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Diphosphane
Stereo structural formula of diphosphane with explicit hydrogens
Stereo structural formula of diphosphane with explicit hydrogens
Ball-and-stick model of diphosphane
Ball-and-stick model of diphosphane
Names
IUPAC name
Diphosphane
Systematic IUPAC name
Diphosphane (substitutive)
Tetrahydridodiphosphorus(P—P) (additive)
Other names
Diphosphine
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
  • InChI=1S/H4P2/c1-2/h1-2H2 ☒N
    Key: VURFVHCLMJOLKN-UHFFFAOYSA-N ☒N
  • PP
Properties
P2H4
Melting point −99 °C (−146 °F; 174 K)
Boiling point 63.5 °C (146.3 °F; 336.6 K) (Extrapolated, decomposes)
Related compounds
Other anions
 ammonia
hydrazine
triazane
Other cations
 diphosphines
Related Binary Phosphorus halides
 diphosphorus tetrafluoride
diphosphorus tetrachloride
diphosphorus tetrabromide
diphosphorus tetraiodide
Related compounds
 phosphane
triphosphane
diphosphene
diphosphenes
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Diphosphane, or diphosphine, is an inorganic compound with the chemical formula P2H4. This colourless liquid is one of several binary phosphorus hydrides. It is the impurity that typically causes samples of phosphine to ignite in air.

Properties, preparation, reactions

[edit]

Diphosphane adopts the gauche conformation (like hydrazine, less symmetrical than shown in the image) with a P−P distance of 2.219 angstroms. It is nonbasic, unstable at room temperature, and spontaneously flammable in air. It is only poorly soluble in water but dissolves in organic solvents. Its 1H NMR spectrum consists of 32 lines resulting from an A2XX'A'2 splitting system.[1]

Diphosphane is produced by the hydrolysis of calcium monophosphide, which can be described as the Ca2+ derivative of P4−2. According to an optimized procedure, hydrolysis of 400 g of CaP at −30 °C gives about 20 g of product, slightly contaminated with phosphine.[citation needed]

Reaction of diphosphane with butyllithium affords a variety of condensed polyphosphine compounds.

Organic diphosphanes

[edit]

A variety of organic derivatives of diphosphane are known, but asymmetric diphosphanes are only stable at cryogenic temperatures. Otherwise, the substituents facily redistribute on the phosphorus centers to give a mixture of products. On the other hand, there appears to be a substantial barrier to chiral inversion.[2]

The central bond is weak, and easily adds substituents.[3]

The simplest synthesis method heats a phosphorus halide and a phosphane:

Ph2PCl + HPPh2 → Ph2P−PPh2 + HCl↑

Alkali metals can replace the hydrogen in that reaction (i.e., a dialkylphosphide), and in some rare cases a dialkylamine can replace the halide. Symmetric diphosphanes are easily prepared by reductive coupling, e.g. tetraphenyldiphosphine from chlorodiphenylphosphine:

2 ClPPh2 + 2 Na → Ph2P−PPh2 + 2 NaCl

Ultraviolet radiation decomposes mercury(II) dialkylphosphides to the metal and a dialkylphosphane.[4]

The methyl compound P2Me4 is prepared by the reduction of Me2P(S)−P(S)Me2, which is produced by methylation of thiophosphoryl chloride with methylmagnesium bromide.[5]

See also

[edit]

References

[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia

Diphosphane

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Diphosphane, also known as diphosphine, is an inorganic compound with the chemical formula P₂H₄, consisting of two phosphorus atoms linked by a single covalent bond, with each phosphorus atom bonded to two hydrogen atoms, making it the phosphorus analogue of hydrazine (N₂H₄).[1][2] This colorless, highly refractive liquid has a molecular weight of 65.98 g/mol and is notable for its extreme instability and reactivity.[3][2] Its physical properties include a melting point of −99 °C and a boiling point of 56 °C, with a density ranging from 1.007 to 1.02 g/cm³ at room temperature; it is insoluble in water but soluble in ethanol and oil of turpentine, though it decomposes in these solvents.[2] Diphosphane ignites spontaneously in air at room temperature, rendering it pyrophoric, and it decomposes readily upon storage or exposure to catalysts like HCl, yielding phosphine (PH₃) and polymeric phosphorus hydrides such as P₅H₂ or P₉H₂.[2][4] Structurally, gas-phase electron diffraction studies reveal a P–P bond length of 2.218 ± 0.004 Å, P–H bond length of 1.451 ± 0.005 Å, ∠PPH angle of 95.2 ± 0.6°, and ∠HPH angle of 91.3 ± 1.4°, with a dihedral angle of approximately 81° suggesting a twisted conformation, though free rotation about the P–P bond cannot be ruled out.[5] The compound can be prepared in the laboratory by hydrolysis of technical calcium phosphide (Ca₃P₂) with water, which produces diphosphane as a minor byproduct (up to 30%) alongside phosphine (PH₃) and hydrogen from the primary reaction Ca₃P₂ + 6 H₂O → 3 Ca(OH)₂ + 2 PH₃; an alternative method is electric discharge through phosphine gas (2 PH₃ → P₂H₄ + H₂), achieving yields up to 50% based on consumed phosphine.[2] Chemically, diphosphane acts as a powerful reducing agent, akin to hydrazine, but its reactions remain underexplored due to handling difficulties; it serves as the parent compound for substituted diphosphanes (R₂P–PR₂) used in coordination chemistry and materials science.[2][6] Recent efforts have focused on its storage and separation using metal-organic frameworks, where it can be adsorbed stably for months without pyrophoricity, highlighting potential applications in phosphorus hydride chemistry.[4]

Structure and Nomenclature

Molecular Geometry

Diphosphane, with the chemical formula P₂H₄, represents the simplest diphosphane, consisting of two phosphanyl (PH₂) groups connected by a direct phosphorus-phosphorus single bond. The molecule exhibits a preferred gauche conformation in the gas phase, featuring a dihedral angle between the lone pairs or H-P-H planes of approximately 67–81°, which minimizes steric repulsion and lone-pair interactions.[7][8] Microwave spectroscopy provides precise structural parameters, including a P-P bond length of 2.219 Å, P-H bond lengths of 1.419 Å, and an H-P-H bond angle of 93.3°; the P-P-H bond angle is inferred to be around 97° based on the pyramidal geometry of the PH₂ units.[7] Complementary gas-phase electron diffraction measurements yield a P-P bond length of 2.218 ± 0.004 Å, P-H bond lengths of 1.451 ± 0.005 Å, an H-P-H angle of 91.3 ± 1.4°, and a P-P-H angle of 95.2 ± 0.6°, confirming the overall tetrahedral-like arrangement at each phosphorus atom with gauche torsional preference.[8] Relative to hydrazine (N₂H₄), diphosphane's P-P bond is markedly longer (2.219 Å compared to the experimental N-N bond length of 1.45 Å), owing to phosphorus's larger atomic radius, which reduces valence orbital overlap and bond strength.[7][9] Ab initio computational analyses of the potential energy surface indicate that the gauche form constitutes the global energy minimum, whereas the trans conformation acts as a transition state for rotation about the P-P bond, separated by a modest barrier of about 655 cm⁻¹ (1.9 kcal/mol).

Naming and Isomers

Diphosphane has the molecular formula P₂H₄ and is the preferred IUPAC name for this compound, reflecting its structure as two phosphorus atoms linked by a single bond, each bearing two hydrogen atoms. Alternative names include diphosphine and phosphanylphosphane, the latter being a substitutive IUPAC designation generated from systematic nomenclature tools.[1][10] This compound is distinct from phosphine (PH₃), the monomeric phosphorus hydride, and belongs to the family of catenated phosphorus hydrides known as polyphosphanes or polyphosphines, which follow the general formula PₙH_{2n+2} for open-chain structures analogous to alkanes. Diphosphane corresponds to the n=2 member of this series, serving as the direct dimer analog to PH₃ in the progression of phosphorus catenation.[11] Due to the identical phosphorus atoms in its symmetric structure, diphosphane exhibits no stable geometric or constitutional isomers under standard conditions. Theoretical ab initio calculations confirm that the molecule prefers a gauche conformation in its ground state, with no evidence for alternative bridged or other hypothetical forms as minima on the potential energy surface.[12][13]

Physical Properties

Appearance and Phase Behavior

Diphosphane is a colorless liquid at room temperature that ignites spontaneously upon exposure to air due to its pyrophoric nature. This high reactivity necessitates handling under an inert atmosphere, such as nitrogen or argon, to avoid ignition and ensure safe manipulation.[14] The compound melts at −99 °C and has an extrapolated boiling point of approximately 64 °C, though it decomposes prior to boiling, limiting direct measurement.[15] Its liquid density is 1.014 g/cm³ at 20 °C, consistent with measurements extrapolated from data between −78 °C and +18 °C.[14] Diphosphane exhibits low solubility in water, with only 0.035 g dissolving per 100 g of solution at 0 °C, reflecting limited miscibility.[14] In contrast, it shows high solubility in organic solvents, including hydrocarbons like n-hexane and ethers, enabling stable solutions for experimental studies.[14]

Spectroscopic Properties

Diphosphane exhibits a complex proton nuclear magnetic resonance (¹H NMR) spectrum due to the coupling between the hydrogen atoms and phosphorus nuclei. The spectrum consists of 32 lines arising from an A₂XX'₂A₂' spin system, reflecting the strong P-H scalar couplings (³J_{PH} ≈ 180-200 Hz) and the P-P coupling across the P-P bond. This intricate splitting pattern is influenced by the gauche geometry of the molecule, which leads to distinct chemical environments for the protons on each phosphorus atom. The ³¹P NMR spectrum of diphosphane displays a single peak at approximately -210 ppm (relative to 85% H₃PO₄), shifted downfield by about 30 ppm compared to phosphane (PH₃ at -240 ppm). This deshielding effect is attributed to the P-P single bond interaction, which alters the electronic environment around each phosphorus nucleus, increasing the paramagnetic contribution to the shielding tensor. Infrared (IR) spectroscopy reveals characteristic absorption bands for diphosphane, including the P-H stretching modes around 2300 cm⁻¹ and the P-P stretching mode near 300 cm⁻¹. These vibrations confirm the presence of the P-H bonds and the weak P-P linkage, with the low-frequency P-P stretch indicative of the single bond character.[16] Raman spectroscopy provides complementary vibrational data, with active modes that support the gauche conformation of diphosphane. The spectra of the solid show polarized P-H stretches aligning with the IR data and additional low-frequency modes around 300 cm⁻¹ for P-P vibration, consistent with a C₂-symmetric structure rather than the trans isomer.[16][13] Mass spectrometry of diphosphane shows the molecular ion [P₂H₄]⁺ at m/z 66, with moderate intensity due to the molecule's instability. Prominent fragments arise from P-P bond cleavage, including [PH₂]⁺ at m/z 33 and [PH₃]⁺ at m/z 34, along with [P₂H₃]⁺ at m/z 65, highlighting the facile dissociation of the central P-P bond under electron impact conditions.[17]

Synthesis and Preparation

Laboratory Methods

The primary laboratory method for synthesizing diphosphane involves the hydrolysis of calcium monophosphide (CaP or Ca₂P₂) with water or dilute acid at low temperatures to control the reaction and limit decomposition. The reaction proceeds according to the equation:
Ca2P2+4H2O→2Ca(OH)2+P2H4 \text{Ca}_2\text{P}_2 + 4 \text{H}_2\text{O} \rightarrow 2 \text{Ca(OH)}_2 + \text{P}_2\text{H}_4
This may produce diphosphane alongside phosphine (PH₃) as an impurity. According to established procedures, the hydrolysis is conducted in a suitable flask under an inert atmosphere, with the product collected in cooled traps. An optimized scale involves hydrolyzing approximately 400 g of CaP at −30 °C, yielding about 20 g of diphosphane.[18] Yields for this method are typically low, ranging from 20-30%, due to side reactions and the instability of diphosphane. The synthesis requires an inert atmosphere of argon or nitrogen to prevent ignition or oxidation, and the process must be performed in low-temperature reactors to maintain the reaction temperature. Vacuum distillation is essential for initial isolation of diphosphane from the phosphine impurity.[18] An alternative laboratory approach is electric discharge on phosphine gas, achieving yields up to 50% based on consumed phosphine.[2]

Purification Techniques

Due to the instability and pyrophoric nature of diphosphane (P₂H₄), purification must be conducted under inert atmospheres at low temperatures to minimize decomposition into phosphine (PH₃) and polymeric phosphorus hydrides. The primary method involves fractional distillation under high vacuum (ca. 10⁻³ mm Hg) to separate P₂H₄ from co-produced PH₃ and H₂. The boiling point of PH₃ is −87.7 °C at standard pressure, enabling its removal by trapping at −90 to −100 °C, while P₂H₄ is collected in subsequent fractions distilled at approximately −35 °C and condensed in traps cooled to −196 °C with liquid nitrogen.[18] Impure P₂H₄ mixtures are further refined by selective absorption techniques targeting PH₃ contaminants, as PH₃ readily forms insoluble salts with heavy metal ions whereas P₂H₄ is less reactive under these conditions. Passage of the gaseous mixture through solutions or filters impregnated with silver nitrate or mercury(II) compounds quantitatively removes PH₃ by precipitation or adsorption, yielding cleaner P₂H₄ fractions for subsequent distillation.[19][20] Analytical confirmation of purity is achieved via gas chromatography (GC), which resolves P₂H₄ from PH₃ and higher phosphorus hydrides using flame photometric or mass spectrometric detection; samples exceeding 95% purity are routinely obtained post-distillation. Complementary assessment employs ³¹P NMR spectroscopy or mass spectrometry detecting the m/z 66 parent ion.[21] Purified P₂H₄ is stored in sealed glass ampoules under inert gas (e.g., argon) at −196 °C in liquid nitrogen to prevent thermal or photolytic decomposition, with samples remaining viable for weeks to months under these conditions.[18]

Stability and Reactivity

Thermal and Chemical Stability

Diphosphane (P₂H₄) displays poor thermal stability, undergoing decomposition above 50 °C primarily via pathways yielding phosphine (PH₃) and phosphorus (such as P₄), though higher phosphanes may also form depending on conditions.[22] This instability arises from the relatively weak P–P single bond, with a dissociation energy of approximately 210 kJ/mol, which is lower than the N–N bond energy in hydrazine (approximately 251 kJ/mol). Under inert conditions at room temperature, diphosphane exhibits kinetic stability with a half-life on the order of hours, but storage requires rigorous exclusion of light and oxygen to prevent accelerated breakdown.[12] Chemically, diphosphane is highly reactive toward oxygen, igniting spontaneously in air due to an exothermic oxidation reaction. This pyrophoric behavior underscores its hazardous nature, as even trace exposure to atmospheric oxygen leads to immediate combustion. Additionally, diphosphane shows sensitivity to hydrolysis and decomposes in the presence of water. These decomposition routes highlight the compound's inherent instability, limiting its practical handling to controlled, anhydrous, and anaerobic environments. Recent studies have demonstrated stabilization of P₂H₄ through adsorption in metal-organic frameworks like α-Mg formate, where it remains non-pyrophoric and stable for months at room temperature.[4][2]

Key Reactions

Diphosphane exhibits redox behavior as a reducing agent, akin to hydrazine, participating in electron-transfer processes to reduce metal ions or organic substrates. In these reactions, it undergoes oxidation to phosphine or phosphorus, facilitating applications in synthetic reductions, though its instability restricts practical use compared to more stable analogs.[2]

Organic Derivatives

Symmetric Derivatives

Symmetric derivatives of diphosphane are organophosphorus compounds characterized by the general formula R₂P–PR₂, where R represents identical alkyl or aryl substituents on each phosphorus atom, such as in tetramethyldiphosphane (Me₂P–PMe₂). These symmetric structures maintain the core P–P connectivity of the parent diphosphane while enhancing stability through organic substitution. Unlike the highly reactive inorganic precursor P₂H₄, these derivatives exhibit improved handling properties due to the steric and electronic effects of the R groups.[23] The primary synthetic route for symmetric diphosphanes involves reductive coupling of the corresponding chlorophosphines (R₂PCl) using alkali or alkaline earth metals. A common method employs magnesium in a Wurtz-type reaction: 2 R₂PCl + 2 Mg → R₂P–PR₂ + MgCl₂. This approach is versatile for various R groups, yielding the desired P–P bonded product under anhydrous conditions in ethereal solvents. Alternative reductants like lithium, sodium, or potassium can also be used, with yields typically ranging from 50–80% depending on the substituent size and reaction conditions.[24] A representative example is tetraphenyldiphosphine (Ph₂P–PPh₂), synthesized by the sodium reduction of chlorodiphenylphosphine: 2 Ph₂PCl + 2 Na → Ph₂P–PPh₂ + 2 NaCl. This compound is isolated as a stable yellow solid, air-sensitive but thermally robust at room temperature.[25][26] The incorporation of bulky substituents, such as tert-butyl or cyclohexyl groups, provides steric shielding against certain reactions but often lengthens the P–P bond due to repulsion, which can reduce thermal stability and promote dissociation. For instance, bis(di-tert-butylphosphino)diphosphane (tBu₂P–PtBu₂) shows greater lability and proneness to radical cleavage compared to less hindered analogs like tetramethyldiphosphane, which is more volatile.[27][28] Symmetric diphosphanes serve as bidentate ligands in coordination chemistry, particularly in transition metal complexes for catalytic applications. Tetraphenyldiphosphine, for example, forms stable nickel(II) and cobalt(II) complexes that exhibit potential in hydrogenation and cross-coupling reactions due to the flexible P–P backbone allowing chelation. Their ability to bridge metals while maintaining redox stability makes them valuable in designing catalysts for selective C–C bond formations.[26]

Asymmetric and Functionalized Derivatives

Asymmetric derivatives of diphosphane feature the general formula R₂P–PR'R'', where the substituents R, R', and R'' differ, leading to structural and electronic asymmetry that can influence reactivity and coordination behavior compared to symmetric analogs. These compounds are often less stable than their symmetric counterparts due to reduced steric protection and potential for disproportionation, but specific substitutions can mitigate this. For instance, mixed alkyl-aryl diphosphanes like Me₂P–PPh₂ exhibit distinct phosphorus environments, with the dimethylphosphino group providing electron-donating properties and the diphenylphosphino group offering π-acceptor capabilities.[29] Synthesis of unsymmetric diphosphanes typically involves salt metathesis reactions between chlorophosphines and lithium phosphides, such as the reaction of Me₂PCl with Ph₂PLi to yield Me₂P–PPh₂ in high yields under inert conditions. These reactions are often conducted at low temperatures, around -78 °C, to prevent P–P bond cleavage or rearrangement, and the products are isolated as air-sensitive oils or solids. Alternative routes include dehalosilylation or reductive coupling, but metathesis remains the most versatile for introducing diverse substituents like alkyl, aryl, or amino groups. No tendency for rearrangement to symmetric species is observed in these systems, allowing isolation of pure unsymmetric products.[29] Functionalized asymmetric derivatives incorporate chelating or rigid frameworks to enhance stability and utility in catalysis. Bicyclic diphosphanes, such as those with a PCNCP core (e.g., derived from phosphole rings bridged by a P–P bond), represent post-2020 advancements, offering rigid geometries that prevent P–P bond dissociation and enable coordination to transition metals without cleavage. These are synthesized in one- or two-step processes from readily available phosphines, yielding gram-scale quantities with isolated yields up to 33%, and exhibit improved thermal stability up to room temperature due to the constrained structure. Such bicyclic systems serve as ligands in dinuclear Pd(II) and Pt(II) complexes, demonstrating selective binding without backbone disruption.[30] Labile unsymmetric diphosphanes, like simple alkyl-aryl variants, require cryogenic isolation (e.g., below -50 °C) to maintain integrity, as they undergo facile P–P bond homolysis at ambient conditions. Stability is enhanced by bulky or chelating substituents that sterically shield the P–P bond or impose geometric constraints, allowing some functionalized examples to be handled briefly at room temperature for catalytic applications.[29] Recent advances include strain-releasing ring-opening diphosphination strategies for generating unsymmetric diphosphine ligands. In a 2024 method, highly strained bicyclo[1.1.0]butane, bicyclo[3.1.1]heptane propellane, and bicyclo[4.1.1]octane propellane scaffolds undergo ring-opening diphosphination using a diarylphosphine oxide and a diarylchlorophosphine under photocatalytic conditions (Ir catalyst or white/blue LED irradiation), yielding unsymmetric diphosphines with differentiated phosphorus centers in good yields (up to 74%). This approach integrates experimental and computational design to optimize regioselectivity.[31]

References

  1. Diphosphane | H4P2 | CID 139283 - PubChem - NIH
  2. [PDF] Phosphorus Hydrides - Russian Chemical Reviews
  3. Diphosphane properties - SpringerMaterials
  4. Solid‐State Investigation, Storage, and Separation of Pyrophoric ...
  5. Electron diffraction studies of the hydrides Si2H6 and P2H4
  6. From Clusters to Unorthodox Pnictogen Sources: Solution-Phase ...
  7. Microwave spectrum, structure, and dipole moment of biphosphine-4
  8. https://doi.org/10.1016/0022-2860(72
  9. https://cccbdb.nist.gov/exp2x.asp?casno=302012
  10. Diphosphane | H4P2 - ChemSpider
  11. Open-Chain Polyphosphorus Hydrides (Phosphines)
  12. Ab initio study on the thermochemistry of diphosphine (P 2 H 4 ) and ...
  13. Photoelectron spectra of Group 5 compounds. II. Conformational ...
  14. Beiträge zur Chemie des Phosphors. 236. Über einige physikalische ...
  15. Phosphorus » diphosphorus tetrahydride - WebElements
  16. Vibrational spectrum and structure of solid diphosphine
  17. Mass Spectrometric Study of Phosphine and Diphosphine
  18. [PDF] handbook of preparative inorganic chemistry - IC-Unicamp
  19. Phosphine and selected metal phosphides (EHC 73, 1988) - INCHEM
  20. determination of phosphine fumigant by silver nitrate - SciELO
  21. [PDF] Analysis of Phosphine in Dried Foodstuffs via Headspace-GC-MSD
  22. From Diphosphane to Diphosphodiide Gold(III) Derivatives of 1,2 ...
  23. [PDF] Organic Phosphorus Compounds with a P-P Bond
  24. Advances in nucleophilic phosphine catalysis of alkenes, allenes ...
  25. [PDF] Review The synthesis of hypodiphosphoric acid and derivatives with ...
  26. Dalton Transactions - RSC Publishing
  27. Phosphine-catalysed reductive coupling of Dihalophosphanes
  28. Reactions of calcium carbide. Novel synthesis of ... - ACS Publications
  29. Tetraphenyldiphosphine complexes of nickel(II) and cobalt(II)
  30. [PDF] Dalton Transactions - MOST Wiedzy
  31. On the energetics of P–P bond dissociation of sterically strained ...
  32. https://doi.org/10.1039/C8DT03775B
  33. Synthesis, reactivities and coordination chemistry of new bicyclic ...
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