锎化合物

锎化合物是锎元素形成的化合物，只有很少一些有所研究。^[1]三氯化锎是最先发现的锎化合物，由伯里斯·坎宁安于1960年在劳伦斯伯克利国家实验室制备出来。^[2]唯一能在水溶液稳定的离子是三价的锎离子，^[3]而二价的具有强还原性，四价的具有强氧化性。^[4]锎的氯化物、硝酸盐、硫酸盐和高氯酸盐都是可溶的，而氟化物、氢氧化物和草酸盐是难溶的。^[5]

锎的+3价态的代表的三氧化二锎（黄绿色固体）、三氟化锎（亮绿色固体）和三碘化锎（柠檬黄色固体）。^[4]其它+3价的还有硫化物和环戊二烯配合物。^[6]+4价的典型化合物有二氧化锎（棕褐色固体）和四氟化锎（绿色固体）。+2价的有二溴化锎（黄色固体）和二碘化锎（暗紫色固体）。^[4]

简单化合物

二氧化锎（CfO₂）是棕褐色固体，属立方晶系，晶体内的晶胞间距为531.0 ± 0.2 pm。^[7]三氧化二锎（Cf₂O₃）通常具有体心立方对称性，加热至1400℃时转变为单斜晶系的晶体，在1750℃熔化。^[7]三氧化二锎在高温下可以被金属镧还原为单质锎。^[8]

三氯化锎（CfCl₃）是翡翠绿色固体，属六方晶系，可以通过Cf₂O₃和HCl气体于500 °C反应得到。^[9] CfCl₃可以当作原料来制备橙黄色的三碘化物CfI₃，它可以进一步被还原为薰衣草紫色的二碘化物CfI₂。^[10]三氯化锎直接用氢气还原，可以得到二氯化锎^[11]，该化合物是稳定的^[12]。

三氟化锎（CfF₃）是黄绿色固体，其晶体结构在加热至室温之上时逐渐由正交转变为六方。^[13]四氟化锎（CfF₄）是亮绿色固体，有单斜结构。^[14]

二碘化锎（CfI₂）是深紫色固体，在室温时有稳定的菱方结构和不稳定的六方结构。三碘化锎（CfI₃）是柠檬黄色固体，有菱方结构，在约800℃升华。^[15]

氟氧化锎（CfOF）可由三氟化锎在高温下的水解反应制得。^[16]氯氧化锎（CfOCl）由三氯化锎的水合物在280–320 °C的水解得到。^[17]氯氧化锎是第一个被发现的锎化合物。^[18]

硫酸锎在1200 °C的空气中加热，再在500 °C的氢气中还原，可以得到Cf₂O₃。^[9]氢氧化物Cf(OH)₃与氟化物CfF₃微溶于水。^[9]

多硼酸锎（英语：Californium(III) polyborate）是一种较为特殊的化合物，化合物中存在锎和硼酸根的共价键。^[19]

氮化锎（CfN）、砷化锎（CfAs）和锑化锎（CfSb）是锎的氮族元素化合物，它们有着氯化钠晶型，可由金属锎和相应的单质化合而成。^[20]

配合物

三价的锎离子可以在水溶液中以[Cf(H₂O)₈]³⁺和[Cf(H₂O)₉]³⁺水配离子的形式存在，成盐[Cf(H₂O)₉](ClO₄)₃或[Cf(H₂O)₉](CF₃SO₃)₃。^[21]β-二酮类配合物（如萘甲酰三氟丙酮等）可以和Cf³⁺形成螯合物，从水溶液中萃取出来。^[22]

三氯化锎和过量的2,6-吡啶二甲酸（PDA）于150℃在1：1的乙醇水溶液中反应，可以制得Cf(HDPA)₃·H₂O^[23]，它是一种电荷转移配合物。^[24]

锎是已知可形成有机金属化合物的金属中，原子序第二大的元素。Cp₃Cf（Cp = C₅H₅）由二茂铍（Cp₂Be）和三氯化锎（CfCl₃）反应得到，并通过X射线衍射进行了表征。^[25]

参见

参考文献

[1]
Krebs, Robert. The History and Use of our Earth's Chemical Elements: A Reference Guide. Westport, Connecticut: Greenwood Publishing Group. 2006: 327–328. ISBN 978-0-313-33438-2.
[2]
Element 98 Prepared. Science News Letters. December 1960, 78 (26).
[3]
CRC 2006，第4-8页.
[4]
Jakubke 1994，第166页.
[5]
Seaborg 2004.
[6]
Cotton 1999，第1163页.
[7]
Baybarz, R. D.; Haire, R. G.; Fahey, J. A. On the Californium Oxide System. Inorganic and Nuclear Chemistry. 1972, 34 (2): 557–565. doi:10.1016/0022-1902(72)80435-4.
[8]
朱文祥. 无机化合物制备手册. 化学工业出版社, 2006. pp 171. ISBN 7-5025-8537-0
[9]
Cunningham 1968，第105页.
[10]
Cotton, Simon. Lanthanide and Actinide Chemistry. West Sussex, England: John Wiley & Sons. 2006: 168. ISBN 978-0-470-01006-8.
[11]
Peterson J R, Fellows R L, Haire R G, et al. Stabilization of californium (II) in the solid state[J]. Radiochemical and Radioanalytical Letters, 1977, 31(4-5): 277-282.
[12]
Greenwood 1997，第1272页.
[13]
Stevenson, J. N.; Peterson, J. R. The Trigonal and Orthorhombic Crystal Structures of CfF₃ and their Temperature Relationship. Inorganic and Nuclear Chemistry. 1973, 35 (10): 3481–3486. doi:10.1016/0022-1902(73)80356-2.
[14]
Chang, C-T. P.; Haire, R. G.; Nave, S. E. Magnetic Susceptibility of Californium Fluorides. Physical Review B. 1990, 41 (13): 9045–9048. Bibcode:1990PhRvB..41.9045C. doi:10.1103/PhysRevB.41.9045.
[15]
Macintyre, J. E.; Daniel, F. M.; Stirling, V. M. Dictionary of inorganic compounds. London: Chapman and Hall, CRC Press. 1992: 2826. ISBN 978-0-412-30120-9.
[16]
Peterson, J. R.; Burns, John H. Preparation and Crystal Structure of Californium Oxyfluoride, CfOF. Inorganic and Nuclear Chemistry. 1968, 30 (11): 2955–2958. doi:10.1016/0022-1902(68)80155-1.
[17]
Copeland, J. C.; Cunningham, B. B. Crystallography of the Compounds of Californium. II. Crystal Structure and Lattice Parameters of Californium Oxychloride and Californium Sesquioxide. Inorganic and Nuclear Chemistry. 1969, 31 (3): 733–740. doi:10.1016/0022-1902(69)80020-5.
[18]
Seaborg, Glenn T. Man-Made Transuranium Elements. Prentice-Hall. 1963.
[19]
Unusual structure, bonding, and properties may provide a new possibility for a californium borate. 1 June 2015 [29 July 2015]. （原始内容存档于2017-08-02）.
[20]
Nave S E, Moore J R, Haire R G, et al. Magnetic susceptibility of CfN, CfAs and CfSb[J]. Journal of the Less Common Metals, 1986, 121: 319-324. DOI: 10.1016/0022-5088(86)90548-5
[21]
Galbis E, Hernández‐Cobos J, den Auwer C, et al. Solving the hydration structure of the heaviest actinide aqua ion known: The californium (III) case[J]. Angewandte Chemie International Edition, 2010, 49(22): 3811-3815. DOI: 10.1002/anie.200906129
[22]
张青莲等. 无机化学丛书第十卷锕系锕系后元素. 科学出版社, 1998. pp 322. "12.2.4 锎的水溶液化学"
[23]
Cary S K, Vasiliu M, Baumbach R E, et al. Emergence of californium as the second transitional element in the actinide series[J]. Nature communications, 2015, 6: 6827. DOI: 10.1038/ncomms7827
[24]
Liu G, Cary S K, Albrecht-Schmitt T E. Metastable charge-transfer state of californium (iii) compounds[J]. Physical Chemistry Chemical Physics, 2015, 17(24): 16151-16157. DOI: 10.1039/C5CP01855B
[25]
Laubereau, Peter G.; Burns, John H. Microchemical preparation of tricyclopentadienyl compounds of berkelium, californium, and some lanthanide elements. Inorganic Chemistry. 1970, 9 (5): 1091–1095. doi:10.1021/ic50087a018.

参考书目

Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred. Advanced Inorganic Chemistry 6th. New York City: John Wiley & Sons. 1999. ISBN 0-471-19957-5.
CRC contributors. David R. Lide , 编. Handbook of Chemistry and Physics 87th. Boca Raton, Florida: CRC Press, Taylor & Francis Group. 2006. ISBN 0-8493-0487-3.
Cunningham, B. B. Californium. Clifford A. Hampel (编). The Encyclopedia of the Chemical Elements. New York City: Reinhold Book Corporation. 1968. LCCN 68-29938.
Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford, England: Butterworth-Heinemann. 1997. ISBN 0-7506-3365-4.
Jakubke, Hans-Dieter; Jeschkeit, Hans (编). Concise Encyclopedia Chemistry. trans. rev. Eagleson, Mary. Berlin: Walter de Gruyter. 1994 [2017-08-02]. ISBN 3-11-011451-8. （原始内容存档于2016-06-03）.
Seaborg, Glenn T. Californium. Geller, Elizabeth (编). Concise Encyclopedia of Chemistry. New York City: McGraw-Hill: 94. 2004. ISBN 0-07-143953-6.

[Krebs2006-1] [1]
Krebs, Robert. The History and Use of our Earth's Chemical Elements: A Reference Guide. Westport, Connecticut: Greenwood Publishing Group. 2006: 327–328. ISBN 978-0-313-33438-2.

[2] [2]
Element 98 Prepared. Science News Letters. December 1960, 78 (26).

[FOOTNOTECRC20064-8-3] [3]
CRC 2006，第4-8页.

[FOOTNOTEJakubke1994166-4] [4]
Jakubke 1994，第166页.

[FOOTNOTESeaborg2004-5] [5]
Seaborg 2004.

[FOOTNOTECotton19991163-6] [6]
Cotton 1999，第1163页.

[CF_OX-7] [7]
Baybarz, R. D.; Haire, R. G.; Fahey, J. A. On the Californium Oxide System. Inorganic and Nuclear Chemistry. 1972, 34 (2): 557–565. doi:10.1016/0022-1902(72)80435-4.

[8] [8]
朱文祥. 无机化合物制备手册. 化学工业出版社, 2006. pp 171. ISBN 7-5025-8537-0

[FOOTNOTECunningham1968105-9] [9]
Cunningham 1968，第105页.

[10] [10]
Cotton, Simon. Lanthanide and Actinide Chemistry. West Sussex, England: John Wiley & Sons. 2006: 168. ISBN 978-0-470-01006-8.

[11] [11]
Peterson J R, Fellows R L, Haire R G, et al. Stabilization of californium (II) in the solid state[J]. Radiochemical and Radioanalytical Letters, 1977, 31(4-5): 277-282.

[FOOTNOTEGreenwood19971272-12] [12]
Greenwood 1997，第1272页.

[13] [13]
Stevenson, J. N.; Peterson, J. R. The Trigonal and Orthorhombic Crystal Structures of CfF₃ and their Temperature Relationship. Inorganic and Nuclear Chemistry. 1973, 35 (10): 3481–3486. doi:10.1016/0022-1902(73)80356-2.

[14] [14]
Chang, C-T. P.; Haire, R. G.; Nave, S. E. Magnetic Susceptibility of Californium Fluorides. Physical Review B. 1990, 41 (13): 9045–9048. Bibcode:1990PhRvB..41.9045C. doi:10.1103/PhysRevB.41.9045.

[dictoc-15] [15]
Macintyre, J. E.; Daniel, F. M.; Stirling, V. M. Dictionary of inorganic compounds. London: Chapman and Hall, CRC Press. 1992: 2826. ISBN 978-0-412-30120-9.

[16] [16]
Peterson, J. R.; Burns, John H. Preparation and Crystal Structure of Californium Oxyfluoride, CfOF. Inorganic and Nuclear Chemistry. 1968, 30 (11): 2955–2958. doi:10.1016/0022-1902(68)80155-1.

[CF_OX_CL_1969-17] [17]
Copeland, J. C.; Cunningham, B. B. Crystallography of the Compounds of Californium. II. Crystal Structure and Lattice Parameters of Californium Oxychloride and Californium Sesquioxide. Inorganic and Nuclear Chemistry. 1969, 31 (3): 733–740. doi:10.1016/0022-1902(69)80020-5.

[18] [18]
Seaborg, Glenn T. Man-Made Transuranium Elements. Prentice-Hall. 1963.

[doe-19] [19]
Unusual structure, bonding, and properties may provide a new possibility for a californium borate. 1 June 2015 [29 July 2015]. （原始内容存档于2017-08-02）.

[20] [20]
Nave S E, Moore J R, Haire R G, et al. Magnetic susceptibility of CfN, CfAs and CfSb[J]. Journal of the Less Common Metals, 1986, 121: 319-324. DOI: 10.1016/0022-5088(86)90548-5

[21] [21]
Galbis E, Hernández‐Cobos J, den Auwer C, et al. Solving the hydration structure of the heaviest actinide aqua ion known: The californium (III) case[J]. Angewandte Chemie International Edition, 2010, 49(22): 3811-3815. DOI: 10.1002/anie.200906129

[22] [22]
张青莲等. 无机化学丛书第十卷锕系锕系后元素. 科学出版社, 1998. pp 322. "12.2.4 锎的水溶液化学"

[23] [23]
Cary S K, Vasiliu M, Baumbach R E, et al. Emergence of californium as the second transitional element in the actinide series[J]. Nature communications, 2015, 6: 6827. DOI: 10.1038/ncomms7827

[24] [24]
Liu G, Cary S K, Albrecht-Schmitt T E. Metastable charge-transfer state of californium (iii) compounds[J]. Physical Chemistry Chemical Physics, 2015, 17(24): 16151-16157. DOI: 10.1039/C5CP01855B

[25] [25]
Laubereau, Peter G.; Burns, John H. Microchemical preparation of tricyclopentadienyl compounds of berkelium, californium, and some lanthanide elements. Inorganic Chemistry. 1970, 9 (5): 1091–1095. doi:10.1021/ic50087a018.

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