d6 metal systems for white phosphorus activation

From Phosphidic to Phosphonium? Umpolung of the P4‐Bonding Situation in [CpFe(CO)(L)(η1‐P4)]+ Cations (L=CO or PPh3)

“…The P 4 ligand itself showed two broad resonances at δ P =−329.4 and −501.4 due to the fluxional binding to the Fe center. In contrast, piano‐stool complexes of the type [Cp ( * ) M(L) 2 (P 4 )] + (M=Fe, Ru, or Os), and related octahedral complexes [Ru(dppm) 2 H(P 4 )] + and [Ru(dppe) 2 H(P 4 )] + , all show separate, well resolved 31 P NMR resonances for the metalated (between δ P =−299.5 and −380.4) and non‐metalated phosphorus atoms (between δ P =−492.5 and −480.2) in the P 4 tetrahedron . This observation is consistent with the slow exchange of phosphorus atoms on the NMR timescale.…”

Iodine Activation of Coordinated White Phosphorus: Formation and Transformation of 1,3‐Dihydride‐2‐iodidecyclotetraphosphane

“…[7,10,11] The 31 P{ 1 H} NMR spectrum of 4 (Figure 5), which fully correlates with a simulated ABA'B'FF'M spin system (Scheme 1 for atom labelling), confirms that the solid-state structure is maintained in solution. Inconsistent with the standard hydrolysis of 1, the hydrolytic degradation of the P 4 tetrahe-dron mediated by iodine does not include the formation of hydroxypolyphosphane species, [18] thus suggesting that a different hydrolytic mechanism might be operative.…”

Iodine Activation of Coordinated White Phosphorus: Formation and Transformation of 1,3‐Dihydride‐2‐iodidecyclotetraphosphane

“…10, 11 The 31 P{ 1 H} NMR spectrum of 4 (Figure 5), which fully correlates with a simulated ABA′B′FF′M spin system (Scheme for atom labelling), confirms that the solid‐state structure is maintained in solution. Inconsistent with the standard hydrolysis of 1 , the hydrolytic degradation of the P 4 tetrahedron mediated by iodine does not include the formation of hydroxypolyphosphane species,18 thus suggesting that a different hydrolytic mechanism might be operative.…”