鐦化合物

鐦化合物是鐦元素形成的化合物，只有很少一些有所研究。^[1]三氯化鐦是最先發現的鐦化合物，由伯里斯·坎寧安於1960年在勞倫斯伯克利國家實驗室製備出來。^[2]唯一能在水溶液穩定的離子是三價的鐦離子，^[3]而二價的具有強還原性，四價的具有強氧化性。^[4]鐦的氯化物、硝酸鹽、硫酸鹽和高氯酸鹽都是可溶的，而氟化物、氫氧化物和草酸鹽是難溶的。^[5]

鐦的+3價態的代表的三氧化二鐦（黃綠色固體）、三氟化鐦（亮綠色固體）和三碘化鐦（檸檬黃色固體）。^[4]其它+3價的還有硫化物和環戊二烯配合物。^[6]+4價的典型化合物有二氧化鐦（棕褐色固體）和四氟化鐦（綠色固體）。+2價的有二溴化鐦（黃色固體）和二碘化鐦（暗紫色固體）。^[4]

簡單化合物

二氧化鐦（CfO₂）是棕褐色固體，屬立方晶系，晶體內的晶胞間距為531.0 ± 0.2 pm。^[7]三氧化二鐦（Cf₂O₃）通常具有體心立方對稱性，加熱至1400℃時轉變為單斜晶系的晶體，在1750℃熔化。^[7]三氧化二鐦在高溫下可以被金屬鑭還原為單質鐦。^[8]

三氯化鐦（CfCl₃）是翡翠綠色固體，屬六方晶系，可以通過Cf₂O₃和HCl氣體於500 °C反應得到。^[9] CfCl₃可以當作原料來製備橙黃色的三碘化物CfI₃，它可以進一步被還原為薰衣草紫色的二碘化物CfI₂。^[10]三氯化鐦直接用氫氣還原，可以得到二氯化鐦^[11]，該化合物是穩定的^[12]。

三氟化鐦（CfF₃）是黃綠色固體，其晶體結構在加熱至室溫之上時逐漸由正交轉變為六方。^[13]四氟化鐦（CfF₄）是亮綠色固體，有單斜結構。^[14]

二碘化鐦（CfI₂）是深紫色固體，在室溫時有穩定的菱方結構和不穩定的六方結構。三碘化鐦（CfI₃）是檸檬黃色固體，有菱方結構，在約800℃升華。^[15]

氟氧化鐦（CfOF）可由三氟化鐦在高溫下的水解反應製得。^[16]氯氧化鐦（CfOCl）由三氯化鐦的水合物在280–320 °C的水解得到。^[17]氯氧化鐦是第一個被發現的鐦化合物。^[18]

硫酸鐦在1200 °C的空氣中加熱，再在500 °C的氫氣中還原，可以得到Cf₂O₃。^[9]氫氧化物Cf(OH)₃與氟化物CfF₃微溶於水。^[9]

多硼酸鐦（英語：Californium(III) polyborate）是一種較為特殊的化合物，化合物中存在鐦和硼酸根的共價鍵。^[19]

氮化鐦（CfN）、砷化鐦（CfAs）和銻化鐦（CfSb）是鐦的氮族元素化合物，它們有着氯化鈉晶型，可由金屬鐦和相應的單質化合而成。^[20]

配合物

三價的鐦離子可以在水溶液中以[Cf(H₂O)₈]³⁺和[Cf(H₂O)₉]³⁺水配離子的形式存在，成鹽[Cf(H₂O)₉](ClO₄)₃或[Cf(H₂O)₉](CF₃SO₃)₃。^[21]β-二酮類配合物（如萘甲酰三氟丙酮等）可以和Cf³⁺形成螯合物，從水溶液中萃取出來。^[22]

三氯化鐦和過量的2,6-吡啶二甲酸（PDA）於150℃在1：1的乙醇水溶液中反應，可以製得Cf(HDPA)₃·H₂O^[23]，它是一種電荷轉移配合物。^[24]

鐦是已知可形成有機金屬化合物的金屬中，原子序第二大的元素。Cp₃Cf（Cp = C₅H₅）由二茂鈹（Cp₂Be）和三氯化鐦（CfCl₃）反應得到，並通過X射線繞射進行了表徵。^[25]

參見

參考文獻

^ 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.
^ Element 98 Prepared. Science News Letters. December 1960, 78 (26).
^ CRC 2006，第4-8頁.
^ ^4.0 ^4.1 ^4.2 Jakubke 1994，第166頁.
^ Seaborg 2004.
^ Cotton 1999，第1163頁.
^ ^7.0 ^7.1 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.
^ 朱文祥. 無機化合物製備手冊. 化學工業出版社, 2006. pp 171. ISBN 7-5025-8537-0
^ ^9.0 ^9.1 ^9.2 Cunningham 1968，第105頁.
^ Cotton, Simon. Lanthanide and Actinide Chemistry. West Sussex, England: John Wiley & Sons. 2006: 168. ISBN 978-0-470-01006-8.
^ 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.
^ Greenwood 1997，第1272頁.
^ 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.
^ 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.
^ 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.
^ 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.
^ 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.
^ Seaborg, Glenn T. Man-Made Transuranium Elements. Prentice-Hall. 1963.
^ Unusual structure, bonding, and properties may provide a new possibility for a californium borate. 1 June 2015 [29 July 2015]. （原始內容存檔於2017-08-02）.
^ 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
^ 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
^ 張青蓮等. 無機化學叢書第十卷錒系錒系後元素. 科學出版社, 1998. pp 322. "12.2.4 鐦的水溶液化學"
^ 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
^ 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
^ 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.

參考書目

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 , 編. 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 (編). 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 (編). Concise Encyclopedia Chemistry. trans. rev. Eagleson, Mary. Berlin: Walter de Gruyter. 1994 [2017-08-02]. ISBN 3-11-011451-8. （原始內容存檔於2016-06-03）.
Seaborg, Glenn T. Californium. Geller, Elizabeth (編). Concise Encyclopedia of Chemistry. New York City: McGraw-Hill: 94. 2004. ISBN 0-07-143953-6.

[Krebs2006-1] 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).

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

[FOOTNOTEJakubke1994166-4] 4.0 ^4.1 ^4.2 Jakubke 1994，第166頁.

[FOOTNOTESeaborg2004-5] Seaborg 2004.

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

[CF_OX-7] 7.0 ^7.1 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. 無機化合物製備手冊. 化學工業出版社, 2006. pp 171. ISBN 7-5025-8537-0

[FOOTNOTECunningham1968105-9] 9.0 ^9.1 ^9.2 Cunningham 1968，第105頁.

[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.

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

[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.

[dictoc-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.

[CF_OX_CL_1969-17] 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.

[doe-19] Unusual structure, bonding, and properties may provide a new possibility for a californium borate. 1 June 2015 [29 July 2015]. （原始內容存檔於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] 張青蓮等. 無機化學叢書第十卷錒系錒系後元素. 科學出版社, 1998. pp 322. "12.2.4 鐦的水溶液化學"

[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.

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