Silicide hydride
A silicide hydride is a mixed anion compound that contains silicide (Si4− or clusters) and hydride (H− ) anions . The hydrogen is not bound to silicon in these compounds. These can be classed as interstitial hydrides, Hydrogenated zintl phases, or Zintl phase hydrides.[ 1] In the related silanides , SiH3 − anions or groups occur. Where hydrogen is bonded to the silicon, this is a case of anionic hydride, and where it is bonded to a more complex anion, it would be termed polyanionic hydride.[ 1]
Silicide hydrides may be prepared by heating a Zintl phase or metal silicide under hydrogen pressure, of perhaps 20 atmospheres.[ 2]
Properties
In CaSiD1+x the deuterium atom (D) fits in a tetrahedral hole between three calcium and one silicon atoms. The Si-D distance is 1.82 Å, quite a bit further than then a Si-H covalent bond.[ 3]
List
formula
system
space group
unit cell Å
volume
density
comment
reference
Li4 Si2 H
orthorhombic
Cmmm
zigzag Si chains Si-Si 2.39
[ 4]
CaSiH
[ 3]
CaSiH1+x x<1.2
orthorhombic
Pnma
a = 14.4884, b = 3.8247, c = 11.2509, Z = 3
zigzag Si chains Si-Si 2.47
[ 4]
CaAlSiH
trigonal
Z=1
Al-H bond semimetal
[ 4]
Ca2 SiH2.41
amorphous
a=5.969 b=3.6146 c=6.815
reversible hydrogen storage
[ 4]
Ca5 Si3 H0.53
tetrahedral
I 4/mcm
a=7.6394 c=14.7935 Z=4
863.33
[ 1] [ 5]
SrSiH1.6
orthorhombic
Pnma
[ 6]
SrAlSiH
P 3m 1
Al-H bond semimetal
[ 4]
SrGaSiH
trigonal
P 3m 1
Z=1
grey; Ga-H 1.71 semimetal
[ 4] [ 7]
Sr21 Si2 O5 H21+x
cubic
Fd 3 m
a = 19.1190
[ 8]
BaSiH3.4
orthorhombic
Pnma
[ 6]
Ba3 Si4 Hx (x = 1–2)
tetrahedral
I 4/mcm
a ≈ 8.44, c ≈ 11.95, Z = 8
Si4 6– in a butterfly-shape
[ 2]
Ba21 Si2 O5 H21+x
cubic
Fd 3 m
a = 20.336
[ 8]
BaAlSiH
Al-H bond semimetal
[ 4]
BaGaSiH
trigonal
P 3m 1
a=4.2934 c=5.186 Z=1
82.79
grey; air stable; Ga-H 1.71 semimetal
[ 4] [ 7]
BaGaSiD
trigonal
P 3m 1
a=4.2776 c=5.1948 Z=1
82.32
grey
[ 7]
LaFeSiH
tetragonal
P 4/nmm
a=4.0270 c=8.0374
[ 9]
LaFeSiH
orthorhombic
Cmme
a=5.6831 b=5.7037 c=7.9728
at 15K; superconductor Tc=9.7K
[ 10]
La3 Pd5 SiD~1.6
orthorhombic
Imma
a=13.193 b=7.638 c=7.916
801.8
<9.5 bar
[ 11]
La3 Pd5 SiD~2.71
orthorhombic
Imma
a=13.102 b=7.673 c=8.168
821.3
[ 11]
La3 Pd5 SiD~5
orthorhombic
Pmnb
a=13.16 b=7.91 c=8.20
854
>75 bar
[ 11]
BaLaSi2 D0.80
orthorhombic
Cmcm
a = 4.6443, b = 15.267, c = 6.7630
[ 12]
NdScSiH1.5
tetrahedral
I 4/mmm
a=4.221 c=16.928 Z=4
[ 13]
EuSiH1.8
orthorhombic
Pnma
[ 6]
GdMnSiH
tetragonal
P 4/nmm
[ 14]
GdFeSiH
tetragonal
P 4/nmm
a=3.901 c=7.503
114.2
[ 14]
GdCoSiH
tetragonal
P 4/nmm
a=3.879 c=7.439
111.9
[ 14]
References
^ a b c Haussermann, U.; Kranak, V. F.; Puhakainen, K. (2011). "Hydrogenous Zintl Phases: Interstitial Versus Polyanionic Hydrides". In Fassler, T. F. (ed.). Zintl Phases: Principles and Recent Developments . pp. 139–161.
^ a b Kranak, Verina F.; Benson, Daryn E.; Wollmann, Lukas; Mesgar, Milad; Shafeie, Samrand; Grins, Jekabs; Häussermann, Ulrich (2 February 2015). "Hydrogenous Zintl Phase Ba 3 Si 4 H x ( x = 1–2): Transforming Si 4 "Butterfly" Anions into Tetrahedral Moieties". Inorganic Chemistry . 54 (3): 756–764. doi :10.1021/ic501421u . PMID 25247666 .
^ a b Wu, H.; Zhou, W.; Udovic, T. J.; Rush, J. J.; Yildirim, T. (2006-12-07). "Structure and hydrogen bonding in CaSiD 1 + x : Issues about covalent bonding" . Physical Review B . 74 (22): 224101. doi :10.1103/PhysRevB.74.224101 . ISSN 1098-0121 .
^ a b c d e f g h Häussermann, Ulrich (October 2008). "Coexistence of hydrogen and polyanions in multinary main group element hydrides" . Zeitschrift für Kristallographie . 223 (10): 628–635. doi :10.1524/zkri.2008.1016 . ISSN 0044-2968 . S2CID 96199481 .
^ Wu, Hui; Zhou, Wei; Udovic, Terrence J.; Rush, John J.; Yildirim, Taner (July 2008). "Structural variations and hydrogen storage properties of Ca5Si3 with Cr5B3-type structure" . Chemical Physics Letters . 460 (4–6): 432–437. doi :10.1016/j.cplett.2008.06.018 .
^ a b c Armbruster, Markus; Wörle, Michael; Krumeich, Frank; Nesper, Reinhard (October 2009). "Structure and Properties of Hydrogenated Ca, Sr, Ba, and Eu Silicides" . Zeitschrift für anorganische und allgemeine Chemie . 635 (12): 1758–1766. doi :10.1002/zaac.200900220 .
^ a b c Evans, Michael J.; Holland, Gregory P.; Garcia-Garcia, Francisco J.; Häussermann, Ulrich (2008-09-10). "Polyanionic Gallium Hydrides from AlB 2 -Type Precursors AeGaE (Ae = Ca, Sr, Ba; E = Si, Ge, Sn)" . Journal of the American Chemical Society . 130 (36): 12139–12147. doi :10.1021/ja803664y . ISSN 0002-7863 . PMID 18698774 .
^ a b Jehle, Michael; Hoffmann, Anke; Kohlmann, Holger; Scherer, Harald; Röhr, Caroline (February 2015). "The 'sub' metallide oxide hydrides Sr 21 Si 2 O 5 H 12 + x and Ba 21 M 2 O 5 H 12 + x ( M = Zn, Cd, Hg, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi)" . Journal of Alloys and Compounds . 623 : 164–177. doi :10.1016/j.jallcom.2014.09.228 .
^ Bernardini, F.; Garbarino, G.; Sulpice, A.; Núñez-Regueiro, M.; Gaudin, E.; Chevalier, B.; Méasson, M.-A.; Cano, A.; Tencé, S. (2018-03-12). "Iron-based superconductivity extended to the novel silicide LaFeSiH" . Physical Review B . 97 (10): 100504. arXiv :1701.05010 . doi :10.1103/PhysRevB.97.100504 . hdl :11584/247860 . ISSN 2469-9950 . S2CID 119004395 .
^ Bernardini, F.; Garbarino, G.; Sulpice, A.; Núñez-Regueiro, M.; Gaudin, E.; Chevalier, B.; Méasson, M.-A.; Cano, A.; Tencé, S. (2018-03-12). "Iron-based superconductivity extended to the novel silicide LaFeSiH" . Physical Review B . 97 (10): 100504. arXiv :1701.05010 . doi :10.1103/PhysRevB.97.100504 . hdl :11584/247860 . ISSN 2469-9950 . S2CID 119004395 .
^ a b c Tencé, Sophie; Mahon, Tadhg; Gaudin, Etienne; Chevalier, Bernard; Bobet, Jean-Louis; Flacau, Roxana; Heying, Birgit; Rodewald, Ute Ch.; Pöttgen, Rainer (October 2016). "Hydrogenation studies on NdScSi and NdScGe" . Journal of Solid State Chemistry . 242 : 168–174. doi :10.1016/j.jssc.2016.02.017 .
^ Werwein, Anton; Kohlmann, Holger (2020-07-31). "Synthesis and Crystal Structure of BaLaSi 2 H 0.80" . Zeitschrift für anorganische und allgemeine Chemie . 646 (14): 1227–1230. doi :10.1002/zaac.202000152 . ISSN 0044-2313 . S2CID 219060294 .
^ Tencé, Sophie; Mahon, Tadhg; Gaudin, Etienne; Chevalier, Bernard; Bobet, Jean-Louis; Flacau, Roxana; Heying, Birgit; Rodewald, Ute Ch.; Pöttgen, Rainer (October 2016). "Hydrogenation studies on NdScSi and NdScGe" . Journal of Solid State Chemistry . 242 : 168–174. doi :10.1016/j.jssc.2016.02.017 .
^ a b c Ovchenkova, I. A.; Nikitin, S. A.; Tereshina, I. S.; Karpenkov, A. Yu.; Ovchenkov, Y. A.; Ćwik, J.; Koshkid’ko, Yu. S.; Drulis, H. (2020-10-14). "Hydrogen-induced extremely large change in Curie temperatures in layered GdTSiH (T = Mn, Fe, Co)" . Journal of Applied Physics . 128 (14): 143903. doi :10.1063/5.0020513 . ISSN 0021-8979 . S2CID 225150947 .
Salts and covalent derivatives of the
silicide ion
SiH4 +H
He
LiSi
Be2 Si
SiB3 SiB6 +B
SiC +C
Si3 N4 -N +N
SiO2
SiF4
Ne
NaSi
Mg2 Si
Al
Si4−
SiP, SiP2 -P +P
SiS2 -S
SiCl4
Ar
KSi
CaSi CaSi2
ScSi Sc5 Si3 Sc2 Si3 Sc5 Si4
TiSi TiSi2
V3 Si V5 Si3 , V6 Si5 , VSi2 , V6 Si5
Cr3 Si Cr5 Si3 , CrSi, CrSi2
MnSi , MnSi2 , Mn9 Si2 , Mn3 Si, Mn5 Si3 , Mn11 Si9
FeSi2 FeSi Fe5 Si3 Fe2 Si Fe3 Si
CoSi , CoSi2 , Co2 Si , Co3 Si
NiSi , more…
Cu17 Si3 , Cu56 Si11 , Cu5 Si, Cu33 Si7 , Cu4 Si, Cu19 Si6 , Cu3 Si, Cu87 Si13
Zn
Ga
GeSi +Ge
SiAs, SiAs2 -As +As
SiSe2 SiSe
SiBr4
Kr
RbSi
SrSi2
YSi Y5 Si3 , Y5 Si4 , Y3 Si5 , YSi1.4
ZrSi Zr5 Si3 , Zr5 Si4 , ZrSi2 , Zr3 Si2 , Zr2 Si, Zr3 Si
Nb4 Si Nb5 Si3
MoSi2 Mo3 Si Mo5 Si3
Tc
RuSi Ru2 Si, Ru4 Si3 , Ru2 Si3
RhSi Rh2 Si, Rh5 Si3 , Rh3 Si2 , Rh20 Si13
PdSi Pd5 Si, Pd9 Si2 , Pd3 Si, Pd2 Si
Ag
Cd
In
Sn
Sb
TeSi2 Te2 Si3
SiI4
Xe
CsSi
Ba2 Si BaSi2 , Ba5 Si3 Ba3 Si4
*
Lu5 Si3
HfSi Hf2 Si, Hf3 Si2 , Hf5 Si4 , HfSi2
Ta9 Si2 , Ta3 Si, Ta5 Si3
WSi2 W5 Si3
ReSi Re2 Si, ReSi1.8 Re5 Si3
OsSi
IrSi
PtSi
Au
Hg
Tl
Pb
Bi
Po
At
Rn
Fr
Ra
**
Lr
Rf
Db
Sg
Bh
Hs
Mt
Ds
Rg
Cn
Nh
Fl
Mc
Lv
Ts
Og
*
LaSi2 La5 Si3 , La3 Si2 , La5 Si4 , LaSi
CeSi2 Ce5 Si3 , Ce3 Si2 , Ce5 Si4 , CeSi , Ce3 Si5
PrSi2 Pr5 Si3 , Pr3 Si2 , Pr5 Si4 , PrSi
NdSi Nd5 Si3 , Nd5 Si4 , Nd5 Si3 , Nd3 Si4 , Nd2 Si3 , NdSix
Pm
SmSi2 Sm5 Si4 , Sm5 Si3 , SmSi, Sm3 Si5
Eu?
GdSi2 Gd5 Si3 , Gd5 Si4 , GdSi
TbSi2 SiTb, Si4 Tb5 , Si3 Tb5
DySi2 DySi
HoSi2 Ho5 Si3 , Ho5 Si4 , HoSi, Ho4 Si5
ErSi2 Er5 Si3 , Er5 Si4 , ErSi
Tm?
YbSi Si1.8 Yb, Si5 Yb3 , Si4 Yb3 , Si4 Yb5 , Si3 Yb5
**
Ac
ThSi
PaSi
USi2
NpSi2
PuSi
Am
Cm
Bk
Cf
Es
Fm
Md
No