次锰酸盐

次锰酸盐
英文名	Hypomanganate
别名	锰(V)酸盐
识别
CAS号	14333-15-4
性质
化学式	MnO3−; 4
摩尔质量	118.94 g·mol⁻¹
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

次锰酸根，又称锰(V)酸根，是一种锰的含氧酸根（英语：Oxyanion），化学式 MnO3−
4，次锰酸盐则是这种阴离子形成的盐。

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次锰酸盐通常是亮蓝色的。^[1]^[2]最著名的次锰酸盐是次锰酸钾 K
3MnO
4，但次锰酸钠 Na
3MnO
4、次锰酸钡 Ba
3(MnO
4)
2和钾钡盐 KBaMnO
4都是已知的。^[3]在磷灰石^[4]^[5]和钙铁铝石（英语：brownmillerite）^[6]的人造变种中，次锰酸根可以取代其中的磷酸根 PO3−
4。

次锰酸根于1946年由Hermann Lux首次报告。他通过氧化钠 Na
2O、二氧化锰 MnO
2和亚硝酸钠 NaNO
2在500 °C的反应，得到了亮蓝色的次锰酸钠。^[7]^[3]他也从其氢氧化钠溶液结晶出了十水合物 Na
3MnO
4·10H
2O。

次锰酸根是四面体形的含氧酸根（英语：Oxyanion），结构类似硫酸根、锰酸根和高锰酸根。作为d²电子构型的四面体形分子，它在基态下为三线态。^[3]

次锰酸根呈亮蓝色，^[1]最大吸收光谱λ_max = 670 nm（ε = 900 dm³ mol⁻¹ cm⁻¹）。^[8]^[9]

次锰酸盐不稳定，会歧化成锰酸盐和二氧化锰。^[10]^[1]在pH 14下，次锰酸盐预测的电极电势（英语：electrode potential）如下：^[11]^[12]^[13]

MnO2−
4 + e⁻ ⇌ MnO3−
4 E = +0.27 V

MnO3−
4 + e⁻ + 2 H₂O ⇌ MnO₂ + 4 OH⁻ E = +0.96 V

然而，歧化反应在强碱性环境下（OH⁻浓度超过5–10 mol/L）会变慢。^[1]^[7]

这个歧化反应被认为有质子化的中间体 HMnO2−
4。^[13]它在反应 HMnO2−
4 ⇌ MnO3−
4 + H⁺中的pK_a为13.7 ± 0.2。^[14]然而，K₃MnO₄已经和Ca₂Cl(PO₄)共结晶，使人们可以研究次锰酸根的紫外-可见分光光度法。^[10]^[15]

次锰酸盐可以由亚硫酸盐、^[1]过氧化氢^[16]或扁桃酸^[9]小心还原锰酸盐而成。

氟化钒酸锶 Sr
5(VO
4)
3F中的一些钒酸根被次锰酸根取代后，可能可用于近红外激光器中。^[17]

次锰酸钡 Ba
3(MnO
4)
2有有趣的磁性性质。^[18]

次锰酸根的共轭酸次锰酸 H
3MnO
4因为会迅速歧化而无法制备，但其第三酸度系数已通过脉冲辐解技术估计：^[14]

HMnO2−
4 ⇌ MnO3−
4 + H⁺ pK_a = 13.7 ± 0.2

次锰酸的环酯被认为是高锰酸盐氧化烯烃的中间体。^[9]

二锰(III)酸盐 Mn
2O6−
6
锰酸盐 MnO2−
4
高锰酸盐 MnO−
4

[1]
Greenwood, Norman N.; Earnshaw, A. Chemistry of the Elements. Oxford: Pergamon. 1984: 1221–22. ISBN 0-08-022057-6..
[2]
Reinen, D.; Rauw, W.; Kesper, U.; Atanasov, M.; Güdel, H.U.; Hazenkamp, M.; Oetliker, U. Colour, luminescence and bonding properties of tetrahedrally coordinated chromium(IV), manganese(V) and iron(VI) in various oxide ceramics. Journal of Alloys and Compounds (Elsevier BV). 1997, 246 (1-2): 193–208. ISSN 0925-8388. doi:10.1016/s0925-8388(96)02461-9.
[3]
zur Loye, K. D.; Chance, W. M.; Yeon, J.; zur Loye, H.-C. Synthesis, Crystal Structure, and Magnetic Properties of the Oxometallates KBaMnO₄ and KBaAsO₄. Solid State Sciences. 2014, 37: 86–90. Bibcode:2014SSSci..37...86Z. doi:10.1016/j.solidstatesciences.2014.08.013 .
[4]
Dardenne, K.; Vivien, D.; Huguenin, D. Color of Mn(V)-Substituted Apatites A10((B, Mn)O4)6F2, A=Ba, Sr, Ca; B=P, V. Journal of Solid State Chemistry (Elsevier BV). 1999, 146 (2): 464–472. ISSN 0022-4596. doi:10.1006/jssc.1999.8394.
[5]
Grisafe, D.A.; Hummel, F.A. Pentavalent ion substitutions in the apatite structure part A. Crystal chemistry. Journal of Solid State Chemistry (Elsevier BV). 1970, 2 (2): 160–166. ISSN 0022-4596. doi:10.1016/0022-4596(70)90064-2.
[6]
Jiang, Peng; Li, Jun; Ozarowski, A.; Sleight, Arthur W.; Subramanian, M. A. Intense Turquoise and Green Colors in Brownmillerite-Type Oxides Based on Mn5+ in Ba2In2–xMnxO5+x. Inorganic Chemistry (American Chemical Society (ACS)). 2013-01-18, 52 (3): 1349–1357. ISSN 0020-1669. doi:10.1021/ic3020332.
[7]
Herrman Lux (1946): "Über Salze des fünfwertigen Mangans （页面存档备份，存于互联网档案馆）." Zeitschrift für Naturforschung, volume 1, pages 281-283.
[8]
Carrington, A.; Symons, M. C. R., Structure and reactivity of the oxy-anions of transition metals. Part I. The manganese oxy-anions, J. Chem. Soc., 1956: 3373–80, doi:10.1039/JR9560003373
[9]
Lee, Donald G.; Chen, Tao, Reduction of manganate(VI) by mandelic acid and its significance for development of a general mechanism of oxidation of organic compounds by high-valent transition metal oxides, J. Am. Chem. Soc., 1993, 115 (24): 11231–36, doi:10.1021/ja00077a023.
[10]
Cotton, F. Albert; Wilkinson, Geoffrey, Advanced Inorganic Chemistry 4th, New York: Wiley: 746, 1980, ISBN 0-471-02775-8.
[11]
Weast, Robert C. (编). CRC Handbook of Chemistry and Physics 62nd. Boca Raton, FL: CRC Press. 1981: D-134. ISBN 0-8493-0462-8..
[12]
Manganese – compounds – standard reduction potentials, WebElements, [2010-06-26], （原始内容存档于2021-01-17）.
[13]
Sekula-Brzezińska, K.; Wrona, P. K.; Galus, Z., Rate of the MnO₄⁻/MnO₄²⁻ and MnO₄²⁻/MnO₄³⁻ electrode reactions in alkaline solutions at solid electrodes, Electrochim. Acta, 1979, 24 (5): 555–63, doi:10.1016/0013-4686(79)85032-X.
[14]
Rush, J. D.; Bielski, B. H. J., Studies of Manganate(V), -(VI), and -(VII) Tetraoxyanions by Pulse Radiolysis. Optical Spectra of Protonated Forms, Inorg. Chem., 1995, 34 (23): 5832–38, doi:10.1021/ic00127a022.
[15]
Carrington, A.; Symons, M. C. R., Structure and reactivity of the oxy-anions of transition metals. Part I. The manganese oxy-anions, J. Chem. Soc., 1956: 3373–80, doi:10.1039/JR9560003373.
[16]
Lee, Donald G.; Chen, Tao, Oxidation of hydrocarbons. 18. Mechanism of the reaction between permanganate and carbon-carbon double bonds, J. Am. Chem. Soc., 1989, 111 (19): 7534–38, doi:10.1021/ja00201a039.
[17]
Merkle, Larry D.; Guyot, Yannick; Chai, Bruce H. T. Spectroscopic and laser investigations of Mn5+:Sr5(VO4)3F. Journal of Applied Physics (AIP Publishing). 1995-01-15, 77 (2): 474–480. ISSN 0021-8979. doi:10.1063/1.359585.
[18]
Stone, M. B.; Lumsden, M. D.; Qiu, Y.; Samulon, E. C.; Batista, C. D.; Fisher, I. R. Dispersive magnetic excitations in theS=1antiferromagnetBa3Mn2O8. Physical Review B (American Physical Society (APS)). 2008-04-02, 77 (13). ISSN 1098-0121. doi:10.1103/physrevb.77.134406.

[G&E-1] [1]
Greenwood, Norman N.; Earnshaw, A. Chemistry of the Elements. Oxford: Pergamon. 1984: 1221–22. ISBN 0-08-022057-6..

[Reinen-2] [2]
Reinen, D.; Rauw, W.; Kesper, U.; Atanasov, M.; Güdel, H.U.; Hazenkamp, M.; Oetliker, U. Colour, luminescence and bonding properties of tetrahedrally coordinated chromium(IV), manganese(V) and iron(VI) in various oxide ceramics. Journal of Alloys and Compounds (Elsevier BV). 1997, 246 (1-2): 193–208. ISSN 0925-8388. doi:10.1016/s0925-8388(96)02461-9.

[Loye-3] [3]
zur Loye, K. D.; Chance, W. M.; Yeon, J.; zur Loye, H.-C. Synthesis, Crystal Structure, and Magnetic Properties of the Oxometallates KBaMnO₄ and KBaAsO₄. Solid State Sciences. 2014, 37: 86–90. Bibcode:2014SSSci..37...86Z. doi:10.1016/j.solidstatesciences.2014.08.013 .

[Dardenne-4] [4]
Dardenne, K.; Vivien, D.; Huguenin, D. Color of Mn(V)-Substituted Apatites A10((B, Mn)O4)6F2, A=Ba, Sr, Ca; B=P, V. Journal of Solid State Chemistry (Elsevier BV). 1999, 146 (2): 464–472. ISSN 0022-4596. doi:10.1006/jssc.1999.8394.

[Grisafe-5] [5]
Grisafe, D.A.; Hummel, F.A. Pentavalent ion substitutions in the apatite structure part A. Crystal chemistry. Journal of Solid State Chemistry (Elsevier BV). 1970, 2 (2): 160–166. ISSN 0022-4596. doi:10.1016/0022-4596(70)90064-2.

[Jiang-6] [6]
Jiang, Peng; Li, Jun; Ozarowski, A.; Sleight, Arthur W.; Subramanian, M. A. Intense Turquoise and Green Colors in Brownmillerite-Type Oxides Based on Mn5+ in Ba2In2–xMnxO5+x. Inorganic Chemistry (American Chemical Society (ACS)). 2013-01-18, 52 (3): 1349–1357. ISSN 0020-1669. doi:10.1021/ic3020332.

[Lux-7] [7]
Herrman Lux (1946): "Über Salze des fünfwertigen Mangans （页面存档备份，存于互联网档案馆）." Zeitschrift für Naturforschung, volume 1, pages 281-283.

[JCS-8] [8]
Carrington, A.; Symons, M. C. R., Structure and reactivity of the oxy-anions of transition metals. Part I. The manganese oxy-anions, J. Chem. Soc., 1956: 3373–80, doi:10.1039/JR9560003373

[Mandelate-9] [9]
Lee, Donald G.; Chen, Tao, Reduction of manganate(VI) by mandelic acid and its significance for development of a general mechanism of oxidation of organic compounds by high-valent transition metal oxides, J. Am. Chem. Soc., 1993, 115 (24): 11231–36, doi:10.1021/ja00077a023.

[C&W-10] [10]
Cotton, F. Albert; Wilkinson, Geoffrey, Advanced Inorganic Chemistry 4th, New York: Wiley: 746, 1980, ISBN 0-471-02775-8.

[11] [11]
Weast, Robert C. (编). CRC Handbook of Chemistry and Physics 62nd. Boca Raton, FL: CRC Press. 1981: D-134. ISBN 0-8493-0462-8..

[12] [12]
Manganese – compounds – standard reduction potentials, WebElements, [2010-06-26], （原始内容存档于2021-01-17）.

[Epot-13] [13]
Sekula-Brzezińska, K.; Wrona, P. K.; Galus, Z., Rate of the MnO₄⁻/MnO₄²⁻ and MnO₄²⁻/MnO₄³⁻ electrode reactions in alkaline solutions at solid electrodes, Electrochim. Acta, 1979, 24 (5): 555–63, doi:10.1016/0013-4686(79)85032-X.

[PulseRad-14] [14]
Rush, J. D.; Bielski, B. H. J., Studies of Manganate(V), -(VI), and -(VII) Tetraoxyanions by Pulse Radiolysis. Optical Spectra of Protonated Forms, Inorg. Chem., 1995, 34 (23): 5832–38, doi:10.1021/ic00127a022.

[15] [15]
Carrington, A.; Symons, M. C. R., Structure and reactivity of the oxy-anions of transition metals. Part I. The manganese oxy-anions, J. Chem. Soc., 1956: 3373–80, doi:10.1039/JR9560003373.

[H2O2-16] [16]
Lee, Donald G.; Chen, Tao, Oxidation of hydrocarbons. 18. Mechanism of the reaction between permanganate and carbon-carbon double bonds, J. Am. Chem. Soc., 1989, 111 (19): 7534–38, doi:10.1021/ja00201a039.

[Merkle-17] [17]
Merkle, Larry D.; Guyot, Yannick; Chai, Bruce H. T. Spectroscopic and laser investigations of Mn5+:Sr5(VO4)3F. Journal of Applied Physics (AIP Publishing). 1995-01-15, 77 (2): 474–480. ISSN 0021-8979. doi:10.1063/1.359585.

[Stone-18] [18]
Stone, M. B.; Lumsden, M. D.; Qiu, Y.; Samulon, E. C.; Batista, C. D.; Fisher, I. R. Dispersive magnetic excitations in theS=1antiferromagnetBa3Mn2O8. Physical Review B (American Physical Society (APS)). 2008-04-02, 77 (13). ISSN 1098-0121. doi:10.1103/physrevb.77.134406.

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次锰酸盐

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