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锿化合物

锿化合物锕系金属元素(Es)形成的化合物。在这些化合物中,锿主要呈现+3价,但+2和+4价的化合物也是已知的。

锿化合物的性质

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锿化合物的晶体学性质
化合物 颜色 晶系 空间群 序号 Pearson符号 晶胞参数(pm)
a b c
Es2O3 无色 Cubic Ia3 206 cI80 1076.6
Es2O3 无色 Monoclinic C2/m 12 mS30 1411 359 880
Es2O3 无色 Hexagonal P3m1 164 hP5 370 600
EsF3 Hexagonal
EsF4 Monoclinic[1] C2/c 15 mS60
EsCl3 橙色 Hexagonal[2] C63/m hP8 727 410
EsBr3 黄色 Monoclinic[3] C2/m 12 mS16 727 1259 681
EsI3 黄褐色 Hexagonal[4][5] R3 148 hR24 753 2084
EsOCl Tetragonal[4] P4/nmm 394.8 670.2

无机锿化合物

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氧化锿(III)(Es2O3)为无色立方晶体,可以通过灼烧硝酸锿(III)制得。[6][7]它的另外两相,单斜和六方也是已知的,[8]其中六方相与氧化镧同构,Es3+有六配位的O2−环绕。[9][4]

锿配合物

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锿具有强放射性,这使之在放射治療中有潜在应用。它的很多配合物已被合成,锿原子在体内会被输送到人体内特定的器官中。目前已有向狗的体内注射檸檬酸锿的实验。[10]锿(III)也能和β-二酮配位,在制备时,会将其用Gd3+稀释1000倍,以减小辐射分解,让化合物在测试所需的20分钟内保持一定程度上的稳定。 由于化合物中的组分阻碍了螯合配体至Es3+的有效能量转移,其发光很弱而无法被检测到。[11]

而Es3+的荧光可以在盐酸溶液中或二(2-乙基己基)磷酸的有机溶液中探测到,被绿光(~495 nm)激发时,它在约1064 nm处有宽峰(半峰宽~100 nm)。[12]

锿单阳离子(Es+)和五甲基环戊二烯的气相反应已有报道。[13]

锿后元素化合物

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锕系元素)的固体化合物尚未制得,仅溶液化学有所研究。镄和钔在溶液中以三价离子的形式存在,它们可以被还原为二价的Fm2+或Md2+[14][15]锘也存在+2价和+3价,但其最稳定的价态是+2价,它也是f区元素中唯一一个+2价最为常见且在水溶液中稳定的元素。[16]铹在溶液中以+3价的形式存在,和类似,试图在水溶液中将Lr3+还原至Lr2+或Lr+的实验未能成功。

参考文献

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  1. ^ Kleinschmidt, P. Thermochemistry of the actinides. Journal of Alloys and Compounds. 1994,. 213–214: 169–172 [2019-07-14]. doi:10.1016/0925-8388(94)90898-2. (原始内容存档于2020-03-16). 
  2. ^ Fujita, D.; Cunningham, B. B.; Parsons, T. C. Crystal structures and lattice parameters of einsteinium trichloride and einsteinium oxychloride. Inorganic and Nuclear Chemistry Letters. 1969, 5 (4): 307–313 [2019-07-14]. doi:10.1016/0020-1650(69)80203-5. (原始内容存档于2020-03-13). 
  3. ^ Fellows, R.; Peterson, J. R.; Noé, M.; Young, J. P.; Haire, R. G. X-ray diffraction and spectroscopic studies of crystalline einsteinium(III) bromide, 253EsBr3. Inorganic and Nuclear Chemistry Letters. 1975, 11 (11): 737–742. doi:10.1016/0020-1650(75)80090-0. 
  4. ^ 4.0 4.1 4.2 Haire, pp. 1595–1596
  5. ^ Seaborg, p. 62
  6. ^ Greenwood, p. 1268
  7. ^ Haire, R. G.; Baybarz, R. D. Identification and analysis of einsteinium sesquioxide by electron diffraction. Journal of Inorganic and Nuclear Chemistry. 1973, 35 (2): 489–496. doi:10.1016/0022-1902(73)80561-5. 
  8. ^ Haire, p. 1598
  9. ^ Haire, R. G. & Eyring, L. Lanthanides and Actinides Chemistry. K.A. Gscheidner, Jr.; et al (编). Handbook on the Physics and Chemistry of Rare Earths 18. North-Holland, New York. 1994: 414–505. ISBN 978-0-444-81724-2. 
  10. ^ Haire, p. 1579
  11. ^ Nugent, Leonard J.; Burnett, J. L.; Baybarz, R. D.; Werner, George Knoll; Tanner, S. P.; Tarrant, J. R.; Keller, O. L. Intramolecular energy transfer and sensitized luminescence in actinide(III) .beta.-diketone chelates. The Journal of Physical Chemistry. 1969, 73 (5): 1540–1549. doi:10.1021/j100725a060. 
  12. ^ Beitz, J.; Wester, D.; Williams, C. 5f state interaction with inner coordination sphere ligands: Es3+ ion fluorescence in aqueous and organic phases. Journal of the Less Common Metals. 1983, 93 (2): 331–338. doi:10.1016/0022-5088(83)90178-9. 
  13. ^ Gibson, John K.; Haire, Richard G. Activation of Pentamethylcyclopentadiene by Bk+, Cf+, and Es+ Ions in the Gas Phase: Probing Electronic Structures of Transcurium Actinides. Organometallics (American Chemical Society (ACS)). 2004-11-30, 24 (1): 119–126. ISSN 0276-7333. doi:10.1021/om049387v. 
  14. ^ Mikheev, N.B.; Spitsyn, V.I.; Kamenskaya, A.N.; Gvozdev, B.A.; Druin, V.A.; Rumer, I.A.; Dyachkova, R.A.; Rozenkevitch, N.A.; Auerman, L.N. Reduction of fermium to divalent state in chloride aqueous ethanolic solutions. Inorganic and Nuclear Chemistry Letters (Elsevier BV). 1972, 8 (11): 929–936. ISSN 0020-1650. doi:10.1016/0020-1650(72)80202-2. 
  15. ^ Silva, Robert J. (2006). "Fermium, Mendelevium, Nobelium, and Lawrencium" (PDF). In Morss, Lester R.; Edelstein, Norman M.; Fuger, Jean (eds.). The Chemistry of the Actinide and Transactinide Elements. Vol. 3 (3rd ed.). Dordrecht: Springer. pp. 1621–1651. doi:10.1007/1-4020-3598-5_13. ISBN 978-1-4020-3555-5. pp. 1635–1636.
  16. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 1278. ISBN 978-0-08-037941-8.
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锿化合物
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