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Hurd, Joseph
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article
31P Nuclear Magnetic Resonance Spectroscopy as a Probe of Thorium–Phosphorus Bond Covalency: Correlating Phosphorus Chemical Shift to Metal–Phosphorus Bond Order
Abstract
We report the use of solution and solid-state <sup>31</sup>P Nuclear Magnetic Resonance (NMR) spectroscopy combined with Density Functional Theory calculations to benchmark the covalency of actinide-phosphorus bonds, thus introducing <sup>31</sup>P NMR spectroscopy to the investigation of molecular f-element chemical bond covalency. The <sup>31</sup>P NMR data for [Th(PH<sub>2</sub>)(Tren<sup>TIPS</sup>)] (<b>1</b>, Tren<sup>TIPS</sup> = {N(CH<sub>2</sub>CH<sub>2</sub>NSiPr<sup>i</sup><sub>3</sub>)<sub>3</sub>}<sup>3–</sup>), [Th(PH)(Tren<sup>TIPS</sup>)][Na(12C4)<sub>2</sub>] (<b>2</b>, 12C4 = 12-crown-4 ether), [{Th(Tren<sup>TIPS</sup>)}<sub>2</sub>(μ-PH)] (<b>3</b>), and [{Th(Tren<sup>TIPS</sup>)}<sub>2</sub>(μ-P)][Na(12C4)<sub>2</sub>] (<b>4</b>) demonstrate a chemical shift anisotropy (CSA) ordering of (μ-P)<sup>3–</sup> > (═PH)<sup>2–</sup> > (μ-PH)<sup>2– </sup>> (−PH<sub>2</sub>)<sup>1–</sup> and for <b>4 </b>the largest CSA for any bridging phosphido unit. The B3LYP functional with 50% Hartree–Fock mixing produced spin–orbit δiso values that closely match the experimental data, providing experimentally benchmarked quantification of the nature and extent of covalency in the Th–P linkages in <b>1–4</b> via Natural Bond Orbital and Natural Localized Molecular Orbital analyses. Shielding analysis revealed that the <sup>31</sup>P δ<sub>iso</sub> values are essentially only due to the nature of the Th–P bonds in <b>1–4</b>, with largely invariant diamagnetic but variable paramagnetic and spin–orbit shieldings that reflect the Th–P bond multiplicities and s-orbital mediated transmission of spin–orbit effects from Th to P. This study has permitted correlation of Th–P δ<sub>iso </sub>values to Mayer bond orders, revealing qualitative correlations generally, but which should be examined with respect to specific ancillary ligand families rather than generally to be quantitative, reflecting that <sup>31</sup>P δ<sub>iso </sub>values are a very sensitive reporter due to phosphorus being a soft donor that responds to the rest of the ligand field much more than stronger, harder donors like nitrogen.<br/><br/>