¹³C_carbene nuclear magnetic resonance chemical shift analysis confirms Ce^IVC double bonding in cerium(IV)–diphosphonioalkylidene complexes

Diphosphonioalkylidene dianions have emerged as highly effective ligands for lanthanide and actinide ions, and the resulting formal metal–carbon double bonds have challenged and developed conventional thinking about f-element bond multiplicity and covalency. However, f-element–diphosphonioalkylidene complexes can be represented by several resonance forms that render their metal–carbon double bond status unclear. Here, we report an experimentally-validated ¹³C Nuclear Magnetic Resonance computational assessment of two cerium(IV)–diphosphonioalkylidene complexes, [Ce(BIPM^TMS)(ODipp)₂] (1, BIPM^TMS = {C(PPh₂NSiMe₃)₂}²⁻; Dipp = 2,6-diisopropylphenyl) and [Ce(BIPM^TMS)₂] (2). Decomposing the experimental alkylidene chemical shifts into their corresponding calculated shielding (σ) tensor components verifies that these complexes exhibit CeC double bonds. Strong magnetic coupling of CeC σ/π* and π/σ* orbitals produces strongly deshielded σ₁₁ values, a characteristic hallmark of alkylidenes, and the largest ¹³C chemical shift tensor spans of any alkylidene complex to date (1, 801 ppm; 2, 810 ppm). In contrast, the phosphonium-substituent shielding contributions are much smaller than the CeC σ- and π-bond components. This study confirms significant Ce 4f-orbital contributions to the CeC bonding, provides further support for a previously proposed inverse-trans-influence in 2, and reveals variance in the 4f spin–orbit contributions that relate to the alkylidene hybridisation. This work thus confirms the metal–carbon double bond credentials of f-element–diphosphonioalkylidenes, providing quantified benchmarks for understanding diphosphonioalkylidene bonding generally.