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Phosphanide

Phosphanides are chemicals containing the [PH2]− anion. This is also known as the phosphino anion or phosphido ligand. The IUPAC name can also be dihydridophosphate(1−).[1]

Phosphanide
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
284
  • InChI=1S/H2P/h1H2/q-1
    Key: JZWFHNVJSWEXLH-UHFFFAOYSA-N
  • [H][P-][H]
Properties
H2P−
Molar mass 32.990 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

It can occur as a group phosphanyl -PH2 in organic compounds or ligand called phosphanido, or dihydridophosphato(1−). A related substance has PH2−. Phosphinidene (PH) has phosphorus in a −1 oxidation state.[2]

As a ligand PH2 can either bond to one atom or be in a μ2-bridged ligand across two metal atoms.[3] With transition metals and actinides, bridging is likely unless the metal atom is mostly enclosed in a ligand.

In phosphanides, phosphorus is in the −3 oxidation state. When phosphanide is oxidised, the first step is phosphinite ([H2PO]−). Further oxidation yields phosphonite ([HPO2]2−) and phosphite ([PO3]3−).[4]

The study of phosphine derivatives is unpopular, because they are unstable, poisonous and malodorous.[5]

Formation

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Alkali metal phosphanides can be made from phosphine and the metal dissolved in liquid ammonia. Sodium phosphanide can also be made from phosphine and triphenylmethyl sodium. Lithium phospahnide can be made from phosphine and butyl lithium or phenyl lithium.[3]

Another way to produce -PH2 complexes is by hydrolysis of a -P(SiMe3)2 compound with an alcohol, such as methanol.[3]

Yet another way is to remove a hydrogen atom from the phosphine in a phosphine complex by using a strong base.[3]

Properties

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When calcium phosphanide is heated, it decomposes by releasing phosphine and yielding the phosphanediide: CaPH. With further heating a binary calcium phosphide is formed.[4] Other compounds may also lose hydrogen as well as phosphine.[6]

Phosphanides can react with CCl4 to substitute Cl for H giving a -PCl2 compound. Similarly CBr4 can produce -PBr2. Also AgBF4 can react to yield -PF2.[7]

Sodium phosphanide can react with ethyl alcohol in a diethyl carbonate solution to yield sodium 2-phosphaethynolate (NaOCP). Na(DME)2OCP is also formed from NaPH2 when reacted with CO in a dimethoxyethane (DME) solution under pressure.[8]

List

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name formula system space group unit cell Å volume density M-P Å comment ref
lithium phosphanide LiPH2
Bis(1,2-dimethoxyethane-O,O′)lithium-phosphanide (dme)2LiPH2 monoclinic a=13.911 b=8.098 c=12.491 β=103.35° 1371.9 1.07 [9]
Li(PH2)(BEt3)2 [10]
LiPH2(BH3)2(THF)2 [10]
sodium dihydrogenphosphide NaPH2 [3]
Na13(PH2)(OtBu)12 [3]
tetraphosphanylsilane Si(PH2)4 [11]
KPH2 [3]
Ca(PH2)2•6NH3 [4]
Ca(PH2)2•2NH3 [4]
Cp2(CO)4Cr2(μ-PH2)(μ-H) [12]
Cp2(CO)4Cr2(μ-PH2)2 [12]
[(CO)4Cr(μ-PH2)]2 orthorhombic Cmca a =12.2545 b =11.5949 c=9.7196 [13]
(CO)4Cr(μ-PH2)2Cr(CO)3(PH3) triclinic P1 a=7.008 b=7.430 c=8.871, α =111.05° β=92.73° γ=114.08° [13]
Mn(PH2)2 · 3 NH3 [14]
K2[Mn(PH2)4] · 2 NH3 [14]
[(CO)4MnPH2]2 triclinic P1 a = 6.804, b = 7.064, c = 9.191, α =110.5°, β = 91.92°, γ =115.65°, Z = 1 [7][15]
(μ-PH2)2 · Mn2(CO8) + (μ-Br)(μ-PH2)Mn2(CO8) monoclinic P21/c a = 9.467, b = 12.181, c = 13.086, β = 109.98° 1418.2 [16]
[(CO)4MnPH2]3 monoclinic P2/n a = 9.052, b = 9.748, c = 12.642, β = 109.1°, Z = 2 [17][15]
(μ-Br)(μ-PH2)Mn2(CO8) [16]
[(CO)3Fe(μ-PH2)]2 monoclinic P21/m a =6.2476 b =12.982 c =7.2193 β =90.14° [13]
Cp(CO)2Fe(μ-PH2)Fe(CO)4 [3]
bis((ethane-1,2-diyl)bis(dimethylphosphine))-(hydrido)-(dihydridophosphide)-iron Fe(dmpe)2(H)PH2 triclinic P1 a=9.2246 b=12.4638 c=17.3198 α=89.872° β=88.482° γ=89.228° [18]
Co(PH2)3 [3][6]
KCo2(PH2)7 [3][6]
cp(CO)2Fe(μ-PH2)Fe(CO)4 monoclinic P21/c a = 7.336, b = 10.898, c = 17.616, β = 99.65°, Z = 4 2.29, 2.265 [17]
cp(CO)2Fe(μ-PH2)Fe(CO)(NO)2 [19]
cp(CO)2Fe(μ-PH2)Vcp(CO)3 [19]
cp(CO)2Fe(μ-PH2)Crcp(CO)(NO) [19]
cp(CO)2Fe(μ-PH2)Cr(CO)5 [19]
cp(CO)Fe(μ-CO, μ-PH2)Crcp(NO) [19]
cp(CO)2Fe(μ-PH2)MnMecp(CO)2 monoclinic P21 a = 7.501, b = 22.345, c = 9.741, β = 106.23°, Z = 4 [19][20]
cp(CO)2Fe(μ-PH2)Mn(NO)3 [19]
cp(CO)2Fe(μ-PH2)Mncp(CO)2 [19]
cp(CO)Fe(μ-CO, μ-PH2)Mncp(CO) [19]
cp(CO)Fe(μ-CO, μ-PH2)MnMecp(CO) [19]
(μ2-phosphido)-octacarbonyl-iron-manganese FeMn(CO)8(μ-PH2) triclinic P1 a=7.8647 b=9.223 c=9.368, α=90.966° β=91.141° γ=110.032° [21]
Li+[FeMn(CO)8(μ3-PH)Mn(CO)4(μ-PH2)Fe(CO)4]− [21]
Na+[FeMn(CO)8(μ3-PH)Mn(CO)4(μ-PH2)Fe(CO)4]− [21]
K+[FeMn(CO)8(μ3-PH)Mn(CO)4(μ-PH2)Fe(CO)4]− [21]
cp(CO)2Fe(μ-PH2)Co(CO)2(NO) [19]
Ni(PH2)2 [3][22]
[cpNiPH2]2 [23]
[cpNiPH2]3 rhombohedral R3 a = 16.861, c = 5.611 Z = 3 6 member ring [24][15]
K[Ni(PH2)3] orange, green or black [3][22]
cp(CO)2Fe(μ-PH2)Ni(CO)3 [17]
CH{(CMe)(2,6-iPr2C6H3N)}2GeIIPH2 monoclinic P21/c a=14.1380 b=16.3244 c=13.8086 β=116.379 Z=4 2855.1 1.213 orange or red [25]
[CH{(CMe)(2,6-iPr2C6H3N)}2GeIIP(H)]2 triclinic P1 a=10.8175 b=12.0783 c=2.6434 α=91.550 β=108.361 γ=111.339 Z=1 1441.49 1.203 red [25]
bisphosphanyl yttriate [(Me3Si)2Cp]2Y(PH2)2[Li(TMEDA)]2Cl [3]
(N,N',N''-[nitrilotri(ethane-2,1-diyl)]tris(t-butyl(dimethyl)silanamino))-phosphanyl-zirconium(iv) Zr(TrenDMBS)(PH2) TrenDMBS=N(CH2CH2NSiMe2But)3 orthorhombic Pbca a=19.978 b=15.4052 c=22.721 Zr−P=2.690 yellow [2]
{Cp(CO)2Mo}2(μ-PH2)(μ-H) [26][27]
Mo2Cp2(μ-PH2)2(CO)2 [28]
cp(CO)2Fe(μ-PH2)Mo(CO)5 [19]
{Cp(CO)2W}2(μ-PH2)(μ-H) [27]
W2Cp2(μ-PH2)2(CO)2 [28]
[(CO)4W(μ-PH2)]2 orthorhombic Cmca a=12.498 b=12.046 c=10.1185 [13]
[(CO)5W(μ-PH2)]2− [3]
(CO)4W(μ-PH2)2W(CO)3(PH3) a=7.008 b=7.430 c=8.871, α =111.05° β =92.73° γ=114.08° [13]
(CO)4W(μ-PH2)2W(CO)2(PH3)2 triclinic P1 a=7.014 b=9.386 c=13.632, α=70.15° β=79.82° γ=68.78° [13]
NMe3•H2BPH2••W(CO)5 [3]
phosphanylalane NMe3•H2AlPH2•W(CO)5 [3]
cp(CO)2Fe(μ-PH2)W(CO)5 [19]
phosphanygallane NMe3•H2GaPH2••W(CO)5 [3]
Re2(μ-PH2)2(CO)8 monoclinic P21/c a=9.808 b=12.326 c=13.299 β=109.08° Z=4 1519.4 2.896 yellow [29]
Re2(μ-H) · (μ-PH2)(CO)8 yellow [29]
Os(η2-O2CCH3)(PH2)(CO)(PPh3)2 [30]
Os(η2-N,N-dimethyldithiocarbamate)(PH2)(CO)(PPh3)2 [30]
Os(η2-acetylacetonate)(PH2)(CO)(PPh3)2 [30]
Os(η2-NO2)(PH2)(CO)(PPh3)2 [30]
OsCl- (PH2)(CO)2(PPh3)2 [31]
OsCl- (PH2)(CO)(PPh3)3 [31]
[Os(μ2-PH2)Cl(CO)(PPh3)2]2 triclinic P1 a 14.101, b 15.091, c 11.708, α 96.68, β 91.71, γ 63.92°, Z = 1 2222.0 [31]
OsH(PH2)(CO)2(PPh3)2 [31]
(μ2-Hydrido)-(μ2-phosphido)-acetonitrilo-henicosacarbonyl-hexa-osmium Os6(μ-H)(CO)21(NCMe)(μ-PH2) monoclinic P21/n a=11.161 b=12.532 c =26.60, β=90.03° [32]
(μ2-Phosphido)-(μ2-hydrido)-bis(undecacarbonyl-tri-osmium) Os6(μ-H)(CO)22(μ-PH2) monoclinic P21/c a =14.328 b =16.658 c =15.258, β =103.79° [32][33]
Os6(μ-H)(CO)21(CNBut)(μ-PH2) [32]
[Os6(μ-H)(CO)20{P(OMe)3}2(μ-PH2)]3 [32]
Ir(CO)ClH(PEt3)2(PH2) [3]
Ir(CO)BrH(PEt3)2(PH2) [3]
(Acetato-O,O')-(μ2-phosphonito)-carbonyl-iodo-bis(triphenylphosphine)-gold-osmium dichloromethane solvate Os(η2-O2CCH3)(PH2AuI)(CO)(PPh3)2 · (CH2Cl2)2 triclinic P1 a=12.320 b=13.962 c=14.122, α=96.76° β=101.93° γ=107.72° [30]
phosphanido-(N'-(triisopropylsilyl)-N,N-bis(2-((triisopropylsilyl)amino)ethyl)ethane-1,2-diaminato)-thorium(iv) Th(TrenTIPS)(PH2) monoclinic P21/n a=18.6189 b=22.6046 c=22.2818 β=113.726° 2.982 colourless [34]
PH2–UH 2.762 in solid argon [35]
TrenTIPS=N(CH2CH2NSiPri3)3 U(TrenTIPS)(PH2) monoclinic P21/n a=12.9994 b=16.2006 c=20.3678 β=91.313 Z=4 4288.3 2.883 yellow [36]

Derivatives

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Some derivatives of phosphanides have also been studied where hydrogen is substituted by another group. They include bis(trimethylsilyl)phosphanide, bis (triisopropylsilyl) phosphanide, bis (trimethylsilyl) phosphanide, diphenyl phosphanide.[37][38]

References

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