Английская Википедия:Germyl

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Germyl, trihydridogermanate(1-), trihydrogermanide, trihydridogermyl or according to IUPAC Red Book: germanide is an anion containing germanium bounded with three hydrogens, with formula Шаблон:Chem2. Germyl is the IUPAC term for the –Шаблон:Chem2 group. For less electropositive elements the bond can be considered covalent rather than ionic as "germanide" indicates. Germanide is the base for germane when it loses a proton.

Шаблон:Chem2

The first germyl compound to be discovered was sodium germyl. Germane was reacted with sodium dissolved in liquid ammonia to produce sodium germyl. Other alkali metal germyl compounds are known. There are also numerous transition metal complexes that contain germyl as a ligand.

Formation

Alkali metal germyl compounds have been made by reacting germane with the alkali metal dissolved in liquid ammonia, or other non-reactive solvent.

Transition metal complexes cam be made by using lithium aluminium hydride to reduce a trichlorogermyl complex (−Шаблон:Chem2), which in turn can be made from the transition metal complex chloride and [[Germanium dichloride|Шаблон:Chem2]].

Salt elimination can be used in a reaction with monochlorogermane and a sodium salt of a transition metal anion:

Шаблон:Chem2.

In the gas phase, the germyl anion Шаблон:Chem2 can be made from germane by capturing an electron with more than 8 eV of energy:

Шаблон:Chem2

The germyl radical can be produced and immobilised in molecular form by exposing germane to vacuum ultraviolet light in a solid argon matrix. On heating, digermane is formed:

Шаблон:Chem2

Properties

Germyl compounds react with water, so water cannot be used as a solvent. Liquids that have been used as solvents include liquid ammonia, ethyl amine, diglyme, or hexamethylphosphoramide. The choice of solvent depends on the temperature desired, whether alkali metals are going to be dissolved, whether the solvent needs to be distilled, and also if it reacts with the solute.

The bond between the metal ion and the germyl ion may be purely ionic, but may also be bonded via two bridging hydrogen atoms.

The energy to rip a hydrogen atom off germane to make the neutral radical is Шаблон:Convert. GeH₄ → GeH₃^• + H^•. Electron affinity for the radical is 1.6 eV: GeH₃^• + e⁻ → GeH₃⁻.

Gas phase acidity of germane is ΔGШаблон:Su is Шаблон:Convert; ΔHШаблон:Su is Шаблон:Convert for Шаблон:Chem2.

Both the anion Шаблон:Chem2 and radical Шаблон:Chem have C_3v symmetry, and are shaped as a triangular pyramid with germanium at the top, and three hydrogen atoms at the bottom. In the radical, the H-Ge-H angle is 110°. In the anion the H-Ge-H angle is about 93°.

Reactions

Germyl compounds gradually decompose at room temperature by releasing hydrogen and forming a metal germide.

Germyl compounds react with alkyl halides to substitute the germyl −Шаблон:Chem2 group for the halogen. With aromatic halide compounds, dihalomethanes, or neopentyl haldes they replace the halogen with hydrogen. Organogermanium compounds that can be produced include methyl germane, dimethyl germane, digermyl methane, digermyl ethane, digermyl propane.

The germyl ion reacts with water to yield germane:

Шаблон:Chem2

Sodium germyl reacts with oxygen to form an orthogermanate:

Шаблон:Chem2

This loses water at room temperature.

K[η⁵-C₅H₅)Mn(CO)₂GeH₃] reacts with acid to yield [η⁵-C₅H₅)Mn(CO)₂]₂Ge which has a Mn=Ge=Mn linkage in it.

List

formula	name	mw	system	space group	unit cell	volume	density	comments	ref
Шаблон:Chem2
Шаблон:Chem
Шаблон:Chem2	Sodium Trihydrogermanide							white
Шаблон:Chem
Шаблон:Chem
Шаблон:Chem
P(GeH3)3
KGeH3			cubic		a=7.235		2.003	NaCl structure
K([18]crown-6)(thf)GeH3		451.13	monoclinic	Pc	a=13.8587 b=9.9670 c=16.9439 β=107.206 Z=4	2235.7	1.34	colourless
K([15]crown-5)2GeH3		555.23	tetrahedral	IШаблон:Overbar	a=12.685 c=16.985 Z=4	2733.0	1.349	colourless
K([12]crown-4)2GeH3		467.13	monoclinic	C2/c	a=40.7694 b=6.623 c=29.6746 β=97.450 Z=16	9144.9	1.357	colourless
K[V(CO)3(η5-C5H5)GeH3]
[PPh4][V(CO)3(η5-C5H5)GeH3]			orthorhombic	Pcab	a=17.47 b=15.68 c=21.49 Z=8	5886	1.39	yellow
K[Cr(CO)5GeH3]
[PPh4][Cr(CO)5GeH3]			monoclinic	C2/c	a=22.301 b=6.989 c=18.002 β=? Z=4	2788.5	1.45	yellow
Mn(GeH3)(CO)5
Mn(GeH3)(CO)2(PPh(OEt)2)3								pale yellow
Mn(GeH3)(CO)3(PPh(OEt)2)2		610.96	triclinic	PШаблон:Overbar	a=10.118 b=11.060 c=13.009 α=97.859 β=98.612 γ=92.856 Z=2	1422.3	1.427	pale yellow
Mn(GeH3)(CO)2(P(OEt)3)3								pale yellow
Mn(GeH3)(CO)3(P(OEt)3)2								pale yellow
K[η5-C5H5)Mn(CO)2GeH3]
[(CH3)4N][η-CH3C5H4Mn(CO)2GeH3]			triclinic	PШаблон:Overbar	a=6.948 b=9.658 c=11.784 α=89.57 β=77.37 γ=88.05 Z=2	772	1.45
[(CH3)4N][η-CH3C5H4Mn(CO)2GeH3]			triclinic	PШаблон:Overbar	a=6.958 b=9.658 c=11.784 α=89.57 β=77.37 γ=88.05 Z=2	772	1.46
(GeH3)2Fe(CO)4	digermyltetracarbonyliron							mp 71°C colourless
GeH3(H)Fe(CO)4	monogermylhydridotetracarbonyliron							mp −30°C colourless
GeH3Fe(C5H5)(CO)2	Germyl(cyclopentadienyl)dicarbonyliron							mp 81°C yellow
Fe(CO)4(GeH2GeH3)(GeH3)
Fe(CO)4(GeH3)(GeMe3)
{Fe(CO)4(GeH2)}2								-Fe-Ge-Fe-Ge- ring
K[Co2(CO)7GeH3]
[PPh4]Co2(CO)7GeH3]
K[Co-(CO)(η5C6H5)GeH3]
[PPh4][Co-(CO)(η5C6H5)GeH3]
K[Co-(CO)(η5C6(CH3)5)GeH3]
[PPh4][Co-(CO)(η5C6(CH3)5)GeH3]
K[(η5-C5H5)-Mn(CO)2GeH3]
K[Ni(CO)3GeH3]
[PPh4][Ni(CO)3GeH3]			monoclinic	C2	a=16.855 b=7.098 c=15.189 β=134.71 Z=2	1291.5	1.43	orange yellow
K[Ni(CO)2(PPh3)GeH3]
[PPh4][Ni(CO)2(PPh3)GeH3]			monoclinic	P21/n	a=10.37 b=22.37 c=16.95 β=96.23 Z=4	2910.6	1.74	orange yellow
As(GeH3)3
Rb([18]crown-6)(thf)GeH3		497.50	monoclinic	Cc	a=13.8336 b=9.9878 c=16.9893 β=107.417 Z=4	2239.7	1.475	colourless
RbGeH3					a=7.518		2.518
K[Nb(CO)3(η5-C5H5)GeH3]
[PPh4][Nb(CO)3(η5-C5H5)GeH3]
K[Mo(CO)5GeH3]
[PPh4][Mo(CO)5GeH3]			monoclinic	C2/c	a=22.25 b=7.021 c=18.545 β=96.14 Z=4	2881	1.5	yellow
Ru(GeH3)(η5-C5H5)(PPh3)P(OMe)3		628.12	monoclinic	P21/c	a=17.932 b=10.067 c=16.375, β=114.508° Z=4	2689.6	1.551	yellow
Ru(GeH3)(η5-C5H5)(PPh3)P(OEt)3								yellow
Ru(GeH3)(η5-C5H5)(PPh3)PPh(OEt)2								yellow
Ru(GeH3)(η5-C9H7)(PPh3)P(OMe)3								yellow
Ru(GeH3)(η5-C9H7)(PPh3)P(OEt)3								yellow
Ru(GeH3)(η5-C9H7)(PPh3)PPh(OEt)2								yellow
Ru(GeH3)(Tp)(PPh3))P(OEt)3								yellow
Ru(GeH3)(Tp)(PPh3)PPh(OEt)2								yellow
cis-[Ru(dppe)2(GeH3)H]•C6H6		1014.4	triclinic	PШаблон:Overbar	a 12.3464 b 13.2412 c 16.2053, α 90.055° β 98.868° γ 116.164° Z=2	2342.3	1.438
trans-[Ru(dppe)2(GeH3)H]
cis-[Ru(depe)2(GeH3)H]
trans-[Ru(depe)2(GeH3)H]
cis-[Ru(dmpe)2(GeH3)H]
trans-[Ru(dmpe)2(GeH3)H]
cis-[Ru(DuPhos)2(GeH3)H]		790.38	orthorhombic	P212121	a 10.1222 b 18.4327 c 19.425 Z=4	3624.4	1.448
Ru(GeH3)(Cp′)L Cp′=η5-C5Me5 L=1,2-[bis(diphenyl) phosphanyloxy]-1,2-diphenylethane
Ru(GeH3)(Cp′)L Cp′=η5-C9H7 L=1,2-[bis(diphenyl) phosphanyloxy]-1,2-diphenylethane
Sb(GeH3)3	trigermylstibine
Cs([18]crown-6)2GeH3		734.12	tetrahedral	P4/n	a=13.2513 c=19.0577 Z=4	3346.5	1.457	colourless
CsGeH3			orthorhombic		a=5.1675 b=14.435 c=5.9664		3.111
K[W(CO)5GeH3]
[PPh4][W(CO)5GeH3]			monoclinic	C2/c	a=22.227 b=7.025 c=18.529 β=96.11 Z=4	2883.2	1.71	yellow
GeH3Re(CO)5	Germylpentacarbonylrhenium							colourless mp 53-54°C
GeH2[Re(CO)5]2	bis(pentacarbonylrhenium)germane
Re(GeH3)(CO)2(PPh(OEt)2)3								white
Re(GeH3)(CO)3(PPh(OEt)2)2								white
Re(GeH3)(CO)2(P(OEt)3)3								white
Re(GeH3)(CO)3(P(OEt)3)2								white
K[Re(CO)2(η5-C5H5)GeH3]
[PPh4][Re(CO)2(η5-C5H5)GeH3]
Os(GeH3)(Tp)(PPh3)P(OMe)3 Tp = tris(pyrazolyl)borate								white

Related

Germylidyne with formula ≡GeH has a triple bond to the metal atom.

Germylidene with base formula =Шаблон:Chem2 has a double bond to the central metal.