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
Li4Si2H 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]
Ca2SiH2.41 amorphous a=5.969 b=3.6146 c=6.815 reversible hydrogen storage [4]
Ca5Si3H0.53 tetrahedral I4/mcm a=7.6394 c=14.7935 Z=4 863.33 [1][5]
SrSiH1.6 orthorhombic Pnma [6]
SrAlSiH P3m1 Al-H bond semimetal [4]
SrGaSiH trigonal P3m1 Z=1 grey; Ga-H 1.71 semimetal [4][7]
Sr21Si2O5H21+x cubic Fd3m a = 19.1190 [8]
BaSiH3.4 orthorhombic Pnma [6]
Ba3Si4Hx (x = 1–2) tetrahedral I4/mcm a ≈ 8.44, c ≈ 11.95, Z = 8 Si46– in a butterfly-shape [2]
Ba21Si2O5H21+x cubic Fd3m a = 20.336 [8]
BaAlSiH Al-H bond semimetal [4]
BaGaSiH trigonal P3m1 a=4.2934 c=5.186 Z=1 82.79 grey; air stable; Ga-H 1.71 semimetal [4][7]
BaGaSiD trigonal P3m1 a=4.2776 c=5.1948 Z=1 82.32 grey [7]
LaFeSiH tetragonal P4/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]
La3Pd5SiD~1.6 orthorhombic Imma a=13.193 b=7.638 c=7.916 801.8 <9.5 bar [11]
La3Pd5SiD~2.71 orthorhombic Imma a=13.102 b=7.673 c=8.168 821.3 [11]
La3Pd5SiD~5 orthorhombic Pmnb a=13.16 b=7.91 c=8.20 854 >75 bar [11]
BaLaSi2D0.80 orthorhombic Cmcm a = 4.6443, b = 15.267, c = 6.7630 [12]
NdScSiH1.5 tetrahedral I4/mmm a=4.221 c=16.928 Z=4 [13]
EuSiH1.8 orthorhombic Pnma [6]
GdMnSiH tetragonal P4/nmm [14]
GdFeSiH tetragonal P4/nmm a=3.901 c=7.503 114.2 [14]
GdCoSiH tetragonal P4/nmm a=3.879 c=7.439 111.9 [14]

References

  1. ^ 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.
  2. ^ 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.
  3. ^ 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.
  4. ^ 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.
  5. ^ 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.
  6. ^ 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.
  7. ^ 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.
  8. ^ 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.
  9. ^ 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.
  10. ^ 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.
  11. ^ 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.
  12. ^ 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.
  13. ^ 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.
  14. ^ 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.
  • v
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Salts and covalent derivatives of the silicide ion
SiH4
+H 		He
LiSi Be2Si SiB3
SiB6
+B 		SiC
+C 		Si3N4
-N
+N 		SiO2 SiF4 Ne
NaSi Mg2Si Al Si4− SiP, SiP2
-P
+P 		SiS2
-S 		SiCl4 Ar
KSi CaSi
CaSi2 		ScSi Sc5Si3 Sc2Si3 Sc5Si4 TiSi
TiSi2 		V3Si V5Si3, V6Si5, VSi2, V6Si5 Cr3Si Cr5Si3, CrSi, CrSi2 MnSi, MnSi2, Mn9Si2, Mn3Si, Mn5Si3, Mn11Si9 FeSi2
FeSi
Fe5Si3
Fe2Si
Fe3Si 		CoSi, CoSi2, Co2Si, Co3Si NiSi, more… Cu17Si3, Cu56Si11, Cu5Si, Cu33Si7, Cu4Si, Cu19Si6, Cu3Si, Cu87Si13 Zn Ga GeSi
+Ge 		SiAs, SiAs2
-As
+As 		SiSe2 SiSe SiBr4 Kr
RbSi SrSi2 YSi Y5Si3, Y5Si4, Y3Si5, YSi1.4 ZrSi Zr5Si3, Zr5Si4, ZrSi2, Zr3Si2, Zr2Si, Zr3Si Nb4Si Nb5Si3 MoSi2
Mo3Si Mo5Si3 		Tc RuSi Ru2Si, Ru4Si3, Ru2Si3 RhSi Rh2Si, Rh5Si3, Rh3Si2, Rh20Si13 PdSi Pd5Si, Pd9Si2, Pd3Si, Pd2Si Ag Cd In Sn Sb TeSi2 Te2Si3 SiI4 Xe
CsSi Ba2Si BaSi2, Ba5Si3 Ba3Si4 * Lu5Si3 HfSi Hf2Si, Hf3Si2, Hf5Si4, HfSi2 Ta9Si2, Ta3Si, Ta5Si3 WSi2 W5Si3 ReSi Re2Si, ReSi1.8 Re5Si3 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 La5Si3, La3Si2, La5Si4, LaSi CeSi2 Ce5Si3, Ce3Si2, Ce5Si4, CeSi, Ce3Si5 PrSi2 Pr5Si3, Pr3Si2, Pr5Si4, PrSi NdSi Nd5Si3, Nd5Si4, Nd5Si3, Nd3Si4, Nd2Si3, NdSix Pm SmSi2 Sm5Si4, Sm5Si3, SmSi, Sm3Si5 Eu? GdSi2 Gd5Si3, Gd5Si4, GdSi TbSi2 SiTb, Si4Tb5, Si3Tb5 DySi2 DySi HoSi2 Ho5Si3, Ho5Si4, HoSi, Ho4Si5 ErSi2 Er5Si3, Er5Si4, ErSi Tm? YbSi Si1.8Yb, Si5Yb3, Si4Yb3, Si4Yb5, Si3Yb5
** Ac ThSi PaSi USi2 NpSi2 PuSi Am Cm Bk Cf Es Fm Md No