Lithium diphenylphosphide

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Lithium diphenylphosphide
LiPPh2.png
Names
Preferred IUPAC name
Lithium diphenylphosphanide
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/C12H10P.Li/c1-3-7-11(8-4-1)13-12-9-5-2-6-10-12;/h1-10H;/q-1;+1
    Key: WKUYEGHEUWHKIU-UHFFFAOYSA-N
  • [Li+].C1=CC=C(C=C1)[P-]C2=CC=CC=C2
Properties
C12H10LiP
Molar mass 192.13 g·mol−1
Appearancepale yellow solid
Reacts with water
Solubility Ethers, hydrocarbons
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-exclam.svg GHS-pictogram-pollu.svg
Danger
H302, H312, H314, H332, H410
P260, P261, P264, P270, P271, P273, P280, P301+P312, P301+P330+P331, P302+P352, P303+P361+P353, P304+P312, P304+P340, P305+P351+P338, P310, P312, P321, P322, P330, P363, P391, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Lithium diphenylphosphide contains lithium and the organophosphorus anion with the formula (C6H5)2PLi. It is a red, air-sensitive solid that is used in the preparation of diphenylphosphino compounds.

Contents

Synthesis and reactions

The lithium, sodium, and potassium salts are prepared by reduction of chlorodiphenylphosphine, [1] triphenylphosphine, [2] [3] or tetraphenyldiphosphine with alkali metals (M):

(C6H5)2PCl + 2 M → (C6H5)2PM + MCl
(C6H5)3P + 2 M → (C6H5)2PM + MC6H5
(C6H5)4P2 + 2 M → 2 (C6H5)2PM

They can also be obtained by deprotonation of diphenylphosphine.

With water, the salts convert to diphenylphosphine: [3]

(C6H5)2PLi + H2O → (C6H5)2PH + LiOH

With halocarbons, the salts react to give tertiary phosphines: [4]

(C6H5)2PM + RX → (C6H5)2PR + MX

When treated with metal halides, lithium diphenylphosphide gives transition metal phosphido complexes.

Structure and physical properties

Although treated as salts, alkali diphenylphosphides are highly aggregated in solution. They adopt polymeric structures as solids.

As an ether complex, the lithium salt is dark red. [6]

Related Research Articles

<span class="mw-page-title-main">Alkali metal</span> Group of highly reactive chemical elements

The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr). Together with hydrogen they constitute group 1, which lies in the s-block of the periodic table. All alkali metals have their outermost electron in an s-orbital: this shared electron configuration results in their having very similar characteristic properties. Indeed, the alkali metals provide the best example of group trends in properties in the periodic table, with elements exhibiting well-characterised homologous behaviour. This family of elements is also known as the lithium family after its leading element.

<span class="mw-page-title-main">Triphenylphosphine</span> Chemical compound

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is versatile compound that is widely used as a reagent in organic synthesis and as a ligand for transition metal complexes, including ones that serve as catalysts in organometallic chemistry. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

<span class="mw-page-title-main">Rhodium(III) chloride</span> Chemical compound

Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic red-brown solids. The soluble trihydrated (n = 3) salt is the usual compound of commerce. It is widely used to prepare compounds used in homogeneous catalysis.

<span class="mw-page-title-main">Phenyllithium</span> Chemical compound

Phenyllithium is an organometallic agent with the empirical formula C6H5Li. It is most commonly used as a metalating agent in organic syntheses and a substitute for Grignard reagents for introducing phenyl groups in organic syntheses. Crystalline phenyllithium is colorless; however, solutions of phenyllithium are various shades of brown or red depending on the solvent used and the impurities present in the solute.

<span class="mw-page-title-main">Borohydride</span> Any chemical compound having a borohydride anion

Borohydride refers to the anion [BH4], which is also called tetrahydridoborate, and its salts. Borohydride or hydroborate is also the term used for compounds containing [BH4−nXn], where n is an integer from 0 to 3, for example cyanoborohydride or cyanotrihydroborate [BH3(CN)] and triethylborohydride or triethylhydroborate [BH(CH2CH3)3]. Borohydrides find wide use as reducing agents in organic synthesis. The most important borohydrides are lithium borohydride and sodium borohydride, but other salts are well known. Tetrahydroborates are also of academic and industrial interest in inorganic chemistry.

<span class="mw-page-title-main">Chloro(triphenylphosphine)gold(I)</span> Chemical compound

Chloro(triphenylphosphine)gold(I) or triphenylphosphinegold(I) chloride is a coordination complex with the formula (Ph3P)AuCl. This colorless solid is a common reagent for research on gold compounds.

<span class="mw-page-title-main">Triphenylarsine</span> Chemical compound

Triphenylarsine is the chemical compound with the formula As(C6H5)3. This organoarsenic compound, often abbreviated AsPh3, is a colorless crystalline solid that is used as a ligand and a reagent in coordination chemistry and organic synthesis. The molecule is pyramidal with As-C distances of 1.942–1.956 Å and C-As-C angles of 99.6–100.5°.

Organophosphines are organophosphorus compounds with the formula PRnH3−n, where R is an organic substituent. These compounds can be classified according to the value of n: primary phosphines (n = 1), secondary phosphines (n = 2), tertiary phosphines (n = 3). All adopt pyramidal structures. Organophosphines are generally colorless, lipophilic liquids or solids. The parent of the organophosphines is phosphine (PH3).

<span class="mw-page-title-main">Bis(triphenylphosphine)iminium chloride</span> Chemical compound

Bis(triphenylphosphine)iminium chloride is the chemical compound with the formula [( 3P)2N]Cl, often abbreviated [(Ph3P)2N]Cl, where Ph is phenyl C6H5, or even abbreviated [PPN]Cl or [PNP]Cl or PPNCl or PNPCl, where PPN or PNP stands for (Ph3P)2N. This colorless salt is a source of the [(Ph3P)2N]+ cation, which is used as an unreactive and weakly coordinating cation to isolate reactive anions. [(Ph3P)2N]+ is a phosphazene.

<span class="mw-page-title-main">Tetraphenylphosphonium chloride</span> Chemical compound

Tetraphenylphosphonium chloride is the chemical compound with the formula [(C6H5)4P]Cl, abbreviated Ph4PCl or PPh4Cl or [PPh4]Cl, where Ph stands for phenyl. Tetraphenylphosphonium and especially tetraphenylarsonium salts were formerly of interest in gravimetric analysis of perchlorate and related oxyanions. This colourless salt is used to generate lipophilic salts from inorganic and organometallic anions. Thus, [Ph4P]+ is useful as a phase-transfer catalyst, again because it allows inorganic anions to dissolve in organic solvents.

<span class="mw-page-title-main">Diphenylphosphine</span> Chemical compound

Diphenylphosphine, also known as diphenylphosphane, is an organophosphorus compound with the formula (C6H5)2PH. This foul-smelling, colorless liquid is easily oxidized in air. It is a precursor to organophosphorus ligands for use as catalysts.

Organosodium chemistry is the chemistry of organometallic compounds containing a carbon to sodium chemical bond. The application of organosodium compounds in chemistry is limited in part due to competition from organolithium compounds, which are commercially available and exhibit more convenient reactivity.

<span class="mw-page-title-main">Metal bis(trimethylsilyl)amides</span>

Metal bis(trimethylsilyl)amides are coordination complexes composed of a cationic metal M with anionic bis(trimethylsilyl)amide ligands (the N 2 monovalent anion, or −N 2 monovalent group, and are part of a broader category of metal amides.

<span class="mw-page-title-main">Molybdenum(III) chloride</span> Chemical compound

Molybdenum(III) chloride is the inorganic compound with the formula MoCl3. It forms purple crystals.

<span class="mw-page-title-main">Bis(triphenylphosphine)platinum chloride</span> Chemical compound

Bis(triphenylphosphine)platinum chloride is a metal phosphine complex with the formula PtCl2[P(C6H5)3]2. Cis- and trans isomers are known. The cis isomer is a white crystalline powder, while the trans isomer is yellow. Both isomers are square planar about the central platinum atom. The cis isomer is used primarily as a reagent for the synthesis of other platinum compounds.

<span class="mw-page-title-main">Tris(trimethylsilyl)phosphine</span> Chemical compound

Tris(trimethylsilyl)phosphine is the organophosphorus compound with the formula P(SiMe3)3 (Me = methyl). It is a colorless liquid that ignites in air and hydrolyses readily.

<span class="mw-page-title-main">Bis(triphenylphosphine)iron tricarbonyl</span> Chemical compound

Tricarbonylbis(triphenylphosphine)iron(0) is a coordination complex with the formula Fe(CO)3(PPh3)2 (Ph = C6H5). A yellow solid, this complex is derived from iron pentacarbonyl by replacement of two carbonyl ligands by triphenylphosphine (PPh3).

cis-1,2-Bis(diphenylphosphino)ethylene (dppv) is an organophosphorus compound with the formula C2H2(PPh2)2 (Ph = C6H5). Both the cis and trans isomers are known, but the cis isomer is of primary interest. Classified as a diphosphine ligand, it is a bidentate ligand in coordination chemistry. For example it gives rise to the complex Ni(dppv)2 and the coordination polymer [Ni(dppv)]n. As a chelating ligand, dppv is very similar to 1,2-bis(diphenylphosphino)benzene.

<span class="mw-page-title-main">Methyldiphenylphosphine</span> Chemical compound


Methyldiphenylphosphine is the organophosphine with the formula CH3(C6H5)2P, often abbreviated PMePh2. It is a colorless, viscous liquid. It is a member of series (CH3)3-n(C6H5)2P that also includes n = 0, n = 1, and n = 3 that are often employed as ligands in metal phosphine complexes.

<span class="mw-page-title-main">(Trimethylsilyl)methyllithium</span> Chemical compound

(Trimethylsilyl)methyllithium is classified both as an organolithium compound and an organosilicon compound. It has the empirical formula LiCH2Si(CH3)3, often abbreviated LiCH2TMS. It crystallizes as the hexagonal prismatic hexamer [LiCH2TMS]6, akin to some polymorphs of methyllithium. Many adducts have been characterized including the diethyl ether complexed cubane [Li43-CH2TMS)4(Et2O)2] and [Li2(μ-CH2TMS)2(TMEDA)2].

References

  1. Goldsberry, R.; Cohn, Kim; Hawthorne, M. F.; Dunks, G. B.; Wilson, R. J. (1972). "Diphenyl(trimethylsilyl)phosphine and Dimethyl(trimethylsilyl)‐phosphine". In Cotton, F. A. (ed.). Inorganic Syntheses. Vol. 13. pp. 26–32. doi:10.1002/9780470132449.ch7. ISBN   9780470132449.
  2. Luther, George W. III; Beyerle, Gordon; Cox, Daniel; Cohn, Kim (1977). "Lithium Diphenylphosphide and Diphenyl(Trimethylsilyl)Phosphine". In MacDiarmid, Alan G. (ed.). Inorganic Syntheses. Vol. 17. pp. 186–188. doi:10.1002/9780470132487.ch51. ISBN   9780470132487.
  3. 1 2 Bianco, V. D.; Doronzo, S.; Chan, J.; Bennett, M. A. (1976). "Diphenylphosphine". In Basolo, Fred (ed.). Inorganic Syntheses. Vol. 16. pp. 161–188. doi:10.1002/9780470132470.ch43. ISBN   9780470132470.
  4. Levason, W.; Mcauliffe, C. A.; Barth, R. C.; Grim, S. O. (1976). "Cis‐2‐Diphenylarsinovinyldiphenylphosphine and 2‐Diphenylarsinoethyldiphenylphosphine". In Basolo, Fred (ed.). Inorganic Syntheses. Vol. 16. pp. 188–192. doi:10.1002/9780470132470.ch50. ISBN   9780470132470.
  5. Bartlett, Ruth A.; Olmstead, Marilyn M.; Power, Philip P. (1986). "Structural Characterization of the Solvate Complexes of the Lithium Diorganophosphides [{Li(Et2O)PPh2}], [{Li(THF)2PPh2}], and [{Li(THF)P(C6H11)2}]". Inorg. Chem. 25: 1243–1247. doi:10.1021/ic00228a034.
  6. Hegedüs, Kristof (12 Dec 2012). "The reaction of triphenylphosphine with lithium..." Pictures from an Organic Chemistry Laboratory. Tumblr. Archived from the original on 12 November 2020. Retrieved 6 January 2025.{{cite web}}: CS1 maint: multiple names: authors list (link)