All the lanthanides (La–Lu) in the +2 oxidation state have been observed (except La, Gd, Lu) in dilute, solid solutions of dihalides of these elements in alkaline earth dihalides (see Bản mẫu:Holleman&Wiberg) and (except Pm) in organometallic molecular complexes, see Lanthanides Topple Assumptions and Meyer, G. (2014). “All the Lanthanides Do It and Even Uranium Does Oxidation State +2”. Angewandte Chemie International Edition. 53 (14): 3550–51. doi:10.1002/anie.201311325. PMID24616202.. Additionally, all the lanthanides (La–Lu) form dihydrides (LnH2), dicarbides (LnC2), monosulfides (LnS), monoselenides (LnSe), and monotellurides (LnTe), but for most elements these compounds have Ln3+ ions with electrons delocalized into conduction bands, e. g. Ln3+(H−)2(e−).
archive.org
Ge(−1), Ge(−2), and Ge(−3) have been observed in germanides; see Holleman, Arnold F.; Wiberg, Egon; Wiberg, Nils (1995). “Germanium”. Lehrbuch der Anorganischen Chemie (bằng tiếng Đức) (ấn bản thứ 101). Walter de Gruyter. tr. 953–959. ISBN3-11-012641-9..
Zr(−1) has been reported in [Zr(bipy)3]− (see Greenwood, Norman N.; Earnshaw, A. (1997), Chemistry of the Elements (ấn bản thứ 2), Oxford: Butterworth-Heinemann, tr. 960, ISBN0-7506-3365-4 and Holleman, Arnold F.; Wiberg, Egon; Wiberg, Nils (1995). “Zirconium”. Lehrbuch der Anorganischen Chemie (bằng tiếng Đức) (ấn bản thứ 101). Walter de Gruyter. tr. 1413. ISBN3-11-012641-9.), but was later shown to be Zr(+4); see Bowman, A. C.; England, J.; Sprouls, S.; Weihemüller, T.; Wieghardt, K. (2013). “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. 52 (4): 2242–56. doi:10.1021/ic302799s. PMID23387926.
I(IV) has been observed in iodine dioxide (IO2); see Pauling, Linus (1988). “Oxygen Compounds of Nonmetallic Elements”. General Chemistry (ấn bản thứ 3). Dover Publications, Inc. tr. 259. ISBN0-486-65622-5.
Pb(−2) has been observed in BaPb, see Ferro, Riccardo (2008). Nicholas C. Norman (biên tập). Intermetallic Chemistry. Elsevier. tr. 505. ISBN978-0-08-044099-6. and Todorov, Iliya; Sevov, Slavi C. (2004). “Heavy-Metal Aromatic Rings: Cyclopentadienyl Anion Analogues Sn56− and Pb56− in the Zintl Phases Na8BaPb6, Na8BaSn6, and Na8EuSn6”. Inorganic Chemistry. 43 (20): 6490–94. doi:10.1021/ic000333x.
books.google.com
Rn(IV) is reported by Greenwood and Earnshaw, but is not known to exist; see Sykes, A. G. (1998). “Recent Advances in Noble-Gas Chemistry”. Advances in Inorganic Chemistry. 46. Academic Press. tr. 91–93. ISBN978-0-12-023646-6. Truy cập ngày 22 tháng 11 năm 2012.
Am(VII) has been observed in AmO5− 6; see Americium, Das Periodensystem der Elemente für den Schulgebrauch (The periodic table of elements for schools) chemie-master.de (in German), Retrieved ngày 28 tháng 11 năm 2010 and Greenwood, Norman N.; Earnshaw, A. (1997), Chemistry of the Elements (ấn bản thứ 2), Oxford: Butterworth-Heinemann, tr. 1265, ISBN0-7506-3365-4
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Ti(−2), V(−3), Cr(−4), Co(−3), Zr(−2), Nb(−3), Mo(−4), Ru(−2), Rh(−3), Hf(−2), Ta(−3), and W(−4) occur in anionic binary metal carbonyls; see [3], p. 4 (in German); [4], pp. 97–100; [5], p. 239
Al(II) has been observed in aluminium(II) oxit (AlO); see D. C. Tyte (1964). “Red (B2Π–A2σ) Band System of Aluminium Monoxide”. Nature. 202 (4930): 383–384. Bibcode:1964Natur.202..383T. doi:10.1038/202383a0., and in dialanes (R2Al—AlR2); see Uhl, Werner "Organoelement Compounds Possessing Al—Al, Ga—Ga, In—In, and Tl—Tl Single Bonds" Advances in Organometallic Chemistry Volume 51, 2004, Pages 53–108. doi:10.1016/S0065-3055(03)51002-4
The equilibrium Cl2O6⇌2ClO3 is mentioned by Greenwood and Earnshaw, but it has been refuted, see Lopez, Maria; Juan E. Sicre (1990). “Physicochemical properties of chlorine oxides. 1. Composition, ultraviolet spectrum, and kinetics of the thermolysis of gaseous dichlorine hexoxide”. J. Phys. Chem. 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 (1994). “Chlorine Trioxide: Spectroscopic Properties, Molecular Structure, and Photochemical Behavior”. Angew. Chem. Int. Ed. 33 (14): 1482–1484. doi:10.1002/anie.199414821.
Ca(I) has been observed; see Krieck, Sven; Görls, Helmar; Westerhausen, Matthias (2010). “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. 132 (35): 12492–501. doi:10.1021/ja105534w. PMID20718434.
Sc(I) has been observed; see Polly L. Arnold; F. Geoffrey; N. Cloke; Peter B. Hitchcock & John F. Nixon (1996). “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. 118 (32): 7630–7631. doi:10.1021/ja961253o.
Sc(II) has been observed; see Woen, David H.; Chen, Guo P.; Ziller, Joseph W.; Boyle, Timothy J.; Furche, Filipp; Evans, William J. (tháng 1 năm 2017). “Solution Synthesis, Structure, and CO Reduction Reactivity of a Scandium(II) Complex”. Angewandte Chemie International Edition. 56: 2050–2053. doi:10.1002/anie.201611758.
Ti(I) has been observed in [Ti(η6-1,3,5-C6H3iPr3)2][BAr4] (Ar = C6H5, p-C6H4F, 3,5-C6H3(CF3)2); see Fausto Calderazzo, Isabella Ferri, Guido Pampaloni, Ulli Englert, Malcolm L. H. Green (1997). “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. 16 (14): 3100–3101. doi:10.1021/om970155o.Quản lý CS1: sử dụng tham số tác giả (liên kết)
Ti(−1) has been reported in [Ti(bipy)3]−, but was later shown to be Ti(+3); see Bowman, A. C.; England, J.; Sprouls, S.; Weihemüller, T.; Wieghardt, K. (2013). “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. 52 (4): 2242–56. doi:10.1021/ic302799s. PMID23387926. However, Ti(−1) occurs in [Ti(η-C6H6]− and [Ti(η-C6H5CH3)]−, see Bandy, J. A.; Berry, A.; Green, M. L. H.; Perutz, R. N.; Prout, K.; Verpeautz, J.-N. (1984). “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. 52 (4): 729–731. doi:10.1039/C39840000729.
Fe(VIII) has been reported; see Yurii D. Perfiliev; Virender K. Sharma (2008). “Higher Oxidation States of Iron in Solid State: Synthesis and Their Mössbauer Characterization – Ferrates – ACS Symposium Series (ACS Publications)”. Platinum Metals Review. 48 (4): 157–158. doi:10.1595/147106704X10801. However, its existence has been disputed.
Fe(−4), Ru(−4), and Os(−4) have been observed in metal-rich compounds containing octahedral complexes [MIn6−xSnx]; Pt(−3) (as a dimeric anion [Pt–Pt]6−), Cu(−2), Zn(−2), Ag(−2), Cd(−2), Au(−2), and Hg(−2) have been observed (as dimeric and monomeric anions; dimeric ions were initially reported to be [T–T]2− for Zn, Cd, Hg, but later shown to be [T–T]4− for all these elements) in La2Pt2In, La2Cu2In, Ca5Au3, Ca5Ag3, Ca5Hg3, Sr5Cd3, Ca5Zn3(structure (AE2+)5(T–T)4−T2−⋅4e−), Yb3Ag2, Ca5Au4, and Ca3Hg2; Au(–3) has been observed in ScAuSn and in other 18-electron half-Heusler compounds. See Changhoon Lee; Myung-Hwan Whangbo (2008). “Late transition metal anions acting as p-metal elements”. Frontiers in Solid State Chemistry. 10 (4): 444–449. doi:10.1016/j.solidstatesciences.2007.12.001. and Changhoon Lee; Myung-Hwan Whangbo; Jürgen Köhler (2010). “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)”. ZAAC. 636 (1): 36–40. doi:10.1002/zaac.200900421.
Ni(−2) has been observed in Li2[Ni(1,5-COD)2], see Jonas, Klaus (1975). “Dilithium-Nickel-Olefin Complexes. Novel Bimetal Complexes Containing a Transition Metal and a Main Group Metal”. Angew. Chem. Int. Ed. 14 (11): 752–753. doi:10.1002/anie.197507521. and Ellis, John E. (2006). “Adventures with Substances Containing Metals in Negative Oxidation States”. Inorganic Chemistry. 45 (8): 3167–86. doi:10.1021/ic052110i.
Zn(I) has been observed in decamethyldizincocene (Zn2(η5–C5Me5)2); see Resa, I.; Carmona, E.; Gutierrez-Puebla, E.; Monge, A. (2004). “Decamethyldizincocene, a Stable Compound of Zn(I) with a Zn-Zn Bond”. Science. 305 (5687): 1136–8. doi:10.1126/science.1101356. PMID15326350.
As(I) has been observed in arsenic(I) iodide (AsI); see Ellis, Bobby D.; MacDonald, Charles L. B. (2004). “Stabilized Arsenic(I) Iodide: A Ready Source of Arsenic Iodide Fragments and a Useful Reagent for the Generation of Clusters”. Inorganic Chemistry. 43 (19): 5981–6. doi:10.1021/ic049281s. PMID15360247.
As(IV) has been observed in arsenic(IV) hydroxide (As(OH)4) and HAsO− 3; see Kläning, Ulrik K.; Bielski, Benon H. J.; Sehested, K. (1989). “Arsenic(IV). A pulse-radiolysis study”. Inorganic Chemistry. 28 (14): 2717–24. doi:10.1021/ic00313a007.
Se(V) has been observed in SeO2− 3 and HSeO2− 4; see Kläning, Ulrik K.; Sehested, K. (1986). “Selenium(V). A pulse radiolysis study”. Inorganic Chemistry. 90 (21): 5460–4. doi:10.1021/j100412a112.
Y(II) has been observed in [(18-crown-6)K][(C5H4SiMe3)3Y]; see MacDonald, M. R.; Ziller, J. W.; Evans, W. J. (2011). “Synthesis of a Crystalline Molecular Complex of Y2+, [(18-crown-6)K][(C5H4SiMe3)3Y]”. J. Am. Chem. Soc. 133 (40): 15914–17. doi:10.1021/ja207151y.
Zr(−1) has been reported in [Zr(bipy)3]− (see Greenwood, Norman N.; Earnshaw, A. (1997), Chemistry of the Elements (ấn bản thứ 2), Oxford: Butterworth-Heinemann, tr. 960, ISBN0-7506-3365-4 and Holleman, Arnold F.; Wiberg, Egon; Wiberg, Nils (1995). “Zirconium”. Lehrbuch der Anorganischen Chemie (bằng tiếng Đức) (ấn bản thứ 101). Walter de Gruyter. tr. 1413. ISBN3-11-012641-9.), but was later shown to be Zr(+4); see Bowman, A. C.; England, J.; Sprouls, S.; Weihemüller, T.; Wieghardt, K. (2013). “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. 52 (4): 2242–56. doi:10.1021/ic302799s. PMID23387926.
Pd(I) has been observed; see Crabtree, R. H. (2002). “CHEMISTRY: A New Oxidation State for Pd?”. Science. 295 (5553): 288–289. doi:10.1126/science.1067921.
The Ag− ion has been observed in metal ammonia solutions: see Tran, N. E.; Lagowski, J. J. (2001). “Metal Ammonia Solutions: Solutions Containing Argentide Ions”. Inorganic Chemistry. 40 (5): 1067–68. doi:10.1021/ic000333x.
In(–5) has been observed in La3InGe, see Guloy, A. M.; Corbett, J. D. (1996). “Synthesis, Structure, and Bonding of Two Lanthanum Indium Germanides with Novel Structures and Properties”. Inorganic Chemistry. 35 (9): 2616–22. doi:10.1021/ic951378e.
Sb(IV) has been observed in [SbCl 6]2− , see Nobuyoshi Shinohara; Masaaki Ohsima (2000). “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. 73 (7): 1599–1604. doi:10.1246/bcsj.73.1599.
Te(V) is mentioned by Greenwood and Earnshaw, but they do not give any example of a Te(V) compound. What was long thought to be ditellurium decafluoride (Te2F10) is actually bis(pentafluorotelluryl) oxide, F5TeOTeF5: see Watkins, P. M. (1974). “Ditellurium decafluoride - A Continuing Myth”. Journal of Chemical Education. 51 (9): 520–521. doi:10.1021/ed051p520. However, Te(V) has been observed in H 2TeO− 4, TeO− 3, HTeO2− 4, and TeO3− 4; see Kläning, Ulrik K.; Sehested, K. (2001). “Tellurium(V). A Pulse Radiolysis Study”. The Journal of Physical Chemistry A. 105 (27): 6637–45. doi:10.1021/jp010577i.
I(VI) has been observed in IO3, IO42−, H5IO6−, H2IO52−, H4IO62−, and HIO53−; see Kläning, Ulrik K.; Sehested, Knud; Wolff, Thomas (1981). “Laser flash photolysis and pulse radiolysis of iodate and periodate in aqueous solution. Properties of iodine(VI)”. J. Chem. Soc., Faraday Trans. 1. 77: 1707–18. doi:10.1039/F19817701707.
All the lanthanides (La–Lu) in the +2 oxidation state have been observed (except La, Gd, Lu) in dilute, solid solutions of dihalides of these elements in alkaline earth dihalides (see Bản mẫu:Holleman&Wiberg) and (except Pm) in organometallic molecular complexes, see Lanthanides Topple Assumptions and Meyer, G. (2014). “All the Lanthanides Do It and Even Uranium Does Oxidation State +2”. Angewandte Chemie International Edition. 53 (14): 3550–51. doi:10.1002/anie.201311325. PMID24616202.. Additionally, all the lanthanides (La–Lu) form dihydrides (LnH2), dicarbides (LnC2), monosulfides (LnS), monoselenides (LnSe), and monotellurides (LnTe), but for most elements these compounds have Ln3+ ions with electrons delocalized into conduction bands, e. g. Ln3+(H−)2(e−).
Os(−1) has been observed in Na 2[Os 4(CO) 13]; see Krause, J.; Siriwardane, Upali; Salupo, Terese A.; Wermer, Joseph R.; Knoeppel, David W.; Shore, Sheldon G. (1993). “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. 454: 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. (1982). “Mononuclear hydrido alkyl carbonyl complexes of osmium and their polynuclear derivatives”. Inorganic Chemistry. 21 (11): 3955–3960. doi:10.1021/ic00141a019.
Ir(VIII) has been observed in iridium tetroxit (IrO4); see Gong, Yu; Zhou, Mingfei; Kaupp, Martin; Riedel, Sebastian (2009). “Formation and Characterization of the Iridium Tetroxide Molecule with Iridium in the Oxidation State +VIII”. Angewandte Chemie International Edition. 48 (42): 7879–7883. doi:10.1002/anie.200902733.
Ir(IX) has been observed in IrO+ 4; see Wang, Guanjun; Zhou, Mingfei; Goettel, James T.; Schrobilgen, Gary G.; Su, Jing; Li, Jun; Schlöder, Tobias; Riedel, Sebastian (ngày 21 tháng 8 năm 2014). “Identification of an iridium-containing compound with a formal oxidation state of IX”. Nature. 514: 475–477. doi:10.1038/nature13795. PMID25341786.
Pt(−1) and Pt(−2) have been observed in the bari platinides Ba2Pt and BaPt, respectively: see Karpov, Andrey; Konuma, Mitsuharu; Jansen, Martin (2006). “An experimental proof for negative oxidation states of platinum: ESCA-measurements on barium platinides”. Chemical Communications (8): 838–840. doi:10.1039/b514631c. PMID16479284.
Tl(−5) has been observed in Na23K9Tl15.3, see Dong, Z.-C.; Corbett, J. D. (1996). “Na23K9Tl15.3: An Unusual Zintl Compound Containing Apparent Tl57−, Tl48−, Tl37−, and Tl5− Anions”. Inorganic Chemistry. 35 (11): 3107–12. doi:10.1021/ic960014z.
Tl(+2) has been observed in tetrakis(hypersilyl)dithallium ([(Me3Si)Si]2Tl—Tl[Si(SiMe3)]2), see Sonja Henkel; Dr. Karl Wilhelm Klinkhammer; Dr. Wolfgang Schwarz (1994). “Tetrakis(hypersilyl)dithallium(Tl—Tl): A Divalent Thallium Compound”. Angew. Chem. Int. Ed. 33 (6): 681–683. doi:10.1002/anie.199406811..
Pb(−2) has been observed in BaPb, see Ferro, Riccardo (2008). Nicholas C. Norman (biên tập). Intermetallic Chemistry. Elsevier. tr. 505. ISBN978-0-08-044099-6. and Todorov, Iliya; Sevov, Slavi C. (2004). “Heavy-Metal Aromatic Rings: Cyclopentadienyl Anion Analogues Sn56− and Pb56− in the Zintl Phases Na8BaPb6, Na8BaSn6, and Na8EuSn6”. Inorganic Chemistry. 43 (20): 6490–94. doi:10.1021/ic000333x.
Pb(+1) and Pb(+3) have been observed in organolead compounds, e.g. hexamethyldiplumbane Pb2(CH3)6; for Pb(I), see Siew-Peng Chia; Hong-Wei Xi; Yongxin Li; Kok Hwa Lim; Cheuk-Wai So (2013). “A Base-Stabilized Lead(I) Dimer and an Aromatic Plumbylidenide Anion”. Angew. Chem. Int. Ed. 52 (24): 6298–6301. doi:10.1002/anie.201301954..
Bi(+2) has been observed in dibismuthines (R2Bi—BiR2), see Arthur J. Ashe III (1990). “Thermochromic Distibines and Dibismuthines”. Advances in Organometallic Chemistry. 30: 77–97. doi:10.1016/S0065-3055(08)60499-2.
Bi(IV) has been observed; see A. I. Aleksandrov, I. E. Makarov (1987). “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. 36 (2): 217–220. doi:10.1007/BF00959349.
Po(V) has been observed in dioxidopolonium(1+) (PoO+ 2); see Thayer, John S. (2010). Relativistic Effects and the Chemistry of the Heavier Main Group Elements. tr. 78. doi:10.1007/978-1-4020-9975-5_2.
Th(I) is known in thorium(I) bromide (ThBr); see Wickleder, Mathias S.; Fourest, Blandine; Dorhout, Peter K. (2006). “Thorium”. Trong Morss, Lester R.; Edelstein, Norman M.; Fuger, Jean (biên tập). The Chemistry of the Actinide and Transactinide Elements(PDF). 3 (ấn bản thứ 3). Dordrecht, the Netherlands: Springer. tr. 52–160. doi:10.1007/1-4020-3598-5_3. Bản gốc(PDF) lưu trữ ngày 7 tháng 3 năm 2016.
U(II) has been observed in [K(2.2.2-Cryptand)][(C5H4SiMe3)3U], see MacDonald, Matthew R.; Fieser, Megan E.; Bates, Jefferson E.; Ziller, Joseph W.; Furche, Filipp; Evans, William J. (2013). “Identification of the +2 Oxidation State for Uranium in a Crystalline Molecular Complex, [K(2.2.2-Cryptand)][(C5H4SiMe3)3U]”. J. Am. Chem. Soc. 135 (36): 13310–13313. doi:10.1021/ja406791t. |ngày truy cập= cần |url= (trợ giúp)
Np(II) has been observed, see Dutkiewicz, Michał S.; Apostolidis, Christos; Walter, Olaf; Arnold, Polly L (2017). “Reduction chemistry of neptunium cyclopentadienide complexes: from structure to understanding”. Chem. Sci. 8: 2553–2561. doi:10.1039/C7SC00034K. |ngày truy cập= cần |url= (trợ giúp)
Pu(II) has been observed in {Pu[C5H3(SiMe3)2]3}−; see 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. (2017). “Identification of the Formal +2 Oxidation State of Plutonium: Synthesis and Characterization of {PuII[C5H3(SiMe3)2]3}−”. J. Am. Chem. Soc. 139 (11): 3970–3973. doi:10.1021/jacs.7b00706.
Cm(VI) has been observed in curium trioxit (CmO3) and dioxidocurium(2+) (CmO2+ 2); see Domanov, V. P.; Lobanov, Yu. V. (tháng 10 năm 2011). “Formation of volatile curium(VI) trioxide CmO3”. Radiochemistry. SP MAIK Nauka/Interperiodica. 53 (5): 453–6. doi:10.1134/S1066362211050018.
Cm(VIII) has been reported to possibly occur in curium tetroxit (CmO4); see Domanov, V. P. (tháng 1 năm 2013). “Possibility of generation of octavalent curium in the gas phase in the form of volatile tetraoxide CmO4”. Radiochemistry. SP MAIK Nauka/Interperiodica. 55 (1): 46–51. doi:10.1134/S1066362213010098. However, new experiments seem to indicate its nonexistence: Zaitsevskii, Andréi; Schwarz, W H Eugen (tháng 4 năm 2014). “Structures and stability of AnO4 isomers, An = Pu, Am, and Cm: a relativistic density functional study”. Physical Chemistry Chemical Physics. 2014 (16): 8997–9001. doi:10.1039/c4cp00235k.
Langmuir, Irving (1919). “The arrangement of electrons in atoms and molecules”. J. Am. Chem. Soc. 41 (6): 868–934. doi:10.1021/ja02227a002.
dx.doi.org
Al(II) has been observed in aluminium(II) oxit (AlO); see D. C. Tyte (1964). “Red (B2Π–A2σ) Band System of Aluminium Monoxide”. Nature. 202 (4930): 383–384. Bibcode:1964Natur.202..383T. doi:10.1038/202383a0., and in dialanes (R2Al—AlR2); see Uhl, Werner "Organoelement Compounds Possessing Al—Al, Ga—Ga, In—In, and Tl—Tl Single Bonds" Advances in Organometallic Chemistry Volume 51, 2004, Pages 53–108. doi:10.1016/S0065-3055(03)51002-4
Negative oxidation states of p-block metals (Al, Ga, In, Sn, Tl, Pb, Bi, Po) and metalloids (Si, Ge, As, Sb, Te, At) may occur in Zintl phases, see: [1], p. 259 and [2] (both in German).
Ti(−2), V(−3), Cr(−4), Co(−3), Zr(−2), Nb(−3), Mo(−4), Ru(−2), Rh(−3), Hf(−2), Ta(−3), and W(−4) occur in anionic binary metal carbonyls; see [3], p. 4 (in German); [4], pp. 97–100; [5], p. 239
In(−2) has been observed in Na2In, see [6], p. 69.
Hs(VIII) has been observed in hassium tetroxide (HsO4); see “Chemistry of Hassium”(PDF). Gesellschaft für Schwerionenforschung mbH. 2002. Truy cập ngày 31 tháng 1 năm 2007.
Al(II) has been observed in aluminium(II) oxit (AlO); see D. C. Tyte (1964). “Red (B2Π–A2σ) Band System of Aluminium Monoxide”. Nature. 202 (4930): 383–384. Bibcode:1964Natur.202..383T. doi:10.1038/202383a0., and in dialanes (R2Al—AlR2); see Uhl, Werner "Organoelement Compounds Possessing Al—Al, Ga—Ga, In—In, and Tl—Tl Single Bonds" Advances in Organometallic Chemistry Volume 51, 2004, Pages 53–108. doi:10.1016/S0065-3055(03)51002-4
Th(I) is known in thorium(I) bromide (ThBr); see Wickleder, Mathias S.; Fourest, Blandine; Dorhout, Peter K. (2006). “Thorium”. Trong Morss, Lester R.; Edelstein, Norman M.; Fuger, Jean (biên tập). The Chemistry of the Actinide and Transactinide Elements(PDF). 3 (ấn bản thứ 3). Dordrecht, the Netherlands: Springer. tr. 52–160. doi:10.1007/1-4020-3598-5_3. Bản gốc(PDF) lưu trữ ngày 7 tháng 3 năm 2016.
Ca(I) has been observed; see Krieck, Sven; Görls, Helmar; Westerhausen, Matthias (2010). “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. 132 (35): 12492–501. doi:10.1021/ja105534w. PMID20718434.
Ti(−1) has been reported in [Ti(bipy)3]−, but was later shown to be Ti(+3); see Bowman, A. C.; England, J.; Sprouls, S.; Weihemüller, T.; Wieghardt, K. (2013). “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. 52 (4): 2242–56. doi:10.1021/ic302799s. PMID23387926. However, Ti(−1) occurs in [Ti(η-C6H6]− and [Ti(η-C6H5CH3)]−, see Bandy, J. A.; Berry, A.; Green, M. L. H.; Perutz, R. N.; Prout, K.; Verpeautz, J.-N. (1984). “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. 52 (4): 729–731. doi:10.1039/C39840000729.
Zn(I) has been observed in decamethyldizincocene (Zn2(η5–C5Me5)2); see Resa, I.; Carmona, E.; Gutierrez-Puebla, E.; Monge, A. (2004). “Decamethyldizincocene, a Stable Compound of Zn(I) with a Zn-Zn Bond”. Science. 305 (5687): 1136–8. doi:10.1126/science.1101356. PMID15326350.
As(I) has been observed in arsenic(I) iodide (AsI); see Ellis, Bobby D.; MacDonald, Charles L. B. (2004). “Stabilized Arsenic(I) Iodide: A Ready Source of Arsenic Iodide Fragments and a Useful Reagent for the Generation of Clusters”. Inorganic Chemistry. 43 (19): 5981–6. doi:10.1021/ic049281s. PMID15360247.
Zr(−1) has been reported in [Zr(bipy)3]− (see Greenwood, Norman N.; Earnshaw, A. (1997), Chemistry of the Elements (ấn bản thứ 2), Oxford: Butterworth-Heinemann, tr. 960, ISBN0-7506-3365-4 and Holleman, Arnold F.; Wiberg, Egon; Wiberg, Nils (1995). “Zirconium”. Lehrbuch der Anorganischen Chemie (bằng tiếng Đức) (ấn bản thứ 101). Walter de Gruyter. tr. 1413. ISBN3-11-012641-9.), but was later shown to be Zr(+4); see Bowman, A. C.; England, J.; Sprouls, S.; Weihemüller, T.; Wieghardt, K. (2013). “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. 52 (4): 2242–56. doi:10.1021/ic302799s. PMID23387926.
All the lanthanides (La–Lu) in the +2 oxidation state have been observed (except La, Gd, Lu) in dilute, solid solutions of dihalides of these elements in alkaline earth dihalides (see Bản mẫu:Holleman&Wiberg) and (except Pm) in organometallic molecular complexes, see Lanthanides Topple Assumptions and Meyer, G. (2014). “All the Lanthanides Do It and Even Uranium Does Oxidation State +2”. Angewandte Chemie International Edition. 53 (14): 3550–51. doi:10.1002/anie.201311325. PMID24616202.. Additionally, all the lanthanides (La–Lu) form dihydrides (LnH2), dicarbides (LnC2), monosulfides (LnS), monoselenides (LnSe), and monotellurides (LnTe), but for most elements these compounds have Ln3+ ions with electrons delocalized into conduction bands, e. g. Ln3+(H−)2(e−).
Ir(IX) has been observed in IrO+ 4; see Wang, Guanjun; Zhou, Mingfei; Goettel, James T.; Schrobilgen, Gary G.; Su, Jing; Li, Jun; Schlöder, Tobias; Riedel, Sebastian (ngày 21 tháng 8 năm 2014). “Identification of an iridium-containing compound with a formal oxidation state of IX”. Nature. 514: 475–477. doi:10.1038/nature13795. PMID25341786.
Pt(−1) and Pt(−2) have been observed in the bari platinides Ba2Pt and BaPt, respectively: see Karpov, Andrey; Konuma, Mitsuharu; Jansen, Martin (2006). “An experimental proof for negative oxidation states of platinum: ESCA-measurements on barium platinides”. Chemical Communications (8): 838–840. doi:10.1039/b514631c. PMID16479284.
Fe(−4), Ru(−4), and Os(−4) have been observed in metal-rich compounds containing octahedral complexes [MIn6−xSnx]; Pt(−3) (as a dimeric anion [Pt–Pt]6−), Cu(−2), Zn(−2), Ag(−2), Cd(−2), Au(−2), and Hg(−2) have been observed (as dimeric and monomeric anions; dimeric ions were initially reported to be [T–T]2− for Zn, Cd, Hg, but later shown to be [T–T]4− for all these elements) in La2Pt2In, La2Cu2In, Ca5Au3, Ca5Ag3, Ca5Hg3, Sr5Cd3, Ca5Zn3(structure (AE2+)5(T–T)4−T2−⋅4e−), Yb3Ag2, Ca5Au4, and Ca3Hg2; Au(–3) has been observed in ScAuSn and in other 18-electron half-Heusler compounds. See Changhoon Lee; Myung-Hwan Whangbo (2008). “Late transition metal anions acting as p-metal elements”. Frontiers in Solid State Chemistry. 10 (4): 444–449. doi:10.1016/j.solidstatesciences.2007.12.001. and Changhoon Lee; Myung-Hwan Whangbo; Jürgen Köhler (2010). “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)”. ZAAC. 636 (1): 36–40. doi:10.1002/zaac.200900421.
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Negative oxidation states of p-block metals (Al, Ga, In, Sn, Tl, Pb, Bi, Po) and metalloids (Si, Ge, As, Sb, Te, At) may occur in Zintl phases, see: [1], p. 259 and [2] (both in German).
Th(I) is known in thorium(I) bromide (ThBr); see Wickleder, Mathias S.; Fourest, Blandine; Dorhout, Peter K. (2006). “Thorium”. Trong Morss, Lester R.; Edelstein, Norman M.; Fuger, Jean (biên tập). The Chemistry of the Actinide and Transactinide Elements(PDF). 3 (ấn bản thứ 3). Dordrecht, the Netherlands: Springer. tr. 52–160. doi:10.1007/1-4020-3598-5_3. Bản gốc(PDF) lưu trữ ngày 7 tháng 3 năm 2016.
