, N2, N2O, NO + , C=CHPh, and CO) is studied, using as the NMR reporter, the phosphorus PA of a coordinated bidentate PAN ligand (PAN = o-diphenylphosphino-N,N'dimethylaniline). The chemical shift of PA in RuCl2(PAN)(PR3)(L) (R = phenyl, p-tolyl or p-FC6H4) was shown to increase as the RuPA bond distance decreases, an observation that was not rationalized. This work, using density functional theory (DFT) calculations, reproduces reasonably well the observed 31 P chemical shifts for these complexes, and the correlation between the shifts and the RuPA bond distance as L varies. An interpretation of this correlation is proposed using a Natural Chemical Shift (NCS) analysis based on the Natural Bonding Orbital (NBO) method. This analysis of the principal components of the chemical shift tensors shows how the s-donating properties of L have a particularly high influence on the phosphine chemical shifts.

Domaines: Chimie de coordination

Christophe Raynaud, Eliott Norbert-Agaisse, Brian R James, Odile Eisenstein. 31 P Chemical Shifts in Ru(II) Phosphine Complexes. A Computational Study of the Influence of the Coordination Sphere. Inorganic Chemistry, 2020, 59 (23), pp.17038-17048. ⟨10.1021/acs.inorgchem.0c02256⟩. ⟨hal-03049747⟩