Chemistry:Phosphinate

From HandWiki

Phosphinates or hypophosphites are a class of phosphorus compounds conceptually based on the structure of hypophosphorous acid. IUPAC prefers the term phosphinate in all cases, however in practice hypophosphite is usually used to describe inorganic species (e.g. sodium hypophosphite), while phosphinate typically refers to organophosphorus species.

Hypophosphites

The hypophosphite ion is (H2PO2)−. The salts are prepared by heating white phosphorus in warm aqueous alkali e.g. Ca(OH)2:[1]

P4 + 2 Ca(OH)2 + 4 H2O → 2 Ca(H2PO2)2 + 2 H2

Hypophosphites are reducing agents:[1]

(H2PO2)− + 3 OH− → (HPO3)2− + 2 H2O + 2 e−

Hypophosphites are used in electroless nickel plating as the reducing agent to deposit for example Ni metal from Ni salts.[1] The hypophosphite ion is thermodynamically unstable, and disproportionates on heating to phosphine and phosphate salts:

2 H2PO2− → PH3 + HPO42−

Reactions

When heated, sodium hypophosphite disproportionates to PH3, Na2H2P2O5, Na2HPO3, Na4P2O7 and H2.[2]

When exposed to light ammonium hypophosphite darkens. A proposed reaction is:[3]

[H2PO2]− → H• + [HP•O2]−
[HP•O2]− + [H2PO2]− → H• + [O2P•PHO2]2−

Uses

Hypophosphite (usually sodium hypophosphite) acts as a reducing agent to deposit nickel onto surfaces without using electricity. Common in electronics, automotive, and aerospace industries for corrosion resistance and hardness. Some hypophosphite compounds are used in medicines, particularly as sources of phosphorus or as stabilizers in formulations.

In polymer and plastic stabilization, they are used today as antioxidants and thermal stabilizers to prevent degradation during the processing of plastics like PVC. Beyond nickel plating, hypophosphites are used in general chemical synthesis where a mild reducing agent is needed.

Additionally, in wood science, sodium hypophosphite in combination with other agents, such as ammonium-, nitrogen- or aluminium-containing chemicals, has been used for in solid wood and particleboard to improve the fire retarding properties.[4][5]

List

name formula system space group unit cell volume density comment ref
lithium di­hydrogenphosphate LiH2PO2 monoclinic C2/c a = 9.356 b = 5.3107 c = 6.543 β = 108.26° Z=4 308.73 1.547 [6][7]
beryllium bis(di­hydrogenphosphate) Be(H2PO2)2 tetragonal P41212 a = 5.0117 c = 20.051 Z=4 503.62 1.833 band gap 7.84 eV [8][7]
ammonium hypophosphite (NH4)H2PO2 orthorhombic Cmma a = 7.5425 b = 11.5204 c = 3.9942 Z = 4 347.07 1.589 [9]
Hydrazinium(2+) phosphinate (N2H6)(H2PO2)2 monoclinic P21/c a = 7.74 b = 6.44 c = 6.77 β = 98.1° [10]
1,3-diaminoguanidinium(1+) hypophosphite (CN5H8)H2PO2 monoclinic P21/c ?P21/m a=6.3673 b=14.5302 c=66452 β=16742° [11]
triethylammonium hypophosphite hydrate (Et3NH)(H2PO2)·H2O [12]
NaH2PO2•0.8H2O monoclinic P21/n a=11.127 b=13.572 c=12.93 β=102.98° Z=20 [13]
Mg(H2PO2)2 [14]
Mg(PO2H2)2.6H2O tetragonal I41/acd a=10.33 c=20.38 Z=8 1.60 [15]
hexa­aqua­magnesium(II) bis­(hypophosphite) [Mg(H2O)6](H2PO2)2 tetragonal P42/nmc a=7.2187 c=10.4639 Z=2 542.27 1.598 [16]
Al(H2PO2)3 [17]
Potassium hypophosphite KH2PO2 monoclinic C2/c a = 7.313 b = 7.2952 c = 7.181 β = 116.20° Z = 4 343.75 [18]
calcium hypophosphite Ca(H2PO2)2 [19]
calcium sodium hypophosphite NaCa(H2PO2)2 cubic P213 a = 9.720 918.3 1.90 [20]
Ti(H2PO2)3 trigonal R3c a=11.7484 c=9.7368 Z=6 1163.9 2.079 blue [21]
vanadium(III) hypophosphite V(H2PO2)3 monoclinic P21/n a = 11.4985 b = 11.7771 c = 11.5999 β = 99.807° 1547.89 2.11 green [22]
VO(H2PO2)·H2O monoclinic C2/c a = 12.046 b = 8.147 c = 7.548 β = 121.83° blue [23][24]
manganese hypophosphite monohydrate Mn(H2PO2)2.H2O monoclinic P21/c a = 7.8601 b = 7.4411 c = 10.7717 β = 102.859° Z=4 [25]
manganese hypophosphite monohydrate β-Mn(H2PO2)2.H2O monoclinic P21/n 12.013 b=8.100 c=12.450 β=106.28° Z=8 [26]
(μ3-Hypophosphito)-(μ2-hypophosphito)-manganese dimethylformamide solvate [Mn(H2PO2)2]n·(DMF)0.11 hexagonal R3 a=20.53 c=8.041 [27]
[NH4][MnII(H2PO2)3(H2O)] monoclinic P21/n a=7.4412 b=15.147 c=9.3051 β=108.230° [28]
guanidinium manganese hypophosphite CN3H6 Mn(H2POO)3 monoclinic I2/m a=8.7596 b=13.2087 c=9.6956 β=89.764° [29]
guanidinium manganese hypophosphite CN3H6 Mn(H2POO)3 triclinic P1 a=9.0994 b=9.2419 c=15.8369 α=105.294° β=90.971° γ=118.618° [29]
formamidinium manganese hypophosphite CN2H5Mn(H2POO)3 monoclinic C2/c a=13.4506 b=10.2196 c=7.5274 β=103.604° [29]
imidazolium manganese hypophosphite C3H52Mn(H2POO)3 monoclinic P21/c a=9.6520 b=12.7066 c=18.4643 β=91.5450° [29]
triazolium manganese hypophosphite C2H4N3Mn(H2POO)3 monoclinic P21/c a=9.8034 b=8.5924 c=13.3120 β=98.554° [29]
dabcon-diium dimanganese hexakis(hypophosphite) C6H14N2Mn2(H2POO)6 hexagonal R3 a=9.8860 c=41.171 [29]
dabcon-diium dimanganese hexakis(hypophosphite) C6H14N2Mn2(H2POO)6 triclinic P1 a=9.8364( b=14.9329 c=16.8019 α=66.631° β=89.585° γ=89.082° [29]
bis(μ2-Phosphinato)-bis(5,10,15,20-tetraphenylporphyrinato)-di-manganese ethanol solvate monohydrate monoclinic P21/n a=13.2131 b=25.263 c=23.477 β=95.31° [30]
Bis(phosphinato)(2,2'-bipyridyl)manganese(II) C10H12N2Mn(H2PO2)2 monoclinic C2/c a=16.827 b=10.745 c=7.170 β=91.46° X=4 1.75 yellow [31]
iron(III) hypophosphite Fe(H2PO2)3 hexagonal R3 a = 11.2800 c = 9.6375 Z = 6 1061.97 2.353 [32]
hexa­aqua­cobalt(II) bis­(hypophosphite) [Co(H2O)6](H2PO2)2 tetragonal I41/acd a=10.3406 c=20.402 Z=8 2181.6 1.809 purple [33][34]
Co(H2PO2)2•0.53H2O monoclinic P112/a a=6.4722 b=5.3411 c=7.4900 γ=90.087° Z=2 layered, can intercallate with more water, or pyridine [35]
Co(H2PO2)2•2H2O
[NH4][CoII(H2PO2)3(H2O)] monoclinic P21/n a=7.367 b=14.914 c=9.205 β=108.38° [28]
CoCl(H2PO2).H2O orthorhombic Pbca a=7.416 b=13.082 c=9.483 Z=8 920 2.56 [36]
bis(μ-hypophosphito)-bis(benzene-1,2-diamine)-cobalt dichloride [Co(H2PO2)(C12N4H16)]Cl2 orthorhombic Pbcn a = 9.554 b = 9.147 c = 21.9222 Z = 2 1915.7 [37]
ortho-phenylenediamine cobalt hypophosphite chloride [Co(H2PO2)(C12N4H16)]Cl2 orthorhombic Pbcn a = 9.554 b = 9.147 c = 21.9222 Z = 2 1915.7 [38]
CoIII(NH3)5(H2PO2)(ClO4)2 [39]
NaCo(H2PO2)3 cubic P213 a = 9.256 Z=4 793.1 [40]
Hexa­aqua­nickel(II) bis­(hypophosphite) [Ni(H2O)6](H2PO2)2 monoclinic C2/c a = 10.1453 b = 10.1467 c = 10.3571 β = 92.632 Z=4 1065.05 1.851 green [33]
[NH4][NiII(H2PO2)3(H2O)] monoclinic P21/n a=7.3202 b=14.7961 c=9.1762 β=108.814° [28]
(μ2-13,27-Di-t-butyl-3,6,9,17,20,23-hexamethyl-3,6,9,17,20,23-hexaazatricyclo[23.3.1.111,15]triaconta-1(29),11(30),12,14,25,27-

hexaene-29,30-dithiolato)-(μ2-phosphinato-O,O')-di-nickel(ii) tetraphenylborate acetonitrile solvate

[Ni2L(μ-O2PH2)]BPh4 triclinic P1 a=13.179 b=15.736 c=16.799 α=108.48° β=91.90° γ=107.61° [41]
" [Ni2L(μ-O2PH2)]ClO4 [41]
NiCl(H2PO2).H2O orthorhombic Pbca a = 7.2986 b = 13.0616 c = 9.4078 Z = 4 896.85 pale green; hypophosphite [42]
hexa­aqua­cobalt(II)/nickel(II) bis(hypophosphite) [Co0.5Ni0.5(H2O)6](H2PO2)2 tetragonal I41/acd a=10.3111 c=20.236 Z=8 2163.2 1.823 green [34]
Cu(H2PO2)2 monoclinic P21/c a = 7.2186 b = 5.3462 c = 6.2521 β = 98.835° Z = 2 T = 270 238.42 2.696 blue [43]
Cu(H2PO2)2 orthorhombic Pbca a = 5.3259 b = 6.2720 c = 14.2590 Z=4 T = 270 476.31 2.699 blue [43]
Cu(H2PO2)2 orthorhombic Pnma a = 6.6738 b = 5.4133 c = 7.1954 Z=2 T = 270 259.95 2.472 blue [43]
Zn(H2PO2)2 orthorhombic Pmma a=6.479 b=5.365 c=7.408 [44]
Zn(H2PO2)2.H2O monoclinic P21/c a=7.685 b=7.376 c=10.468 β=104.16° [44]
Ge2(H2PO2)6 trigonal R3 a=11.86 c=9.58 Z=3 2.18 colourless [45]
Chloro(phosphinato)germanium(II) GeCl(H2PO2) orthorhombic Pnam a=8.178 b=9.595 c=5.299 Z=4 2.764 [46]
Rubidium hypophosphite RbH2PO2 orthorhombic Pnma a = 7.9835 b = 6.3678 c = 7.575 Z = 4 385.12 [18]
Sr(H2PO2)2 monoclinic C2/c a = 15.655 b = 5.9436 c = 5.9177 β = 93.905° Z=4 549.4 2.631 colourless [47]
Cadmium bis­[dihydrogenphosphate(I)] Cd(H2PO2)2•H2O monoclinic C2/c a = 15.156 b = 5.4692 c = 6.5516 β=102.487 Z=4 530.22 3.036 [48][49]
Chloro(phosphinato)tin(II) SnCl(H2PO2) orthorhombic Pnam a=8.045 b=9.915 c=5.517 Z=4 3.308 [46]
Calcium hexa­kis(di­hydrogen­phosphito)­stannate(IV) Ca[Sn(H2PO2)6] hexagonal R3 a = 11.8619 c = 9.8668 Z = 3 1202.31 2.273 [50]
[Sn2(H2PO2)3]Br orthorhombic Pmn21 a=5.4177 b=7.1467 c=13.8359 Z=2 535.71 3.176 [51]
RbSb(SO4)(H2PO2)F orthorhombic Pnma a=15.1004 b=5.4481 c=8.8857 Z=4 731.01 3.519 dark [52]
Cesium hypophosphite CsH2PO2 orthorhombic Pnma a = 8.3776 b = 6.6271 c = 7.916 Z = 4 439.52 [18]
barium bis­(di­hydrogen­phos­phate) Ba(H2PO2)2 orthorhombic Ccca a = 6.2390 b = 15.584 c = 6.1726 Z=4 600.2 2.958 colourless [47]
BaSb(H2PO2)3Cl2 monoclinic P21 a=8.5451 b=7.6108 c=9.0163 β=95.680° SHG 5.0 × KDP; birefringence (0.09@546 nm); bandgap 4.2 eV [53]
La(H2PO2)3 triclinic P1 a = 6.7912 b = 7.0801 c = 8.863 α = 82.64° β = 74.43o γ = 71.91° Z=2 [54]
La(H2PO2)3•H2O triclinic P1 a = 7.2291 b = 7.983 c = 8.934 α =110.57° β = 98.26° γ = 104.35° Z=2 [54]
Ce(H2PO2)3(H2O) triclinic P1 a=7.1729 b=7.9827 c=8.871 α=110.643° β=98.101° γ=104.97° [55]
Pr(H2PO2)3 [54]
[Pr(H2PO2)(HPO3)(H2O)]·H2O orthorhombic P212121 a=6.6558 b=7.1539 c=16.5506 [55]
Nd(H2PO2)3 [54]
Dy(H2PO2)3 monoclinic C2/m a=14.368 b=5.734 c=12.123 β=122.33° [55]
Yb(H2PO2)3 monoclinic C2/m a=14.281 b =5.658 c=12.006 β=122.26° [56]
Thallous hypophosphite TlH2PO2 melt 114°C [49][57]
Pb(H2PO2)2 monoclinic C2/c a = 15.516 b = 6.008 c = 5.969 β = 93.30° Z=4 555.5 4.032 colourless [47]
U(H2PO2)4 orthorhombic Pbca a=7.467 b=13.394 c=19.904 Z=8 1990.7 3.323 green [43]
UO2(H2PO2)2·H2O monoclinic P21/n a = 7.686 b = 9.275 c = 11.027 β = 92.32° Z=4 785.4 3.535 colourless [58]
UO2(H2PO2)2·H3PO orthorhombic P212121 a = 7.1572 b = 7.2363 c = 17.554 901.0 3.435 yellow [58]

See also

References

  1. ↑ 1.0 1.1 1.2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 512. ISBN 978-0-08-037941-8. 
  2. ↑ Liu, Dapeng; Li, Xiang; Wei, Ling; Zhang, Tingting; Wang, Anjie; Liu, Chenguang; Prins, Roel (2017). "Disproportionation of hypophosphite and phosphite" (in en). Dalton Transactions 46 (19): 6366–6378. doi:10.1039/C7DT00243B. ISSN 1477-9226. PMID 28466903. https://xlink.rsc.org/?DOI=C7DT00243B. 
  3. ↑ Morton, J.R. (May 1962). "The E.S.R. spectrum of irradiated ammonium hypophosphite". Molecular Physics 5 (3): 217–223. doi:10.1080/00268976200100231. 
  4. ↑ Pan, Fangya; Jia, Hongyu; Huang, Yuxiang; Chen, Zhilin; Liang, Shanqing; Jiang, Peng (2023-11-21). "Analyzing Temperature Distribution Patterns on the Facing and Backside Surface: Investigating Combustion Performance of Flame-Retardant Particle Boards Using Aluminum Hypophosphite, Intumescent, and Magnesium Hydroxide Flame Retardants". Polymers (MDPI AG) 15 (23): 4479. doi:10.3390/polym15234479. ISSN 2073-4360. 
  5. ↑ Kim, Injeong; Ross, Lone; Alfredsen, Gry; Karlsson, Olov; Kaynak, Elif; Das, Oisik; Jones, Dennis; Mantanis, George I. et al. (2025-03-16). "Enhancement of Biological Durability and Fire Safety in Wood Modified with Maleic Anhydride and Sodium Hypophosphite". Forests (MDPI AG) 16 (3): 526. doi:10.3390/f16030526. ISSN 1999-4907. 
  6. ↑ Lozanov, Ivo I.; Romanova, J.; Mitrev, B.; Kolev, K.; Todorova, St.; Lyutov, L. (August 2026). "Spectroscopic, thermal and physicochemical characterization of LiH2PO2 – the underexplored alkali hypophosphite" (in en). Journal of Solid State Chemistry 360. doi:10.1016/j.jssc.2026.126068. https://linkinghub.elsevier.com/retrieve/pii/S0022459626002641. 
  7. ↑ 7.0 7.1 Naumov, Dmitry Yu.; Naumova, Marina I.; Podberezskaya, Nina V.; Kuratieva, Natalia V. (2004-08-15). "Lithium and beryllium hypophosphites". Acta Crystallographica Section C Crystal Structure Communications 60 (8): i73–i75. doi:10.1107/S0108270104013691. ISSN 0108-2701. PMID 15295160. https://journals.iucr.org/paper?S0108270104013691. 
  8. ↑ Liu, Xin; Wu, Li-Ming; Kang, Lei; Lin, Zheshuai; Chen, Ling (October 2024). "Theoretical Prediction of Monolayer BeP 2 O 4 H 4 with Excellent Nonlinear-Optical Properties in Deep-Ultraviolet Range" (in en). Small 20 (40). doi:10.1002/smll.202404155. ISSN 1613-6810. PMID 38855996. Bibcode: 2024Small..2004155L. https://onlinelibrary.wiley.com/doi/10.1002/smll.202404155. 
  9. ↑ Naumova, M. I.; Kuratieva, N. V.; Naumov, D. Yu.; Podberezskaya, N. V. (May 2004). "Synthesis and crystal structures of anhydrous lithium and ammonium hypophosphites" (in en). Journal of Structural Chemistry 45 (3): 465–470. doi:10.1007/s10947-005-0014-9. ISSN 0022-4766. Bibcode: 2004JStCh..45..465N. https://link.springer.com/10.1007/s10947-005-0014-9. 
  10. ↑ Weakley, T. J. R. (2011-08-18). "The Crystal Structures of Ammonium Phosphinate (Hypophosphite) and Guanidinium Ph08phinate, and the Cell Parameters of Hydrazinium(2+) Phosphinate". Journal of The Chemical Society of Pakistan 1 (2): 37. https://jcsp.org.pk/home.aspx. 
  11. ↑ Kohúteková, Soňa; Matulková, Irena; Zábranský, Martin; Martín, Jaime Lledó; Císařová, Ivana; Gyepes, Róbert; Němec, Petr; Gryl, Marlena et al. (November 2023). "New group of inorganic salts of 1,3-diaminoguanidinium(1+) cation – crystal structures, vibrational spectra, linear and nonlinear optical properties" (in en). Journal of Solid State Chemistry 327. doi:10.1016/j.jssc.2023.124288. Bibcode: 2023JSSCh.32724288K. https://linkinghub.elsevier.com/retrieve/pii/S0022459623004565. 
  12. ↑ Bui The Khai; Arcelli, Antonio (February 1989). "A new hydrogen source. 3. Chemoselective reduction with triethylammonium hypophosphite hydrate/Raney nickel and tris(triphenylphosphine)ruthenium dichloride reagents." (in en). The Journal of Organic Chemistry 54 (4): 949–953. doi:10.1021/jo00265a040. ISSN 0022-3263. https://pubs.acs.org/doi/abs/10.1021/jo00265a040. 
  13. ↑ Catti, M. (1979-05-15). "Pseudo-symmetry and hydrogen bonding in the crystal structure of NaH2PO2.4/5H2O". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 35 (5): 1041–1046. doi:10.1107/S0567740879005537. Bibcode: 1979AcCrB..35.1041C. https://journals.iucr.org/paper?S0567740879005537. 
  14. ↑ Gao, Shou-zhi; Shi, Xin-ying; Yin, Jian-nan; Wan, Zhao-yuan; Zhou, Huan; Li, Guang-bi (March 2016). "Solid–liquid phase equilibria of (Mg(H2PO2)2 + H2O), (Mg(H2PO2)2 + NaH2PO2 + H2O) and (Mg(H2PO2)2 + MgCl2 + H2O) systems" (in en). Fluid Phase Equilibria 411: 7–12. doi:10.1016/j.fluid.2015.11.033. https://linkinghub.elsevier.com/retrieve/pii/S0378381215302387. 
  15. ↑ Galigné, J. L.; Dumas, Y. (1973-05-01). "Nouvelle détermination de la structure cristalline de l'hypophosphite de magnésium hexahydraté Mg(PO 2 H 2 ) 2 .6H 2 O". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 29 (5): 1115–1119. doi:10.1107/S0567740873003961. ISSN 0567-7408. https://journals.iucr.org/paper?S0567740873003961. 
  16. ↑ Kuratieva, Natalia V.; Naumova, Marina I.; Naumov, Dmitry Yu.; Podberezskaya, Nina V. (2003-06-15). "A new polymorph of hexaaquamagnesium(II) bis(hypophosphite)". Acta Crystallographica Section E Structure Reports Online 59 (6): i89–i91. doi:10.1107/S160053680300758X. ISSN 1600-5368. https://journals.iucr.org/paper?S160053680300758X. 
  17. ↑ Wu, Weihong; Lv, Shufang; Liu, Xin; Qu, Hongqiang; Zhang, Hongchao; Xu, Jianzhong (December 2014). "Using TG–FTIR and TG–MS to study thermal degradation of metal hypophosphites" (in en). Journal of Thermal Analysis and Calorimetry 118 (3): 1569–1575. doi:10.1007/s10973-014-4085-8. ISSN 1388-6150. http://link.springer.com/10.1007/s10973-014-4085-8. 
  18. ↑ 18.0 18.1 18.2 Naumova, M. I.; Kuratieva, N. V.; Naumov, D. Yu.; Podberezskaya, N. V. (January 2004). "Crystal Structures of Anhydrous Potassium, Rubidium, and Cesium Hypophosphites" (in en). Journal of Structural Chemistry 45 (1): 107–113. doi:10.1023/B:JORY.0000041508.85103.9f. ISSN 0022-4766. Bibcode: 2004JStCh..45..107N. https://link.springer.com/10.1023/B:JORY.0000041508.85103.9f. 
  19. ↑ Yin, Jian-nan; Shi, Xin-ying; Zhou, Huan; Tang, Jing-jing; Dai, Ya-ping; Bai, Xiao-qin (2017-02-09). "Solid–Liquid Phase Equilibria of (Ca(H 2 PO 2 ) 2 + H 2 O), (Ca(H 2 PO 2 ) 2 + CaCl 2 + H 2 O), and (Ca(H 2 PO 2 ) 2 + NaH 2 PO 2 + H 2 O) Systems" (in en). Journal of Chemical & Engineering Data 62 (2): 744–751. doi:10.1021/acs.jced.6b00813. ISSN 0021-9568. https://pubs.acs.org/doi/10.1021/acs.jced.6b00813. 
  20. ↑ Matsuzaki, T.; Iitaka, Y. (1969-10-01). "The crystal structure of calcium sodium hypophosphite, CaNa(H 2 PO 2 ) 3". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 25 (10): 1932–1938. doi:10.1107/S0567740869004985. ISSN 0567-7408. https://journals.iucr.org/paper?S0567740869004985. 
  21. ↑ Hung, Ling-I; Hsieh, Dai-Yi; Hsieh, Tsung-Hsiu; Chen, Pei-Lin; Lin, Chia-Her; Wang, Sue-Lein (2022-01-24). "Ca 2 [Ti(HPO 4 ) 2 (PO 4 )·H 2 O, Ca[Ti 2 (H 2 O)(HPO 3 ) 4 ]·H 2 O, and Ti(H 2 PO 2 ) 3: Solid-State Oxidation via Proton-Coupled Electron Transfer"] (in en). Inorganic Chemistry 61 (3): 1327–1334. doi:10.1021/acs.inorgchem.1c02685. ISSN 0020-1669. PMID 34994560. https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c02685. 
  22. ↑ Maouel, Hind A.; Alonzo, Véronique; Roisnel, Thierry; Rebbah, Houria; Le Fur, Eric (2009-07-15). "The first three-dimensional vanadium hypophosphite". Acta Crystallographica Section C Crystal Structure Communications 65 (7): i36–i38. doi:10.1107/S0108270109021325. ISSN 0108-2701. PMID 19578249. https://journals.iucr.org/paper?S0108270109021325. 
  23. ↑ Le Bail, A.; Marcos, M. D.; Amoros, P. (1994-10-25). "ChemInform Abstract: Ab initio Crystal Structure Determination of VO(H2PO2)2×H2O from X-Ray and Neutron Powder Diffraction Data. A Monodimensional Vanadium( IV) Hypophosphite." (in en). ChemInform 25 (43). doi:10.1002/chin.199443002. ISSN 0931-7597. https://onlinelibrary.wiley.com/doi/10.1002/chin.199443002. 
  24. ↑ Baran, Enrique J.; Etcheverry, Susana B.; Diemann, Ekkehard (January 1985). "Preparation and properties of vanadyl(IV) hypophosphite, VO(PO2H2)2·H2O" (in en). Polyhedron 4 (10): 1711–1715. doi:10.1016/S0277-5387(00)84164-9. https://linkinghub.elsevier.com/retrieve/pii/S0277538700841649. 
  25. ↑ Noisong, Pittayagorn; Danvirutai, Chanaiporn; Srithanratana, Tipaporn; Boonchom, Banjong (November 2008). "Synthesis, characterization and non-isothermal decomposition kinetics of manganese hypophosphite monohydrate" (in en). Solid State Sciences 10 (11): 1598–1604. doi:10.1016/j.solidstatesciences.2008.02.020. Bibcode: 2008SSSci..10.1598N. https://linkinghub.elsevier.com/retrieve/pii/S1293255808000769. 
  26. ↑ Weakley, T. J. R. (1979-01-01). "The crystal structures of manganese(II) phosphinate monohydrate, zinc phosphinate monohydrate, and anhydrous zinc phosphinate". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 35 (1): 42–45. doi:10.1107/S056774087900248X. ISSN 0567-7408. Bibcode: 1979AcCrB..35...42W. https://journals.iucr.org/paper?S056774087900248X. 
  27. ↑ Bhat, Gulzar A.; Vishnoi, Pratap; Gupta, Sandeep K.; Murugavel, Ramaswamy (September 2015). "Anhydrous manganese hypophosphite dense framework solid: Synthesis, structure and magnetic studies" (in en). Inorganic Chemistry Communications 59: 84–87. doi:10.1016/j.inoche.2015.07.006. https://linkinghub.elsevier.com/retrieve/pii/S1387700315300186. 
  28. ↑ 28.0 28.1 28.2 Yoshida, Yusuke; Inoue, Katsuya; Kyritsakas, Natalie; Kurmoo, Mohamedally (April 2009). "Syntheses, structures and magnetic properties of zig-zag chains of transition metals with O–P–O bridges" (in en). Inorganica Chimica Acta 362 (5): 1428–1434. doi:10.1016/j.ica.2008.07.009. https://linkinghub.elsevier.com/retrieve/pii/S0020169308004714. 
  29. ↑ 29.0 29.1 29.2 29.3 29.4 29.5 29.6 Wu, Yue; Shaker, Sammy; Brivio, Federico; Murugavel, Ramaswamy; Bristowe, Paul D.; Cheetham, Anthony K. (2017-11-29). "[AmMn(H 2 POO) 3: A New Family of Hybrid Perovskites Based on the Hypophosphite Ligand"] (in en). Journal of the American Chemical Society 139 (47): 16999–17002. doi:10.1021/jacs.7b09417. ISSN 0002-7863. PMID 29069898. Bibcode: 2017JAChS.13916999W. https://pubs.acs.org/doi/10.1021/jacs.7b09417. 
  30. ↑ Richeter, Sébastien; Larionova, Joulia; Long, Jérôme; van der Lee, Arie; Leclercq, Dominique (2013-06-12). "Syntheses, Crystal Structures, and Magnetic Properties of Mn III (L)phosphinate Complexes (L = meso ‐tetraphenylporphyrin or Schiff base)" (in en). European Journal of Inorganic Chemistry 2013 (18): 3206–3216. doi:10.1002/ejic.201300246. ISSN 1434-1948. https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.201300246. 
  31. ↑ Weakley, T. J. R. (1978-01-01). "catena -Bis(phosphinato)(2,2'-bipyridyl)manganese(II)". Acta Crystallographica Section B 34 (1): 281–282. doi:10.1107/S0567740878002812. ISSN 0567-7408. https://journals.iucr.org/paper?S0567740878002812. 
  32. ↑ Kuratieva, Natalia V.; Naumov, Dmitry Yu. (2006-01-15). "Iron(III) dihydrogenphosphate(I)". Acta Crystallographica Section C Crystal Structure Communications 62 (1): i9–i10. doi:10.1107/S0108270105038035. ISSN 0108-2701. PMID 16397325. https://journals.iucr.org/paper?S0108270105038035. 
  33. ↑ 33.0 33.1 Kuratieva, Natalia V.; Naumova, Marina I.; Naumov, Dmitry Yu.; Podberezskaya, Nina V. (2003-01-15). "Hexaaquanickel(II) bis(hypophosphite)". Acta Crystallographica Section C Crystal Structure Communications 59 (1): i1–i3. doi:10.1107/S0108270102018541. ISSN 0108-2701. PMID 12506208. https://journals.iucr.org/paper?S0108270102018541. 
  34. ↑ 34.0 34.1 Kuratieva, Natalia V.; Naumova, Marina I.; Naumov, Dmitry Yu. (2002-09-15). "Hexaaquacobalt(II) bis(hypophosphite) and hexaaquacobalt(II)/nickel(II) bis(hypophosphite)". Acta Crystallographica Section C Crystal Structure Communications 58 (9): i129–i131. doi:10.1107/S0108270102013094. ISSN 0108-2701. PMID 12205368. https://journals.iucr.org/paper?S0108270102013094. 
  35. ↑ Marcos, M. Dolores; Amoros, Pedro; Beltran, Daniel; Beltran, Aurelio (March 1994). "Topotactic Intercalation of Water and Pyridine into Co(H2PO2)2.cntdot.nH2O (0 .ltoreq. n .ltoreq. 0.69). Crystal Structure of Co(H2PO2)2.cntdot.0.53H2O Solved from X-ray Powder Diffraction Data" (in en). Inorganic Chemistry 33 (6): 1220–1226. doi:10.1021/ic00084a042. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic00084a042. 
  36. ↑ Marcos, M. D.; Ibáñez, R.; Amorós, P.; Le Bail, A. (1991-06-15). "Layer structure of [CoCl(H2PO2).H2O"] (in en). Acta Crystallographica Section C: Crystal Structure Communications 47 (6): 1152–1155. doi:10.1107/S0108270190013580. ISSN 0108-2701. Bibcode: 1991AcCrC..47.1152M. https://journals.iucr.org/c/issues/1991/06/00/pa0177/. 
  37. ↑ Ngopoh, F. Atipo Itoua; Lachkar, M.; Đorđević, T.; Lengauer, C. L.; El Bali, B. (September 2015). "Synthesis, Crystal Structure and Characterization of a 2D-Hybrid Cobalt Hypophosphite" (in en). Journal of Chemical Crystallography 45 (8-9): 369–375. doi:10.1007/s10870-015-0603-1. ISSN 1074-1542. http://link.springer.com/10.1007/s10870-015-0603-1. 
  38. ↑ Ngopoh, F. Atipo Itoua; Lachkar, M.; Đorđević, T.; Lengauer, C. L.; El Bali, B. (September 2015). "Synthesis, Crystal Structure and Characterization of a 2D-Hybrid Cobalt Hypophosphite" (in en). Journal of Chemical Crystallography 45 (8–9): 369–375. doi:10.1007/s10870-015-0603-1. ISSN 1074-1542. Bibcode: 2015JCCry..45..369N. http://link.springer.com/10.1007/s10870-015-0603-1. 
  39. ↑ Linn, D. E.; Gould, E. S. (October 1987). "Electron transfer. 88. Cobalt(III)-bound phosphite and hypophosphite" (in en). Inorganic Chemistry 26 (21): 3442–3446. doi:10.1021/ic00268a007. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic00268a007. 
  40. ↑ El Bali, Brahim; Lachkar, Mohammed; Essehli, Rachid; Dusek, Michal; Rohlicek, Jan; Mircescu, Nicoleta; Haisch, Christoph (November 2016). "NaCo(H2PO2)3: Crystal structure and physical study" (in en). Journal of Molecular Structure 1123: 30–34. doi:10.1016/j.molstruc.2016.06.022. https://linkinghub.elsevier.com/retrieve/pii/S0022286016305968. 
  41. ↑ 41.0 41.1 Lach, Jochen; Jeremies, Alexander; Lozan, Vasile; Loose, Claudia; Hahn, Torsten; Kortus, Jens; Kersting, Berthold (2012-11-19). "Stabilization of Hypophosphite in the Binding Pocket of a Dinuclear Macrocyclic Complex: Synthesis, Structure, and Properties of [Ni 2 L(μ-O 2 PH 2 )BPh 4 (L = N 6 S 2 Donor Ligand)"] (in en). Inorganic Chemistry 51 (22): 12380–12388. doi:10.1021/ic301710b. ISSN 0020-1669. PMID 23126334. https://pubs.acs.org/doi/10.1021/ic301710b. 
  42. ↑ Marcos, M. Dolores; Amoros, Pedro; Sapina, Fernando; Beltran-Porter, Aurelio; Martinez-Manez, Ramon; Attfield, J. Paul (November 1993). "New lamellar oxophosphorus derivatives of nickel(II): x-ray powder diffraction structure determinations and magnetic studies of Ni(HPO3).H2O, NiCl(H2PO2).H2O, and NixCo1-x(HPO3).H2O solid solutions" (in en). Inorganic Chemistry 32 (23): 5044–5052. doi:10.1021/ic00075a017. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic00075a017. 
  43. ↑ 43.0 43.1 43.2 43.3 Tanner, Peter A.; Sze, To-Hung; Mak, Thomas C.; Yip, Wai-Hing (February 1992). "Synthesis, crystal structure and vibrational spectra of uranium(IV) hypophosphite" (in en). Journal of Crystallographic and Spectroscopic Research 22 (1): 25–30. doi:10.1007/BF01161359. ISSN 0277-8068. Bibcode: 1992JCCry..22...25T. http://link.springer.com/10.1007/BF01161359. 
  44. ↑ 44.0 44.1 Tanner, Peter A.; Liu Yu-Long; Mak, Thomas C.W. (January 1997). "Synthesis, crystal structures and vibrational spectra of zinc hypophosphites" (in en). Polyhedron 16 (3): 495–505. doi:10.1016/0277-5387(96)00273-2. https://linkinghub.elsevier.com/retrieve/pii/0277538796002732. 
  45. ↑ Weakley, T J R (1983). "The crystal structure of germanium(II,IV) phosphinate, Ge2(H2PO2)6". Journal of The Chemical Society of Pakistan 5 (4): 279-281. https://jcsp.org.pk/issueDetail.aspx?aid=fbc6667a-df53-4d7a-8ada-aa4ee37655a8. 
  46. ↑ 46.0 46.1 Weakley, T. J. R.; Watt, W. W. L. (1979-12-15). "Chloro(phosphinato)germanium(II) and chloro(phosphinato)tin(II)". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 35 (12): 3023–3024. doi:10.1107/S0567740879011213. Bibcode: 1979AcCrB..35.3023W. https://journals.iucr.org/paper?S0567740879011213. 
  47. ↑ 47.0 47.1 47.2 Kuratieva, Natalia V.; Naumova, Marina I.; Podberezskaya, Nina V.; Naumov, Dmitry Yu. (2005-02-15). "The bivalent metal hypophosphites Sr(H 2 PO 2 ) 2 , Pb(H 2 PO 2 ) 2 and Ba(H 2 PO 2 ) 2". Acta Crystallographica Section C Crystal Structure Communications 61 (2): i14–i16. doi:10.1107/S010827010403166X. ISSN 0108-2701. PMID 15695880. https://journals.iucr.org/paper?S010827010403166X. 
  48. ↑ Naumov, Dmitry Yu.; Naumova, Marina I.; Kuratieva, Natalia V. (2005-11-15). "Cadmium bis[dihydrogenphosphate(I)"]. Acta Crystallographica Section E Structure Reports Online 61 (11): i251–i252. doi:10.1107/S1600536805034562. ISSN 1600-5368. https://journals.iucr.org/paper?S1600536805034562. 
  49. ↑ 49.0 49.1 Romanova, N V; Demidenko, N V (1975-12-31). "Hypophosphorous Acid Acid and Its Salts". Russian Chemical Reviews 44 (12): 1036–1047. doi:10.1070/RC1975v044n12ABEH002547. ISSN 0036-021X. https://iopscience.iop.org/article/10.1070/RC1975v044n12ABEH002547. 
  50. ↑ Gieschen, Tobias; Reuter, Hans (2013-08-15). "Calcium hexakis(dihydrogenphosphito)stannate(IV), Ca[Sn(H 2 PO 2 ) 6 , with some remarks on the so-called Ge 2 (H 2 PO 2 ) 6 structure type"]. Acta Crystallographica Section E Structure Reports Online 69 (8): i44–i44. doi:10.1107/S1600536813018205. ISSN 1600-5368. https://journals.iucr.org/paper?S1600536813018205. 
  51. ↑ Xie, Jie-Ling; Zhou, Yu-Hua; Li, Long-Hua; Zhang, Jian-Han; Song, Jun-Ling (2017). "A new method for the preparation of a [Sn 2 (H 2 PO 2 ) 3 Br SHG-active polar crystal via surfactant-induced strategy"] (in en). Dalton Transactions 46 (29): 9339–9343. doi:10.1039/C7DT02116J. ISSN 1477-9226. https://xlink.rsc.org/?DOI=C7DT02116J. 
  52. ↑ Tan, Jinwen; Luo, Han; Wang, Shiyi; Huang, Ling; Cao, Liling; Dong, Xuehua; Zou, Guohong (2024). "RbSb(SO 4 )(H 2 PO 2 )F: a short-wave UV antimony( iii ) oxysalt with mixed-anions demonstrating enhanced birefringence" (in en). Journal of Materials Chemistry C 12 (34): 13230–13235. doi:10.1039/D4TC02926G. ISSN 2050-7526. https://xlink.rsc.org/?DOI=D4TC02926G. 
  53. ↑ Long, Y.; Dong, X.; Huang, L.; Zeng, H.; Lin, Z.; Zhou, L.; Zou, G. (November 2022). "BaSb(H2PO2)3Cl2: An excellent UV nonlinear optical hypophosphite exhibiting strong second-harmonic generation response" (in en). Materials Today Physics 28. doi:10.1016/j.mtphys.2022.100876. https://linkinghub.elsevier.com/retrieve/pii/S2542529322002747. 
  54. ↑ 54.0 54.1 54.2 54.3 Tanner, Peter A.; Faucher, Michele D.; Mak, Thomas C. W. (1999-12-01). "Synthesis, Structure, and Spectroscopy of Rare Earth Hypophosphites. 1. Anhydrous and Monohydrated Lanthanide Hypophosphites" (in en). Inorganic Chemistry 38 (26): 6008–6023. doi:10.1021/ic990187z. ISSN 0020-1669. PMID 11671308. https://pubs.acs.org/doi/10.1021/ic990187z. 
  55. ↑ 55.0 55.1 55.2 Seddon, Joanne A.; Jackson, Andrew R. W.; Kresiński, Roman A.; Platt, Andrew W. G. (1999). "Complexes of the lanthanide metals (La–Nd, Sm–Lu) with hypophosphite and phosphite ligands: crystal structures of [Ce(H2PO2)3(H2O), [Dy(H2PO2)3] and [Pr(H2PO2)(HPO3)(H2O)]·H2O"]. Journal of the Chemical Society, Dalton Transactions (13): 2189–2196. doi:10.1039/a807727d. https://xlink.rsc.org/?DOI=a807727d. 
  56. ↑ Tanner, Peter A.; Mak, Chris S.K.; Mak, Thomas C.W. (April 2000). "Synthesis, structure and spectroscopy of rare earth hypophosphites: 3. ytterbium hypophosphite" (in en). Polyhedron 19 (7): 863–870. doi:10.1016/S0277-5387(00)00333-8. https://linkinghub.elsevier.com/retrieve/pii/S0277538700003338. 
  57. ↑ Jenkins, Wilmer A.; Yost, Don M. (June 1951). "Preparation and Thermal Stability of Thallous Hypophosphite" (in en). Journal of the American Chemical Society 73 (6): 2945–2946. doi:10.1021/ja01150a514. ISSN 0002-7863. https://pubs.acs.org/doi/abs/10.1021/ja01150a514. 
  58. ↑ 58.0 58.1 Tanner, Peter A.; Mak, Thomas C. W. (1999-12-01). "Synthesis, Structure, and Spectroscopy of Rare Earth Hypophosphites. 2. Uranyl Hypophosphite Monohydrate and Uranyl Hypophosphite−Hypophosphorous Acid (1/1)" (in en). Inorganic Chemistry 38 (26): 6024–6031. doi:10.1021/ic990188r. ISSN 0020-1669. PMID 11671309. https://pubs.acs.org/doi/10.1021/ic990188r. 



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