元素氧化态列表列出目前已知的118种化学元素之所有已知的整数氧化态,其中最常见的氧化态以粗体标记。所有元素以单质存在时(无论单原子或多原子,包括同素异形体)氧化态均为0,因此下表中氧化态0的栏位只列出已发现在化合物中存在氧化态0的元素。
该列表主要参考《元素化学》(Chemistry of the Elements)[1],显示出元素周期律在元素价态上的一些趋势。
+1 粗体表示其为该元素之主要氧化态
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下图是欧文·朗缪尔1919年在研究八隅体规则时所画:[150]
Greenwood, N. N.; Earnshaw, A. (1997). Chemistry of the Elements, 2nd Edition, Oxford:Butterworth-Heinemann. ISBN 0-7506-3365-4, p. 28.
已合成出在高压下热力学稳定的氦化钠((Na+)2He(e-)2),参见:Dong, Xiao; Oganov, Artem R.; Goncharov, Alexander F.; Stavrou, Elissaios; Lobanov, Sergey; Saleh, Gabriele; Qian, Guang-Rui; Zhu, Qiang; Gatti, Carlo; Deringer, Volker L.; Dronskowski, Richard; Zhou, Xiang-Feng; Prakapenka, Vitali B.; Konôpková, Zuzana; Popov, Ivan A.; Boldyrev, Alexander I.; Wang, Hui-Tian. A stable compound of helium and sodium at high pressure. Nature Chemistry. 6 February 2017, 9 (5): 440–445. Bibcode:2017NatCh...9..440D. PMID 28430195. S2CID 20459726. arXiv:1309.3827 . doi:10.1038/nchem.2716.
Na(−1)、K(−1)、Rb(−1)和Cs(−1)已知存在于碱化物中。《元素化学》中仅标示了钠的-1态,且还错误标示了Li(−1)的存在:目前尚未发现锂(−1)化物。
Be(I)已在一氢化铍(BeH)中观察到,参见:Shayesteh, A.; Tereszchuk, K.; Bernath, P. F.; Colin, R. Infrared Emission Spectra of BeH and BeD (PDF). J. Chem. Phys. 2003, 118 (3): 1158 [2007-12-10]. Bibcode:2003JChPh.118.1158S. doi:10.1063/1.1528606. (原始内容 (PDF)存档于2007-12-02). and in [(CAAC)2Be]+• [CAAC = cyclic (alkyl)(amino)carbene], see Wang, Guocang; Walley, Jacob E.; Dickie, Diane E.; Pan, Sudip; Frenking, Gernot; Gilliard Jr., Robert G. A Stable, Crystalline Beryllium Radical Cation. J. Am. Chem. Soc. 2020, 142 (10): 4560–4 [2020-11-17]. PMID 32088963. S2CID 211262005. doi:10.1021/jacs.9b13777. (原始内容存档于2022-09-24).
四唑环中有一对以双键键结、氧化态为0的氮原子。母体1-H-四唑(CH2N4)的合成过程参见Ronald A. Henry and William G. Finnegan, "An Improved Procedure for the Deamination of 5-Aminotetrazole", _J. Am. Chem. Soc._ (1954), 76, 1, 290–291,
https://doi.org/10.1021/ja01630a086.
已知含有氦原子的SF6+团簇中有氟(0)原子作为配基,参见:Albertini, Simon; Bergmeister, Stefan; Laimer, Felix; Martini, Paul; Gruber, Elisabeth; Zappa, Fabio; Ončák, Milan; Scheier, Paul; Echt, Olof. SF 6 + : Stabilizing Transient Ions in Helium Nanodroplets. The Journal of Physical Chemistry Letters. 2021-04-22, 12 (17): 4112–4117 [2023-05-28]. ISSN 1948-7185. PMC 8154854 . PMID 33886323. doi:10.1021/acs.jpclett.1c01024 . (原始内容存档于2022-09-24) (英语).
Ne(0)已在Cr(CO)5Ne中观察到,参见:Perutz, Robin N.; Turner, James J. Photochemistry of the Group 6 hexacarbonyls in low-temperature matrices. III. Interaction of the pentacarbonyls with noble gases and other matrices. Journal of the American Chemical Society. August 1975, 97 (17): 4791–4800. doi:10.1021/ja00850a001.
实验表明,氯化钠在高压下存在几种不寻常的化学计量,例如Na3Cl,其中包含一层Na(0)原子,参见:Zhang, W.; Oganov, A. R.; Goncharov, A. F.; Zhu, Q.; Boulfelfel, S. E.; Lyakhov, A. O.; Stavrou, E.; Somayazulu, M.; Prakapenka, V. B.; Konôpková, Z. Unexpected Stable Stoichiometries of Sodium Chlorides. Science. 2013, 342 (6165): 1502–1505. Bibcode:2013Sci...342.1502Z. PMID 24357316. S2CID 15298372. arXiv:1310.7674 . doi:10.1126/science.1244989.
Al(−2)已在Sr14[Al4]2[Ge]3中观察到,参见:Wemdorff, Marco; Röhr, Caroline. Sr14[Al4]2[Ge]3: Eine Zintl-Phase mit isolierten [Ge]4–- und [Al4]8–-Anionen / Sr14[Al4]2[Ge]3: A Zintl Phase with Isolated [Ge]4–- and [Al4]8– Anions. Zeitschrift für Naturforschung B. 2007, 62 (10): 1227. S2CID 94972243. doi:10.1515/znb-2007-1001 (德语).
P(0)已被观察到,参见:Wang, Yuzhong; Xie, Yaoming; Wei, Pingrong; King, R. Bruce; Schaefer, Iii; Schleyer, Paul v. R.; Robinson, Gregory H. Carbene-Stabilized Diphosphorus. Journal of the American Chemical Society. 2008, 130 (45): 14970–1. PMID 18937460. doi:10.1021/ja807828t.
Cl2O6⇌2ClO3反应的化学平衡曾被Greenwood & Earnshaw提及,但已被驳回。参见:Lopez, Maria; Juan E. Sicre. Physicochemical properties of chlorine oxides. 1. Composition, ultraviolet spectrum, and kinetics of the thermolysis of gaseous dichlorine hexoxide. J. Phys. Chem. 1990, 94 (9): 3860–3863. doi:10.1021/j100372a094., and Cl2O6 is actually chlorine(V,VII) oxide. However, ClO3 has been observed, see Grothe, Hinrich; Willner, Helge. Chlorine Trioxide: Spectroscopic Properties, Molecular Structure, and Photochemical Behavior. Angew. Chem. Int. Ed. 1994, 33 (14): 1482–1484. doi:10.1002/anie.199414821.
Ar(0)已在氟氩化氢(HArF)及ArCF22+中观察到,参见:Lockyear, J.F.; Douglas, K.; Price, S.D.; Karwowska, M.; et al. Generation of the ArCF22+ Dication. Journal of Physical Chemistry Letters. 2010, 1: 358. doi:10.1021/jz900274p.
已在以氖作为基质的隔离下观察到钙、锶、钡的八羰基配合物,但尚不清楚这些是否为其0价态配合物,因为计算结果否定了配合物中金属原子和配体形成共价键或离子键与否,参见:Wu, X.; Zhao, L.; Jin, J.; Pan, S.; Li, W.; Jin, X.; Wang, G.; Zhou, M.; Frenking, G. Observation of alkaline earth complexes M(CO)8 (M = Ca, Sr, or Ba) that mimic transition metals. Science. 2018, 361 (6405): 912–916. Bibcode:2018Sci...361..912W. PMID 30166489. S2CID 52131470. doi:10.1126/science.aau0839
Ca(I)已被观察到,参见:Krieck, Sven; Görls, Helmar; Westerhausen, Matthias. Mechanistic Elucidation of the Formation of the Inverse Ca(I) Sandwich Complex [(thf)3Ca(μ-C6H3-1,3,5-Ph3)Ca(thf)3] and Stability of Aryl-Substituted Phenylcalcium Complexes. Journal of the American Chemical Society. 2010, 132 (35): 12492–501. PMID 20718434. doi:10.1021/ja105534w.
Sc(0)已被观察到,参见:F. Geoffrey N. Cloke; Karl Khan & Robin N. Perutz. η-Arene complexes of scandium(0) and scandium(II). J. Chem. Soc., Chem. Commun. 1991, (19): 1372–1373. doi:10.1039/C39910001372.
Sc(I)已被观察到,参见:Polly L. Arnold; F. Geoffrey; N. Cloke; Peter B. Hitchcock & John F. Nixon. The First Example of a Formal Scandium(I) Complex: Synthesis and Molecular Structure of a 22-Electron Scandium Triple Decker Incorporating the Novel 1,3,5-Triphosphabenzene Ring. J. Am. Chem. Soc. 1996, 118 (32): 7630–7631. doi:10.1021/ja961253o.
Sc(II)已被观察到,参见:Woen, David H.; Chen, Guo P.; Ziller, Joseph W.; Boyle, Timothy J.; Furche, Filipp; Evans, William J. Solution Synthesis, Structure, and CO Reduction Reactivity of a Scandium(II) Complex. Angewandte Chemie International Edition. January 2017, 56 (8): 2050–2053. PMID 28097771. doi:10.1002/anie.201611758.
Ti(−2)、V(−3)、Cr(−4)、Co(−3)、Zr(−2)、Nb(−3)、Mo(−4)、Ru(−2)、Rh( −3)、Hf(−2)、Ta(−3)和W(−4)存在于阴离子二元金属羰基错合物中,参见:[1] (页面存档备份,存于互联网档案馆), p. 4 (in German); [2], pp. 97–100; [3], p. 239
Ti(−1)最初被报告存在于[Ti(bipy)3]− 中,但后来证明其为Ti(+3),参见Bowman, A. C.; England, J.; Sprouls, S.; Weihemüller, T.; Wieghardt, K. Electronic structures of homoleptic [tris(2,2'-bipyridine)M]n complexes of the early transition metals (M = Sc, Y, Ti, Zr, Hf, V, Nb, Ta; n = 1+, 0, 1-, 2-, 3-): an experimental and density functional theoretical study. Inorganic Chemistry. 2013, 52 (4): 2242–56. PMID 23387926. doi:10.1021/ic302799s. 不过,Ti(−1)被发现存在于[Ti(η-C6H6]−和[Ti(η-C6H5CH3)]−中, 参见:Bandy, J. A.; Berry, A.; Green, M. L. H.; Perutz, R. N.; Prout, K.; Verpeautz, J.-N. Synthesis of anionic sandwich compounds: [Ti(η-C6H5R)2]– and the crystal structure of [K(18-crown-6)(µ-H)Mo(η-C5H5)2]. Inorganic Chemistry. 1984, 52 (4): 729–731. doi:10.1039/C39840000729.
Ti(I)已在[Ti(η6-1,3,5-C6H3iPr3)2][BAr4] (Ar = C6H5, p-C6H4F, 3,5-C6H3(CF3)2)中观察到,参见:Calderazzo, Fausto; Ferri, Isabella; Pampaloni, Guido; Englert, Ulli; Green, Malcolm L. H. Synthesis of [Ti(η6-1,3,5-C6H3iPr3)2][BAr4] (Ar = C6H5, p-C6H4F, 3,5-C6H3(CF3)2), the First Titanium(I) Derivatives. Organometallics. 1997, 16 (14): 3100–3101. doi:10.1021/om970155o.
Jilek, Robert E.; Tripepi, Giovanna; Urnezius, Eugenijus; Brennessel, William W.; Young, Victor G. Jr.; Ellis, John E. Zerovalent titanium–sulfur complexes. Novel dithiocarbamato derivatives of Ti(CO)6: [Ti(CO)4(S2CNR2)]−. Chem. Commun. 2007, (25): 2639–2641. PMID 17579764. doi:10.1039/B700808B.
Fe(VIII)已被报告,参见:Yurii D. Perfiliev; Virender K. Sharma. Higher Oxidation States of Iron in Solid State: Synthesis and Their Mössbauer Characterization – Ferrates – ACS Symposium Series (ACS Publications). Platinum Metals Review. 2008, 48 (4): 157–158. doi:10.1595/147106704X10801. 然而,其存在与否一直有所争议。
Fe(−4)、Ru(−4)和Os(−4)已在含有八面体配合物[MIn6−xSnx]的富金属化合物中观察到;Pt(−3)(以二聚体阴离子[Pt–Pt]6−的形式)、Cu(−2)、Zn(−2)、Ag(−2)、Cd(−2)、Au(−2)和Hg(−2)(以二聚体和单体阴离子之形式;Zn、Cd、Hg的二聚体离子最初被报告为[T–T]2−的形式、但后来的研究显示所有这些元素的二聚体阴离子皆为[T–T]4−形式)已在下列化合物中观察到:La2Pt2In、La2Cu2In、Ca5Au3、Ca5Ag3、Ca5Hg3、Sr5Cd3、Ca5Zn3(结构为(AE2+)5(T–T)4−T2 −⋅4e−)、Yb3Ag2、Ca5Au4和Ca3Hg2;Au(-3)已在ScAuSn及其他18电子的半赫斯勒化合物中观察到。参见:Changhoon Lee; Myung-Hwan Whangbo. Late transition metal anions acting as p-metal elements. Solid State Sciences. 2008, 10 (4): 444–449. Bibcode:2008SSSci..10..444K. doi:10.1016/j.solidstatesciences.2007.12.001. and Changhoon Lee; Myung-Hwan Whangbo; Jürgen Köhler. Analysis of Electronic Structures and Chemical Bonding of Metal-rich Compounds. 2. Presence of Dimer (T–T)4– and Isolated T2– Anions in the Polar Intermetallic Cr5B3-Type Compounds AE5T3 (AE = Ca, Sr; T = Au, Ag, Hg, Cd, Zn). Zeitschrift für Anorganische und Allgemeine Chemie. 2010, 636 (1): 36–40. doi:10.1002/zaac.200900421.
Ni(−2)已在Li2[Ni(1,5-COD)2]中观察到,参见:Jonas, Klaus. Dilithium-Nickel-Olefin Complexes. Novel Bimetal Complexes Containing a Transition Metal and a Main Group Metal. Angew. Chem. Int. Ed. 1975, 14 (11): 752–753. doi:10.1002/anie.197507521. and Ellis, John E. Adventures with Substances Containing Metals in Negative Oxidation States. Inorganic Chemistry. 2006, 45 (8): 3167–86. PMID 16602773. doi:10.1021/ic052110i.
Zn(0)已被观察到,参见:Singh, Amit Pratap; Samuel, Prinson P.; Roesky, Herbert W.; Schwarzer, Martin C.; Frenking, Gernot; Sidhu, Navdeep S.; Dittrich, Birger. A Singlet Biradicaloid Zinc Compound and Its Nonradical Counterpart. J. Am. Chem. Soc. 2013, 135 (19): 7324–9. PMID 23600486. doi:10.1021/ja402351x. and Soleilhavoup, Michèle; Bertrand, Guy. Cyclic (Alkyl)(Amino)Carbenes (CAACs): Stable Carbenes on the Rise. Acc. Chem. Res. 2015, 48 (2): 256–266. PMID 25515548. doi:10.1021/ar5003494.
As(0)已被观察到,参见:Abraham, Mariham Y.; Wang, Yuzhong; Xie, Yaoming; Wei, Pingrong; Shaefer III, Henry F.; Schleyer, P. von R.; Robinson, Gregory H. Carbene Stabilization of Diarsenic: From Hypervalency to Allotropy. Chemistry: A European Journal. 2010, 16 (2): 432–5. PMID 19937872. doi:10.1002/chem.200902840.
As(I)已在AsI中观察到,参见:Ellis, Bobby D.; MacDonald, Charles L. B. Stabilized Arsenic(I) Iodide: A Ready Source of Arsenic Iodide Fragments and a Useful Reagent for the Generation of Clusters. Inorganic Chemistry. 2004, 43 (19): 5981–6. PMID 15360247. doi:10.1021/ic049281s.
As(IV)已在As(OH)4及HAsO−
中观察到,参见:Kläning, Ulrik K.; Bielski, Benon H. J.; Sehested, K. Arsenic(IV). A pulse-radiolysis study. Inorganic Chemistry. 1989, 28 (14): 2717–24. doi:10.1021/ic00313a007.
Se(−1)已在二硒化物 (Se22−)中观察到。
已使用DFT在[ReOSe(2-pySe)3]中识别出Se(0)原子,参见:Cargnelutti, Roberta; Lang, Ernesto S.; Piquini, Paulo; Abram, Ulrich. Synthesis and structure of [ReOSe(2-Se-py)3]: A rhenium(V) complex with selenium(0) as a ligand. Inorganic Chemistry Communications. 2014, 45: 48–50. ISSN 1387-7003. doi:10.1016/j.inoche.2014.04.003.
Se(III)已在Se2NBr3中观察到,参见:Lau, Carsten; Neumüller, Bernhard; Vyboishchikov, Sergei F.; Frenking, Gernot; Dehnicke, Kurt; Hiller, Wolfgang; Herker, Martin. Se2NBr3, Se2NCl5, Se2NCl−6: New Nitride Halides of Selenium(III) and Selenium(IV). Chemistry: A European Journal. 1996, 2 (11): 1393–1396. doi:10.1002/chem.19960021108.
氧化态为0的钇和所有镧系元素(铈及钷除外)已在双(1,3,5-三叔丁基苯)错合物中观察到,参见:Cloke, F. Geoffrey N. Zero Oxidation State Compounds of Scandium, Yttrium, and the Lanthanides. Chem. Soc. Rev. 1993, 22: 17–24. doi:10.1039/CS9932200017. and Arnold, Polly L.; Petrukhina, Marina A.; Bochenkov, Vladimir E.; Shabatina, Tatyana I.; Zagorskii, Vyacheslav V.; Cloke. Arene complexation of Sm, Eu, Tm and Yb atoms: a variable temperature spectroscopic investigation. Journal of Organometallic Chemistry. 2003-12-15, 688 (1–2): 49–55. doi:10.1016/j.jorganchem.2003.08.028.
Y(II)已在[(18-crown-6)K][(C5H4SiMe3)3Y]中观察到,参见:MacDonald, M. R.; Ziller, J. W.; Evans, W. J. Synthesis of a Crystalline Molecular Complex of Y2+, [(18-crown-6)K][(C5H4SiMe3)3Y]. J. Am. Chem. Soc. 2011, 133 (40): 15914–17. PMID 21919538. doi:10.1021/ja207151y.
Zr(−1)曾被报告存在于[Zr(bipy)3]−中(参见 Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997: 960. ISBN 0-7506-3365-4. 及 Holleman, Arnold F.; Wiberg, Egon; Wiberg, Nils. Zirconium. Lehrbuch der Anorganischen Chemie 101. Walter de Gruyter. 1995: 1413. ISBN 978-3-11-012641-9 (德语).), 但后来被证明是Zr(+4),参见:Bowman, A. C.; England, J.; Sprouls, S.; Weihemüller, T.; Wieghardt, K. Electronic structures of homoleptic [tris(2,2'-bipyridine)M]n complexes of the early transition metals (M = Sc, Y, Ti, Zr, Hf, V, Nb, Ta; n = 1+, 0, 1-, 2-, 3-): an experimental and density functional theoretical study. Inorganic Chemistry. 2013, 52 (4): 2242–56. PMID 23387926. doi:10.1021/ic302799s.
Zr(0)及Hf(0)出现在(η6-(1,3,5-tBu)3C6H3)2M (M=Zr, Hf)及[(η5-C5R5M(CO)4]−中,参见:Chirik, P. J.; Bradley, C. A. 4.06 - Complexes of Zirconium and Hafnium in Oxidation States 0 to ii. Comprehensive Organometallic Chemistry III. From Fundamentals to Applications 4. Elsevier Ltd. 2007: 697–739. ISBN 9780080450476. doi:10.1016/B0-08-045047-4/00062-5.
Nb(0)及Ta(0)的配合物已被观察到,参见:Holleman, Arnold F.; Wiberg, Egon; Wiberg, Nils. 4.5.7. Niobium(0) and Tantalum(0). J. A. McCleverty; T.J. Meyer (编). Comprehensive Coordination Chemistry II: From Biology to Nanotechnology 4 2. Newnes. 2003: 297–299. ISBN 978-0-08-091316-2.
Rh(VII)已知存在于RhO3+阳离子中,参见:The Highest Oxidation State of Rhodium: Rhodium(VII) in [RhO3]+. Angew. Chem. Int. Ed. 2022. doi:10.1002/anie.202207688.
Pd(V)已被确认存在于含有五配位数钯原子的有机矽化合物之络合物中,参见:Shimada, Shigeru; Li, Yong-Hua; Choe, Yoong-Kee; Tanaka, Masato; Bao, Ming; Uchimaru, Tadafumi. Multinuclear palladium compounds containing palladium centers ligated by five silicon atoms. Proceedings of the National Academy of Sciences. 2007, 104 (19): 7758–7763. doi:10.1073/pnas.0700450104.
Ag−离子已在金属与液态氨之溶液中观察到,参见:Tran, N. E.; Lagowski, J. J. Metal Ammonia Solutions: Solutions Containing Argentide Ions. Inorganic Chemistry. 2001, 40 (5): 1067–68. doi:10.1021/ic000333x.
Ag(0)已在低温基质隔离条件下的羰基络合物中观察到,参见McIntosh, D.; Ozin, G. A. Synthesis using metal vapors. Silver carbonyls. Matrix infrared, ultraviolet-visible, and electron spin resonance spectra, structures, and bonding of silver tricarbonyl, silver dicarbonyl, silver monocarbonyl, and disilver hexacarbonyl. J. Am. Chem. Soc. 1976, 98 (11): 3167–75. doi:10.1021/ja00427a018.
Cd(I)已在四氯铝酸镉(I)(Cd2(AlCl4)2)中观察到,参见:Holleman, Arnold F.; Wiberg, Egon; Wiberg, Nils. Cadmium. Lehrbuch der Anorganischen Chemie 91–100. Walter de Gruyter. 1985: 1056–1057. ISBN 978-3-11-007511-3 (德语).
In(–5)已在La3InGe中观察到,参见:Guloy, A. M.; Corbett, J. D. Synthesis, Structure, and Bonding of Two Lanthanum Indium Germanides with Novel Structures and Properties. Inorganic Chemistry. 1996, 35 (9): 2616–22. PMID 11666477. doi:10.1021/ic951378e.
In(−2)已在Na2In中观察到,参见:[5], p. 69.
Sb(−2)已在[Sb2]4−及RbBa4[Sb2][Sb][O]中观察到,参见:Boss, Michael; Petri, Denis; Pickhard, Frank; Zönnchen, Peter; Röhr, Caroline. Neue Barium-Antimonid-Oxide mit den Zintl-Ionen [Sb]3−, [Sb2]4− und 1∞[Sbn]n− / New Barium Antimonide Oxides containing Zintl Ions [Sb]3−, [Sb2]4− and 1∞[Sbn]n−. Zeitschrift für Anorganische und Allgemeine Chemie. 2005, 631 (6–7): 1181–1190. doi:10.1002/zaac.200400546 (德语).
Sb(I)及Sb(II)已在有机锑化合物中观察到;关于Sb(I),参见:Šimon, Petr; de Proft, Frank; Jambor, Roman; Růžička, Aleš; Dostál, Libor. Monomeric Organoantimony(I) and Organobismuth(I) Compounds Stabilized by an NCN Chelating Ligand: Syntheses and Structures. Angewandte Chemie International Edition. 2010, 49 (32): 5468–5471. PMID 20602393. doi:10.1002/anie.201002209.
Sb(IV)已在[SbCl
6]2−中观察到,参见:Nobuyoshi Shinohara; Masaaki Ohsima. Production of Sb(IV) Chloro Complex by Flash Photolysis of the Corresponding Sb(III) and Sb(V) Complexes in CH3CN and CHCl3. Bulletin of the Chemical Society of Japan. 2000, 73 (7): 1599–1604. doi:10.1246/bcsj.73.1599.
Te(0)已在碲醇盐(tellurolates)中观察到。
I(VI)已在IO3、IO42−、H5IO6−、H2IO52−、H4IO62−及HIO53−中观察到,参见:Kläning, Ulrik K.; Sehested, Knud; Wolff, Thomas. Laser flash photolysis and pulse radiolysis of iodate and periodate in aqueous solution. Properties of iodine(VI). J. Chem. Soc., Faraday Trans. 1. 1981, 77 (7): 1707–18. doi:10.1039/F19817701707.
Pr(I)已在[PrB4]−中观察到,参见:Chen, Xin; Chen, Teng-Teng; Li, Wang-Lu; Lu, Jun-Bo; Zhao, Li-Juan; Jian, Tian; Hu, Han-Shi; Wang, Lai-Sheng; Li, Jun. Lanthanides with Unusually Low Oxidation States in the PrB3– and PrB4– Boride Clusters. Inorganic Chemistry. 2018-12-13, 58 (1): 411–418. PMID 30543295. S2CID 56148031. doi:10.1021/acs.inorgchem.8b02572.
Pr(V)已在[PrO2]+中观察到,参见:Zhang, Qingnan; Hu, Shu-Xian; Qu, Hui; Su, Jing; Wang, Guanjun; Lu, Jun-Bo; Chen, Mohua; Zhou, Mingfei; Li, Jun. Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides. Angewandte Chemie International Edition. 2016-06-06, 55 (24): 6896–6900. ISSN 1521-3773. PMID 27100273. doi:10.1002/anie.201602196.
Nd(IV)已在不稳定的固体化合物中观察到,参见:Holleman, Arnold Frederik; Wiberg, Egon, Wiberg, Nils , 编, Inorganic Chemistry, 由Eagleson, Mary; Brewer, William翻译, San Diego/Berlin: Academic Press/De Gruyter, 2001, ISBN 0-12-352651-5
所有镧系元素(镧至镏)的+2氧化态均已在其二卤化物和碱土金属二卤化物形成的稀固溶体中(参阅:Holleman, Arnold Frederik; Wiberg, Egon, Wiberg, Nils , 编, Inorganic Chemistry, 由Eagleson, Mary; Brewer, William翻译, San Diego/Berlin: Academic Press/De Gruyter, 2001, ISBN 0-12-352651-5,镧、钆、镏除外)以及其有机金属分子错合物中(钷除外)观察到,参见:Lanthanides Topple Assumptions (页面存档备份,存于互联网档案馆) and Meyer, G. All the Lanthanides Do It and Even Uranium Does Oxidation State +2. Angewandte Chemie International Edition. 2014, 53 (14): 3550–51. PMID 24616202. doi:10.1002/anie.201311325.。此外,虽然所有镧系元素皆形成二氢化物(LnH2)、二碳化物(LnC2)、一硫化物(LnS)、一硒化物(LnSe)和一碲化物(LnTe),但对于大多数镧系元素,这些化合物中的镧系离子实为+3态,伴随著离域至导带的电子,例如:Ln3+(H−)2(e−)。
SmB6-团簇阴离子已被报告,其中含有罕见的+1态钐,参见:Paul, J. Robinson; Xinxing, Zhang; Tyrel, McQueen; Kit, H. Bowen; Anastassia, N. Alexandrova. SmB6– Cluster Anion: Covalency Involving f Orbitals. J. Phys. Chem. A 2017, 121, 8, 1849–1854. 2017, 121 (8): 1849–1854 [2023-05-28]. (原始内容存档于2022-09-25)..
Dy(IV)已在不稳定的固态化合物中观察到,参见:Holleman, Arnold Frederik; Wiberg, Egon, Wiberg, Nils , 编, Inorganic Chemistry, 由Eagleson, Mary; Brewer, William翻译, San Diego/Berlin: Academic Press/De Gruyter, 2001, ISBN 0-12-352651-5
Os(−1)已在Na[Os(CO)
13]中观察到,参见:Krause, J.; Siriwardane, Upali; Salupo, Terese A.; Wermer, Joseph R.; Knoeppel, David W.; Shore, Sheldon G. Preparation of [Os3(CO)11]2− and its reactions with Os3(CO)12; structures of [Et4N] [HOs3(CO)11] and H2OsS4(CO). Journal of Organometallic Chemistry. 1993, 454 (1–2): 263–271. doi:10.1016/0022-328X(93)83250-Y. and Carter, Willie J.; Kelland, John W.; Okrasinski, Stanley J.; Warner, Keith E.; Norton, Jack R. Mononuclear hydrido alkyl carbonyl complexes of osmium and their polynuclear derivatives. Inorganic Chemistry. 1982, 21 (11): 3955–3960. doi:10.1021/ic00141a019.
Ir(−3)已在Ir(CO)33−已在一溴化铪 (HfBr) 中观察到,参见:Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997: 1117. ISBN 0-7506-3365-4.
Ir(VIII)已在四氧化铱(IrO4)中观察到,参见:Gong, Yu; Zhou, Mingfei; Kaupp, Martin; Riedel, Sebastian. Formation and Characterization of the Iridium Tetroxide Molecule with Iridium in the Oxidation State +VIII. Angewandte Chemie International Edition. 2009, 48 (42): 7879–7883. PMID 19593837. doi:10.1002/anie.200902733.
Pt(−1)及Pt(−2)已分别在钡的铂化物BaPt及Ba2Pt中观察到,参见:Karpov, Andrey; Konuma, Mitsuharu; Jansen, Martin. An experimental proof for negative oxidation states of platinum: ESCA-measurements on barium platinides. Chemical Communications. 2006, (8): 838–840. PMID 16479284. doi:10.1039/b514631c.
Au(0)已被观察到,参见:Mézaille, Nicolas; Avarvari, Narcis; Maigrot, Nicole; Ricard, Louis; Mathey, François; Le Floch, Pascal; Cataldo, Laurent; Berclaz, Théo; Geoffroy, Michel. Gold(I) and Gold(0) Complexes of Phosphinine‐Based Macrocycles. Angewandte Chemie International Edition. 1999, 38 (21): 3194–3197. PMID 10556900. doi:10.1002/(SICI)1521-3773(19991102)38:21<3194::AID-ANIE3194>3.0.CO;2-O.
Tl(−5)已在Na23K9Tl15.3中观察到,参见:Dong, Z.-C.; Corbett, J. D. Na23K9Tl15.3: An Unusual Zintl Compound Containing Apparent Tl57−, Tl48−, Tl37−, and Tl5− Anions. Inorganic Chemistry. 1996, 35 (11): 3107–12. PMID 11666505. doi:10.1021/ic960014z.
Tl(−1)已在铊化铯(CsTl)中观察到,参见:King, R. B.; Schleyer, R. Theory and concepts in main-group cluster chemistry. Driess, M.; Nöth, H. (编). Molecular clusters of the main group elements. Wiley-VCH, Chichester. 2004: 19. ISBN 978-3-527-61437-0.
Tl(+2)已在四(超甲矽烷基)二铊([(Me3Si)Si]2Tl—Tl[Si(SiMe3)]2)中观察到,参见:Sonja Henkel; Dr. Karl Wilhelm Klinkhammer; Dr. Wolfgang Schwarz. Tetrakis(hypersilyl)dithallium(Tl—Tl): A Divalent Thallium Compound. Angew. Chem. Int. Ed. 1994, 33 (6): 681–683. doi:10.1002/anie.199406811.
Pb(−2)已在BaPb中观察到,参见:Ferro, Riccardo. Nicholas C. Norman , 编. Intermetallic Chemistry. Elsevier. 2008: 505. ISBN 978-0-08-044099-6. and Todorov, Iliya; Sevov, Slavi C. Heavy-Metal Aromatic Rings: Cyclopentadienyl Anion Analogues Sn56− and Pb56− in the Zintl Phases Na8BaPb6, Na8BaSn6, and Na8EuSn6. Inorganic Chemistry. 2004, 43 (20): 6490–94. doi:10.1021/ic000333x.
Pb(+1)及Pb(+3)已在有机铅化合物中观察到,如六甲基二铅烷(Pb2(CH3)6)等;有关Pb(I)的资讯,参阅:Siew-Peng Chia; Hong-Wei Xi; Yongxin Li; Kok Hwa Lim; Cheuk-Wai So. A Base-Stabilized Lead(I) Dimer and an Aromatic Plumbylidenide Anion. Angew. Chem. Int. Ed. 2013, 52 (24): 6298–6301. PMID 23629949. doi:10.1002/anie.201301954.
Bi(I)已在一溴化铋(BiBr)及一碘化铋(BiI)中观察到,参见:Godfrey, S. M.; McAuliffe, C. A.; Mackie, A. G.; Pritchard, R. G. Nicholas C. Norman , 编. Chemistry of arsenic, antimony, and bismuth. Springer. 1998: 67–84. ISBN 978-0-7514-0389-3.
Bi(IV)已被观察到,参见:A. I. Aleksandrov, I. E. Makarov. Formation of Bi(II) and Bi(IV) in aqueous hydrochloric solutions of Bi(III). Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science. 1987, 36 (2): 217–220. S2CID 94865394. doi:10.1007/BF00959349.
Po(V)已在dioxidopolonium(1+)(PoO+
)中观察到,参见:Thayer, John S. Relativistic Effects and the Chemistry of the Heavier Main Group Elements. Relativistic Methods for Chemists. Challenges and Advances in Computational Chemistry and Physics 10. 2010: 78. ISBN 978-1-4020-9974-8. doi:10.1007/978-1-4020-9975-5_2.
Th(-I)及U(-I)已在气相中以八羰基阴离子的形式被检测到,参见:Chaoxian, Chi; Sudip, Pan; Jiaye, Jin; Luyan, Meng; Mingbiao, Luo; Lili, Zhao; Mingfei, Zhou; Gernot, Frenking. Octacarbonyl Ion Complexes of Actinides [An(CO)8]+/− (An=Th, U) and the Role of f Orbitals in Metal–Ligand Bonding. Chemistry (Weinheim an der Bergstrasse, Germany). 25 (50): 11772–11784. 2019, 25 (50): 11772–11784. ISSN 0947-6539. PMC 6772027 . PMID 31276242. doi:10.1002/chem.201902625.
Th(-I)及U(-I)已在气相中以八羰基阴离子的形式被检测到,参见:Chaoxian, Chi; Sudip, Pan; Jiaye, Jin; Luyan, Meng; Mingbiao, Luo; Lili, Zhao; Mingfei, Zhou; Gernot, Frenking. Octacarbonyl Ion Complexes of Actinides [An(CO)8]+/− (An=Th, U) and the Role of f Orbitals in Metal–Ligand Bonding. Chemistry (Weinheim an der Bergstrasse, Germany). 25 (50): 11772–11784. 2019, 25 (50): 11772–11784. ISSN 0947-6539. PMC 6772027 . PMID 31276242. doi:10.1002/chem.201902625.
U(II)已在[K(2.2.2-Cryptand)][(C5H4SiMe3)3U]中观察到,参见:MacDonald, Matthew R.; Fieser, Megan E.; Bates, Jefferson E.; Ziller, Joseph W.; Furche, Filipp; Evans, William J. Identification of the +2 Oxidation State for Uranium in a Crystalline Molecular Complex, [K(2.2.2-Cryptand)][(C5H4SiMe3)3U]. J. Am. Chem. Soc. 2013, 135 (36): 13310–13313. PMID 23984753. doi:10.1021/ja406791t.
Pu(II)已在{Pu[C5H3(SiMe3)2]3}−中观察到,参见:Windorff, Cory J.; Chen, Guo P; Cross, Justin N; Evans, William J.; Furche, Filipp; Gaunt, Andrew J.; Janicke, Michael T.; Kozimor, Stosh A.; Scott, Brian L. Identification of the Formal +2 Oxidation State of Plutonium: Synthesis and Characterization ofref name="curium5" {PuII[C5H3(SiMe3)2]3}−. J. Am. Chem. Soc. 2017, 139 (11): 3970–3973. PMID 28235179. doi:10.1021/jacs.7b00706.
Pu(VIII)已在PuO
4中观察到,参见:Nikonov, M. V.; Kiselev, Yu. M.; Tananaev, I. G.; Myasoedov, B. F. Plutonium volatility in ozonization of alkaline solutions of Pu(VI) hydroxo complexes. Doklady Chemistry. March 2011, 437 (1): 69–71. S2CID 95951175. doi:10.1134/S0012500811030104.,以及 Kiselev, Yu. M.; Nikonov, M. V.; Dolzhenko, V. D.; Ermilov, A. Yu.; Tananaev, I. G.; Myasoedov, B. F. On existence and properties of plutonium(VIII) derivatives. Radiochimica Acta. 17 January 2014, 102 (3): 227–237. S2CID 100915090. doi:10.1515/ract-2014-2146.
Am(VII)已在AmO−
5中观察到,参见:Americium (页面存档备份,存于互联网档案馆), Das Periodensystem der Elemente für den Schulgebrauch (The periodic table of elements for schools) chemie-master.de (in German), Retrieved 28 November 2010 and Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997: 1265. ISBN 0-7506-3365-4.
Cm(VI)已在三氧化锔(CmO3)及二氧化锔(2+)离子(CmO+
2)中观察到,参见:Domanov, V. P.; Lobanov, Yu. V. Formation of volatile curium(VI) trioxide CmO3. Radiochemistry. October 2011, 53 (5): 453–6. S2CID 98052484. doi:10.1134/S1066362211050018.
Cm(VIII)曾被报告可能存在于四氧化锔(CmO4)中,参阅:Domanov, V. P. Possibility of generation of octavalent curium in the gas phase in the form of volatile tetraoxide CmO4. Radiochemistry. January 2013, 55 (1): 46–51. S2CID 98076989. doi:10.1134/S1066362213010098.然而,后续的实验显示该物质似乎不存在:Zaitsevskii, Andréi; Schwarz, W H Eugen. Structures and stability of AnO4 isomers, An = Pu, Am, and Cm: a relativistic density functional study. Physical Chemistry Chemical Physics. April 2014, 2014 (16): 8997–9001. Bibcode:2014PCCP...16.8997Z. PMID 24695756. doi:10.1039/c4cp00235k.
Sullivan, Jim C.; Schmidt, K. H.; Morss, L. R.; Pippin, C. G.; Williams, C. Pulse radiolysis studies of berkelium(III): preparation and identification of berkelium(II) in aqueous perchlorate media. Inorganic Chemistry. 1988, 27 (4): 597. doi:10.1021/ic00277a005.
Sg(0)已在六羰基𬭳(Sg(CO)6)中观察到,参见:Even, J.; Yakushev, A.; Dullmann, C. E.; Haba, H.; Asai, M.; Sato, T. K.; Brand, H.; Di Nitto, A.; Eichler, R.; Fan, F. L.; Hartmann, W.; Huang, M.; Jager, E.; Kaji, D.; Kanaya, J.; Kaneya, Y.; Khuyagbaatar, J.; Kindler, B.; Kratz, J. V.; Krier, J.; Kudou, Y.; Kurz, N.; Lommel, B.; Miyashita, S.; Morimoto, K.; Morita, K.; Murakami, M.; Nagame, Y.; Nitsche, H.; et al. Synthesis and detection of a seaborgium carbonyl complex. Science. 2014, 345 (6203): 1491–3. Bibcode:2014Sci...345.1491E. PMID 25237098. S2CID 206558746. doi:10.1126/science.1255720.
Hs(VIII)已在四氧化𬭶(HsO4)中观察到,参见:Chemistry of Hassium (PDF). Gesellschaft für Schwerionenforschung mbH. 2002 [2007-01-31]. (原始内容存档 (PDF)于2012-03-11).