Silanide

A silanide is a chemical compound containing an anionic silicon(IV) centre, the parent ion being SiH−3. The hydrogen atoms can also be substituted to produced more complex derivative anions such as tris(trimethylsilyl)silanide (hypersilyl),[1] tris(tert-butyl)silanide, tris(pentafluoroethyl)silanide, or triphenylsilanide.[2] The simple silanide ion can also be called trihydridosilanide or silyl hydride.

Silanide
Names
Other names
Trihydridosilanide
Trihydridosilicate(1-)
Trihydridosilicate(IV)
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
266
  • InChI=1S/H3Si/h1H3/q-1
    Key: LNVJLOIIRUIQCP-UHFFFAOYSA-N
  • [SiH3-]
Properties
SiH−3
Molar mass 31.109 g·mol−1
Related compounds
Related compounds
 Methyl anion, Germyl, Stannyl, Phosphinide, Arsinide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Formation

The simplest trihydridosilanides can be produced from a triphenylsilanide in a reaction with hydrogen or PhSiH3 at standard conditions. The triphenylsilanide can be made in a reaction of Ph3SiSiMe3 with the metal tert-butoxy compound.[3]

Reacting hydrogen with potassium triphenylsilyl K(Me6TREN)SiPh3 can yield potassium silanide.[4]

Other method to form silanides are to heat a heavy metal silicide with hydrogen,[5] or react the dissolved metal with silane.[3]

Atomic metals can react directly with silane to yield unstable molecules with HMSiH3 formulae. These can be condensed into a noble gas matrix. With titanium this also yields molecules with hydrogen bridging between silicon and titanium.[6]

Properties

The silanide ion has an effective ionic radius of 2.26 Å. In salts at room temperature the ion's orientation is not stable, and it rotates. But at lower temperatures (under 200K) silanide becomes fixed in orientation.[7] The ordered structure forms the β- phase, whereas the higher temperature and more symmetrical disordered structure is called α- phase. The β- phase is about 15% more compact than the α-phase.[8]

The silanide ion has C3v symmetry. The silicon to hydrogen bond length is 1.52 Å and the H-Si-H bond angle is 92.2°, not far off a right angle.[8] In a range of compounds, the stretching force constant for the Si-H bond is 1.9 to 2.05 N cm–1, which is much softer than that of silane's 2.77 N cm–1.[8]

Silanide salts are very easily damaged by air or water.[7]

Heating to under 414K results in the release of hydrogen and the formation of a Zintl-phase MSi. If an alkali silande is rapidly heated to 500K another irreversible reaction occurs:

46KSiH3 → K8Si46 + 38KH + 50H2.[9]

Use

Trihydridosilanides have been investigated as hydrogen storage materials.[10] Potassium silanide can reversibly gain or lose hydrogen over several hours at 373K. However this does not work for sodium silanide.[5] The rate of hydrogen exchange may be improved by a catalyst. Unwanted reactions may reduce the number of times this process can happen.[11]

List
name formula Crystal system space group unit cell volume density comment references
tetramethyl-1,4,7,10-tetraaminocyclododecane lithium silanide Li(Me4TACD)SiH3 colourless; unstable [3]
trisilylamine N(SiH3)3 mp -105 °C; planar [12]
tetramethyl-1,4,7,10-tetraaminocyclododecane sodium silanide Na(Me4TACD)SiH3 tetragonal P4/n a=9.77 c=9.45 Z=2 901 1.041 colourless [3]
Na8(OC2H4OC2H4OCH3)6(SiH3)2 H is bridge [13]
trisilylphosphine P(SiH3)3 [14]
Potassium silanide KSiH3 cubic a=7.23 377.9 1.241 pale yellow [7][15]
β-KSiH3 orthorhombic Pnma a = 8.800, b = 5.416, c = 6.823, Z = 4 325.2 [16]
tetramethyl-1,4,7,10-tetraaminocyclododecane potassium silanide K(Me4TACD)SiH3•2C6H6 tetragonal P42/mnm a=12.3401 c=14.9372 Z=2 2274.6 1.10 colourless [3]
[K(18-crown-6)SiH3·THF] [17]
[K(18-crown-6)SiH3·HSiPh3] H is bridge [17]
Cp2(Me3P)TiSiH3 purple [6]
[(C5H5)2TiSiH2]2 tetragonal P42/mnm a = 8.018, c = 16.113, Z = 2 olive green; Ti-SiH2-Ti-SiH2- ring [18]
[Cp2Ti(μ-HSiH2)]2 dark blue [19]
Cp2Ti(μ-HSiH2)(μ-H)TiCp2 dark yellowish green [19]
HCrSiH3 [6]
[Cp(OC)2Fe]2SiH2 triclinic P1 a=6.318 b=10.653 c=12.453 α=67.884 β=75.35 γ=72.79 Z=2 732.1 1.742 light yellow [20]
[(μ2-CO)Cp2(OC)2Fe2]SiH2 dark red [20]
[(μ2-CO)Cp2(OC)2Fe2][Cp(OC)2Fe]SiH dark red [20]
HNiSiH3 [6]
HZnSiH3 [6]
[(dtbpCbz)GeSiH3]2•C6H18 monoclinic P21/n a 16.144 b 15.0369 c 21.974 β 91.927° [21]
trisilylarsine As(SiH3)3 [14]
rubidium silanide RbSiH3 cubic a=7.52 425.3 1.824 yellow [7]
tetramethyl-1,4,7,10-tetraaminocyclododecane rubidium silanide Rb(Me4TACD)SiH3•2C6H6 tetragonal P42/mnm a=12.3934 c=14.9632 Z=2 2298.3 1.223 yellow [3]
K0.5Rb0.5SiH3 cubic P43m a=12.832 2112.7 [22]
Mo(CO)(H)(SiH3)(depe)2 [6]
[Cp(OC)2Ru]2SiH2 beige mp 25 [20]
trisilylstibine Sb(SiH3)3 [14]
caesium silanide CsSiH3 cubic a=7.86 485.6 2.243 yellow [3][7]
Cs0.5K0.5SiH3 cubic P43m a=13.0965 2246.3 [22]
Cs0.5Rb0.5SiH3 cubic P43m a=13.2982 2351.7 [22]
bis(di-tert-butylphenyl)di-tert-butylcanozalide [(dtbpCbz)BaSiH3]8 P4/nnc a=38.7375 c=44.8635 [21]
[Cp2SmSiH3]3 orange [6]
(C5Me5)Sm(SiH3)(THF)(C5Me5)K(THF) dark red [23]
(C5Me5)Eu(SiH3)(THF)(C5Me5)K(THF) orthorhombic Pna21 a=19.320 b=16.742 c=10.027 Z=4 3240.0 1.406 orange-red [23]
(C5Me5)Yb(SiH3)(THF)(C5Me5)K(THF) orthorhombic Pna21 a=19.321 b=16.496 c=9.926 Z=4 3163.7 dark red [23]
Cp(iPr3P)Os(H)(Br)SiH3 yellow [6]
trans-(Cy3P)2HPtSiH3 [6]

Under high hydrogen pressure, pentacoordinated and hexacoordinated silicon hydride ions are stabilised including SiH−5 and SiH2−6.[24]

More complex derivatives include silanimine -NHSiH3,[25]

With a double bond between silicon and the metal a silylene complex is formed. With a triple bond, M≡SiH forms with metals such as molybdenum and tungsten.

With less hydrogen, a polyanionic hydride ∞
1[(SiH)−] can be formed.[26]

General organic compounds are termed silylium ions.

References
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  2. Lickiss, Paul D.; Smith, Colin M. (November 1995). "Silicon derivatives of the metals of groups 1 and 2". Coordination Chemistry Reviews. 145: 75–124. doi:10.1016/0010-8545(95)90218-X.
  3. Schuhknecht, Danny; Leich, Valeri; Spaniol, Thomas P.; Douair, Iskander; Maron, Laurent; Okuda, Jun (2 March 2020). "Alkali Metal Triphenyl‐ and Trihydridosilanides Stabilized by a Macrocyclic Polyamine Ligand". Chemistry – A European Journal. 26 (13): 2821–2825. doi:10.1002/chem.202000187. PMC 7079104. PMID 31943432.
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