双环辛四烯合锕系元素
双环辛四烯合锕系元素是一类有机锕系元素化合物,包含以锕系元素为中心的茂金属。它们通常呈夹心结构,里面有两个环辛四烯基配体(COT2-,即C
8H2−
8)与4价锕系元素(An)中心结合,因此通式为An(C8H8)2。[1][2]
性质已知的双环辛四烯合锕系元素
名称 | 化学式 | An中心 | 首次合成 | 晶体颜色 | An–COT距离(Å) | 空间群 |
---|---|---|---|---|---|---|
双环辛四烯合钍 | Th(C8H8)2 | Th | 1969年 | 鲜黄色 | 2.004 | P21/n |
双环辛四烯合镤 | Pa(C8H8)2 | Pa | 1974年 | 淡黄色 | – | P21/n |
双环辛四烯合铀 | U(C8H8)2 | U | 1968年 | 深绿色 | 1.926 | P21/n |
双环辛四烯合镎 | Np(C8H8)2 | Np | 1970年 | 黄棕色 | 1.909 | P21/n |
双环辛四烯合钚 | Pu(C8H8)2 | Pu | 1970年 | 深红色 | 1.898 | I2/m |
其中得到最多研究的化合物是双环辛四烯合铀(U(C8H8)2)。它于1968年合成,是该系列中第一个得到合成的成员,至今仍被视为原型。[2][3]该系列中其他得到合成的成员为双环辛四烯合镤[4](Pa(C8H8)2)、双环辛四烯合钍[5](Th(C8H8)2)、双环辛四烯合镎[6](Np(C8H8)2)和双环辛四烯钚[7][8](Pu(C8H8)2)。由于双环辛四烯合镎和双环辛四烯合钚的辐射危害可以很严重,它们自1980年代以来就没有得到广泛的实验研究。[9][10]
其他双环辛四烯合元素
镧系元素(M(C8H8)2,M = Nd、Tb和Yb)也存在类似的夹心化合物,但其中键合主要是离子键而不是共价键(参见双环辛四烯合镧系元素)。[3]
参见
参考文献
- ^ Minasian, Stefan G.; Keith, Jason M. New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory. Chem. Sci. 2014, 5 (1): 351–359 [2022-12-01]. doi:10.1039/C3SC52030G. (原始内容存档于2022-12-01).
- ^ 2.0 2.1 Greenwood, Norman N.; Earnshaw, Alan. Chemistry of the Elements. Butterworth-Heinemann. 1997: 1278–1280. ISBN 978-0-08-037941-8.
- ^ 3.0 3.1 Seyferth, D. Uranocene. The First Member of a New Class of Organometallic Derivatives of the f Elements. Organometallics. 2004, 23 (15): 3562–3583. doi:10.1021/om0400705 .
- ^ Goffart, J.; Fuger, J.; Brown, D.; Duyckaerts, G. On the cyclooctatetraenyl compounds of actinide elements part II. Bis-(cyclooctatetraenyl) protactinium(IV). Inorganic and Nuclear Chemistry Letters. 1974-05-01, 10 (5): 413–419. ISSN 0020-1650. doi:10.1016/0020-1650(74)80119-4 (英语).
- ^ Avdeef, Alex; Raymond, Kenneth N.; Hodgson, Keith O.; Zalkin, Allan. Two isostructural actinide .pi. complexes. Crystal and molecular structure of bis(cyclooctatetraenyl)uranium(IV), U(C8H8)2, and bis(cyclooctatetraenyl)thorium(IV), Th(C8H8)2. Inorganic Chemistry. 1972-05-01, 11 (5): 1083–1088. ISSN 0020-1669. doi:10.1021/ic50111a034.
- ^ De Ridder, D. J. A.; Rebizant, J.; Apostolidis, C.; Kanellakopulos, B.; Dornberger, E. Bis(cyclooctatetraenyl)neptunium(IV). Acta Crystallographica Section C: Crystal Structure Communications. 1996-03-15, 52 (3): 597–600 [2022-12-01]. ISSN 0108-2701. doi:10.1107/S0108270195013047. (原始内容存档于2022-12-01) (英语).
- ^ Windorff, Cory J.; Sperling, Joseph M.; Albrecht-Schönzart, Thomas E.; Bai, Zhuanling; Evans, William J.; Gaiser, Alyssa N.; Gaunt, Andrew J.; Goodwin, Conrad A. P.; Hobart, David E.; Huffman, Zachary K.; Huh, Daniel N. A Single Small-Scale Plutonium Redox Reaction System Yields Three Crystallographically-Characterizable Organoplutonium Complexes. Inorganic Chemistry. 2020-09-21, 59 (18): 13301–13314 [2022-12-01]. ISSN 0020-1669. OSTI 1680020. PMID 32910649. S2CID 221623763. doi:10.1021/acs.inorgchem.0c01671. (原始内容存档于2022-12-01) (英语).
- ^ Apostolidis, Christos; Walter, Olaf; Vogt, Jochen; Liebing, Phil; Maron, Laurent; Edelmann, Frank T. A Structurally Characterized Organometallic Plutonium(IV) Complex. Angewandte Chemie International Edition. 2017-04-24, 56 (18): 5066–5070. PMC 5485009 . PMID 28371148. doi:10.1002/anie.201701858 (英语).
- ^ Windorff, Cory J.; Sperling, Joseph M.; Albrecht-Schönzart, Thomas E.; Bai, Zhuanling; Evans, William J.; Gaiser, Alyssa N.; Gaunt, Andrew J.; Goodwin, Conrad A. P.; Hobart, David E.; Huffman, Zachary K.; Huh, Daniel N. A Single Small-Scale Plutonium Redox Reaction System Yields Three Crystallographically-Characterizable Organoplutonium Complexes. Inorganic Chemistry. 2020-09-21, 59 (18): 13301–13314 [2022-12-01]. ISSN 0020-1669. OSTI 1680020. PMID 32910649. S2CID 221623763. doi:10.1021/acs.inorgchem.0c01671. (原始内容存档于2022-12-01) (英语).
- ^ Apostolidis, Christos; Walter, Olaf; Vogt, Jochen; Liebing, Phil; Maron, Laurent; Edelmann, Frank T. A Structurally Characterized Organometallic Plutonium(IV) Complex. Angewandte Chemie International Edition. 2017-04-24, 56 (18): 5066–5070. PMC 5485009 . PMID 28371148. doi:10.1002/anie.201701858 (英语).