Phosphanide Explained

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]

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

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.

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

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

Properties

When calcium phosphanide is heated, it decomposes by releasing phosphine and yielding the phosphanediide: CaPH. With further heating a binary calcium phosphide is formed. 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

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
sodium dihydrogenphosphide	NaPH2
	Na13(PH2)(O^tBu)12
tetraphosphanylsilane	Si(PH2)4								^[11]
	KPH2
	Ca(PH2)2•6NH3
	Ca(PH2)2•2NH3
	Cp2(CO)4Cr2(μ-PH2)(μ-H)								^[12]
	Cp2(CO)4Cr2(μ-PH2)2
	[(CO)<sub>4</sub>Cr(μ-PH<sub>2</sub>)]2	orthorhombic	Cmca	a =12.2545 b =11.5949 c=9.7196					^[13]
	(CO)4Cr(μ-PH2)2Cr(CO)3(PH3)	triclinic	P	a=7.008 b=7.430 c=8.871, α =111.05° β=92.73° γ=114.08°
	Mn(PH2)2 · 3 NH3								^[14]
	K2[Mn(PH<sub>2</sub>)<sub>4</sub>] · 2 NH3
	[(CO)<sub>4</sub>MnPH<sub>2</sub>]2	triclinic	P	a = 6.804, b = 7.064, c = 9.191, α =110.5°, β = 91.92°, γ =115.65°, Z = 1					^[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)<sub>4</sub>MnPH<sub>2</sub>]3	monoclinic	P2/n	a = 9.052, b = 9.748, c = 12.642, β = 109.1°, Z = 2
	(μ-Br)(μ-PH2)Mn2(CO8)
	[(CO)<sub>3</sub>Fe(μ-PH<sub>2</sub>)]2	monoclinic	P21/m	a =6.2476 b =12.982 c =7.2193 β =90.14°
	Cp(CO)2Fe(μ-PH2)Fe(CO)4
bis((ethane-1,2-diyl)bis(dimethylphosphine))-(hydrido)-(dihydridophosphide)-iron	Fe(dmpe)2(H)PH2	triclinic	P	a=9.2246 b=12.4638 c=17.3198 α=89.872° β=88.482° γ=89.228°					^[17]
	Co(PH2)3
	KCo2(PH2)7
	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		^[18]
	cp(CO)2Fe(μ-PH2)Fe(CO)(NO)2								^[19]
	cp(CO)2Fe(μ-PH2)Vcp(CO)3
	cp(CO)2Fe(μ-PH2)Crcp(CO)(NO)
	cp(CO)2Fe(μ-PH2)Cr(CO)5
	cp(CO)Fe(μ-CO, μ-PH2)Crcp(NO)
	cp(CO)2Fe(μ-PH2)MnMecp(CO)2	monoclinic	P21	a = 7.501, b = 22.345, c = 9.741, β = 106.23°, Z = 4					^[20]
	cp(CO)2Fe(μ-PH2)Mn(NO)3
	cp(CO)2Fe(μ-PH2)Mncp(CO)2
	cp(CO)Fe(μ-CO, μ-PH2)Mncp(CO)
	cp(CO)Fe(μ-CO, μ-PH2)MnMecp(CO)
(μ2-phosphido)-octacarbonyl-iron-manganese	FeMn(CO)8(μ-PH2)	triclinic	P	a=7.8647 b=9.223 c=9.368, α=90.966° β=91.141° γ=110.032°					^[21]
	Li^+[FeMn(CO)<sub>8</sub>(μ<sub>3</sub>-PH)Mn(CO)<sub>4</sub>(μ-PH<sub>2</sub>)Fe(CO)<sub>4</sub>]^−
	Na^+[FeMn(CO)<sub>8</sub>(μ<sub>3</sub>-PH)Mn(CO)<sub>4</sub>(μ-PH<sub>2</sub>)Fe(CO)<sub>4</sub>]^−
	K^+[FeMn(CO)<sub>8</sub>(μ<sub>3</sub>-PH)Mn(CO)<sub>4</sub>(μ-PH<sub>2</sub>)Fe(CO)<sub>4</sub>]^−
	cp(CO)2Fe(μ-PH2)Co(CO)2(NO)
	Ni(PH2)2								^[22]
	[cpNiPH<sub>2</sub>]2								^[23]
	[cpNiPH<sub>2</sub>]3	rhombohedral	R3	a = 16.861, c = 5.611 Z = 3				6 member ring	^[24]
	K[Ni(PH<sub>2</sub>)<sub>3</sub>]							orange, green or black
	cp(CO)2Fe(μ-PH2)Ni(CO)3
	CH2Ge^IIPH2	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-<sup>''i''</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>N)}<sub>2</sub>Ge<sup>II</sup>P(H)]2	triclinic	P	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
bisphosphanyl yttriate	[(Me<sub>3</sub>Si)<sub>2</sub>Cp]2Y(PH2)2[Li(TMEDA)]2Cl
(N,N',N''-[nitrilotri(ethane-2,1-diyl)]tris(t-butyl(dimethyl)silanamino))-phosphanyl-zirconium(iv)	Zr(Tren^DMBS)(PH2) Tren^DMBS=N(CH2CH2NSiMe2Bu^t)3	orthorhombic	Pbca	a=19.978 b=15.4052 c=22.721			Zr−P=2.690	yellow
	2(μ-PH2)(μ-H)								^[26] ^[27]
	Mo2Cp2(μ-PH2)2(CO)2								^[28]
	cp(CO)2Fe(μ-PH2)Mo(CO)5
	2(μ-PH2)(μ-H)
	W2Cp2(μ-PH2)2(CO)2
	[(CO)<sub>4</sub>W(μ-PH<sub>2</sub>)]2	orthorhombic	Cmca	a=12.498 b=12.046 c=10.1185
	[(CO)<sub>5</sub>W(μ-PH<sub>2</sub>)]2^−
	(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°
	(CO)4W(μ-PH2)2W(CO)2(PH3)2	triclinic	P	a=7.014 b=9.386 c=13.632, α=70.15° β=79.82° γ=68.78°
	NMe3•H2BPH2••W(CO)5
phosphanylalane	NMe3•H2AlPH2•W(CO)5
	cp(CO)2Fe(μ-PH2)W(CO)5
phosphanygallane	NMe3•H2GaPH2••W(CO)5
	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
	Os(η^2-O2CCH3)(PH2)(CO)(PPh3)2								^[30]
	Os(η^2-N,N-dimethyldithiocarbamate)(PH2)(CO)(PPh3)2
	Os(η^2-acetylacetonate)(PH2)(CO)(PPh3)2
	Os(η^2-NO2)(PH2)(CO)(PPh3)2
	OsCl- (PH2)(CO)2(PPh3)2								^[31]
	OsCl- (PH2)(CO)(PPh3)3
	[Os(μ2-PH<sub>2</sub>)Cl(CO)(PPh<sub>3</sub>)<sub>2</sub>]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
	OsH(PH2)(CO)2(PPh3)2
(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°					^[33]
	Os6(μ-H)(CO)21(CNBu^t)(μ-PH2)
	[Os<sub>6</sub>(μ-H)(CO)<sub>20</sub>{P(OMe)<sub>3</sub>}<sub>2</sub>(μ-PH<sub>2</sub>)]3
	Ir(CO)ClH(PEt3)2(PH2)
	Ir(CO)BrH(PEt3)2(PH2)
(Acetato-O,O')-(μ2-phosphonito)-carbonyl-iodo-bis(triphenylphosphine)-gold-osmium dichloromethane solvate	Os(η^2-O2CCH3)(PH2AuI)(CO)(PPh3)2 · (CH2Cl2)2	triclinic	P	a=12.320 b=13.962 c=14.122, α=96.76° β=101.93° γ=107.72°
phosphanido-(N'-(triisopropylsilyl)-N,N-bis(2-((triisopropylsilyl)amino)ethyl)ethane-1,2-diaminato)-thorium(iv)	Th(Tren^TIPS)(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]
Tren^TIPS=N(CH2CH2NSiPr^i3)3	U(Tren^TIPS)(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

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]}

Notes and References

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