Phospha neutral
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Summary
9 papers analyzed
These studies suggest that neutral phospha compounds and ligands offer advantages in synthetic methods, coordination chemistry, and catalysis, with potential applications in metal-organic frameworks, high-resolution measurements, and electrochemical cells.
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Neutral Tris(Azolyl)Phosphanes: Versatile Ligands in Coordination Chemistry
Neutral tris(azolyl)phosphanes have emerged as a significant class of ligands in coordination chemistry due to their advantageous synthetic methods and high yields compared to their methane and anionic borate analogues. These ligands, which incorporate nitrogen-containing five-membered azole rings, have been extensively studied for their synthesis, spectroscopic and structural characterization, and applications in metal complex formation. The growing body of research highlights their potential in developing new azolyl phosphane chemistry and their diverse applications in coordination chemistry.
Catalytic Phosphite Hydrolysis Under Neutral Conditions
Cationic phosphametallocene-based platinum(II) aqua complexes have been identified as efficient precatalysts for the hydrolysis of aromatic and aliphatic tertiary phosphites under neutral reaction conditions. This process, conducted at room temperature, selectively cleaves one P-O bond of the phosphite. NMR labeling experiments, stoichiometric model reactions, and density functional theory calculations have elucidated the catalytic cycle, which involves intramolecular water molecule transfer to the cis-coordinated phosphite molecule.
Neutral Phospha(III)Guanidines and Metallacyclobut-1-ene Rings
Neutral phospha(III)guanidine compounds, such as Ph2PC{NR}{NHR}, have been synthesized and characterized, revealing the presence of the Esyn isomer in solution and solid-state. These compounds react with M(CO)4(pip)2 (where M = Mo, W) to form complexes featuring 1-aza-3-phospha-4-metallacyclobut-1-ene rings. These structures represent the first structurally characterized examples of such rings, showcasing the unique coordination chemistry of neutral phospha(III)guanidines.
Hyperstrong Neutral Organic Bases: Phosphazeno Azacalix3Pyridines
Tris(phosphazeno)-substituted azacalix3pyridine compounds have been identified as hyperstrong neutral bases. Their gas-phase basicities and pKa values in acetonitrile are exceptionally high, attributed to strong bifurcated hydrogen bonds and substantial cationic resonance effects. These properties make them highly effective in various chemical applications requiring strong bases.
Metal Coordination of Neutral Open-Shell P-Ligands
Phosphanoxyl complexes, derived from low-coordinate phosphorus radicals, exhibit unique reactivity and electron delocalization properties. These complexes, particularly those involving tungsten(0) centers, have been studied for their thermal stability and spin density distributions. The reactivity of these complexes in radical polymerizations and their potential applications in coordination chemistry have been explored, highlighting the versatility of neutral open-shell P-ligands.
Cationic Phosphinidene as a Versatile P1 Building Block
Cationic imidazoliumyl(phosphonio)-phosphanides serve as [LC-P]+ transfer reagents in phospha-Wittig-type reactions, leading to the formation of cationic phosphaalkenes and phosphanides. These reactions involve intermediates such as three-membered cyclic thiophosphiranes and diphosphirane salts. The versatility of [LC-P]+ as a P1 building block is demonstrated through various substitution reactions, providing access to otherwise difficult-to-synthesize compounds.
Neutral Analogue of Phosphamethine Cyanine
A neutral analogue of a phosphamethine cyanine cation has been synthesized through the reaction of an imidazolio-phosphide with an N-heterocyclic bromo-borane and NaH. DFT studies have analyzed the dative bonding across P-C/B bonds and the conformational preferences, revealing steric influences on the observed conformation.
Basicity Scale in Nonpolar Media
A self-consistent basicity scale in THF solution has been developed, ranging from 2-methoxypyridine to EtP(1)(pyrr) phosphazene. This scale, anchored to the pKa value of triethylamine, provides a reliable measure of basicity in nonpolar media. The predictability and suitable spectral properties of phenylphosphazenes make them convenient neutral indicators in high basicity ranges.
High-Efficiency Neutral-pH Water Splitting with Nickel Cobalt Phosphide Catalyst
A ternary Ni0.1Co0.9P catalyst has been developed for efficient and robust neutral-pH water splitting. This catalyst, synthesized as porous nanosheets on conductive carbon fiber paper, demonstrates remarkable activity and stability for both hydrogen evolution and water oxidation in phosphate buffer electrolyte. The performance is attributed to the synergistic interplay between nickel and cobalt, making ternary metal phosphides promising candidates for low-cost, efficient water splitting devices.
Conclusion
The research on neutral phospha compounds spans a wide range of applications, from coordination chemistry and catalysis to the development of strong bases and efficient water-splitting catalysts. The versatility and unique properties of these compounds continue to drive advancements in various fields of chemistry.
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