查看“︁锇化合物”︁的源代码

<div style="float:right; margin:5px;">
{|class="wikitable"
|-
! colspan=2|锇的氧化态
|-
| −2 || {{chem|Na|2|[Os(CO)|4|]}}
|-
| −1 || {{chem|Na|2|[Os|4|(CO)|13|]}}
|-
| 0 ||[[十二羰基三锇|{{chem|Os|3|(CO)|12|}}]]
|-
| +1 ||{{chem|OsI}}
|-
| '''+2''' ||{{chem|OsI|2}}
|-
| '''+3''' || {{chem|OsBr|3|}}
|-
| '''+4''' || [[二氧化锇|{{chem|OsO|2}}]], [[四氯化锇|{{chem|OsCl|4}}]]
|-
| +5 ||{{chem|OsF|5}}
|-
| +6 ||[[六氟化锇|{{chem|OsF|6}}]]
|-
| +7 ||{{chem|OsOF|5}}
|-
| '''+8''' ||[[四氧化锇|{{chem|OsO|4}}]], {{chem|Os|(|NCH|3|)|4}}
|}</div>
<!--Common [[oxidation state]]s of osmium are +4 and +3, but oxidation states from +1 to +8 are observed.
-->
'''锇化合物'''是含有[[锇]]（Os）的化合物，锇化合价在−2至+8范围内的化合物均是已知的。{{chem|Na|2|[Os|4|(CO)|13|]}}和{{chem|Na|2|[Os(CO)|4|]}}分别是−1和−2价的锇化合物，用于合成锇的簇合物。<ref>{{cite journal|doi=10.1016/0022-328X(93)83250-Y|title=Preparation of [Os<sub>3</sub>(CO)<sub>11</sub>]<sup>2−</sup> and its reactions with Os<sub>3</sub>(CO)<sub>12</sub>; structures of [Et<sub>4</sub>N] [HOs<sub>3</sub>(CO)<sub>11</sub>] and H<sub>2</sub>OsS<sub>4</sub>(CO)|date=1993|last1 =Krause|first1=J.|journal=Journal of Organometallic Chemistry|volume=454|issue=1–2|pages=263–271|display-authors=4|last2=Siriwardane|first2=Upali|last3=Salupo|first3=Terese A.|last4=Wermer|first4=Joseph R.|last5=Knoeppel|first5=David W.|last6=Shore|first6=Sheldon G.}}</ref><ref>{{cite journal|doi=10.1021/ic00141a019|title=Mononuclear hydrido alkyl carbonyl complexes of osmium and their polynuclear derivatives|date=1982|first=Willie J.|last=Carter|display-authors=4|author2=Kelland, John W. |author3=Okrasinski, Stanley J. |author4=Warner, Keith E. |author5= Norton, Jack R. | journal=Inorganic Chemistry|volume=21|issue=11|pages=3955–3960}}</ref>

== 氧化物 ==
[[File:Osmiumtetroxide1.jpg|thumb|left|四氧化锇样品]]
[[File:CSD CIF KEWMEE.png|thumb|144px|right|OsO<sub>3</sub>(N-t-Bu)的结构，其中，多重键未特别标出。图片展示了以亚胺氧化锇(VIII)制备氨基醇时对烯烃的加成。<ref>{{cite journal|title=Reactions of Dimesityldioxo-Osmium(VI) with Donor Ligands; Reactions of MO<sub>2</sub>(2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>)<sub>2</sub>, M = Os or Re, with Nitrogen Oxides. X-Ray Crystal Structures of [2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>N<sub>2</sub>]<sup>+</sup>[OsO<sub>2</sub>(ONO<sub>2</sub>)<sub>2</sub>(2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>)]<sup>–</sup>, OsO(NBu<sup>t</sup>)(2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>)<sub>2</sub>, OsO<sub>3</sub>(NBu<sup>t</sup>), and ReO<sub>3</sub>[N(2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>)<sub>2</sub>]|authors=Brian S. McGilligan, John Arnold, Geoffrey Wilkinson, Bilquis Hussain-Bates, Michael B. Hursthouse|journal=J. Chem. Soc., Dalton Trans.|year=1990|issue=8|pages=2465–2475 |doi=10.1039/DT9900002465}}</ref>]]

[[四氧化锇]]是最著名的锇化合物，元素锇的名称音译自“osmium”，源自古希腊语“{{lang-grc|ὀσμή|osme|气味|label=none}}”，而其气味来自于四氧化锇。<ref name="weeks">{{cite book|title=Discovery of the Elements|url=https://archive.org/details/discoveryofeleme0000week|url-access=registration|pages=[https://archive.org/details/discoveryofeleme0000week/page/414 414–418]|author=Weeks, M. E.|date= 1968|edition=7|publisher=Journal of Chemical Education|isbn=978-0-8486-8579-9|oclc=23991202}}</ref>它是无色挥发性固体，但一些样品略带黄色，<ref>{{cite journal | last1 = Girolami | first1 = Gregory | year = 2012 | title = Osmium weighs | journal = Nature Chemistry | volume = 4 | issue = 11| page = 954 | doi = 10.1038/nchem.1479 | pmid = 23089872 | bibcode = 2012NatCh...4..954G }}</ref>这源自于黄棕色的[[二氧化锇|OsO<sub>2</sub>]]杂质。<ref>Cotton and Wilkinson, Advanced Inorganic Chemistry, p.1002</ref>锇粉在空气中氧化便得到四氧化锇，块状的锇发生这一反应则需加热至400 °C。<ref name = h&s>{{Housecroft2nd|pages=671–673, 710}}</ref>

:<chem>Os + 2O2 ->[\Delta T] OsO4</chem>

OsO<sub>4</sub>是路易斯酸，为温和的氧化剂。它和碱的水溶液反应，得到高锇酸盐（{{chem|OsO|4|(OH)|2|2−}}）<ref>{{Greenwood&Earnshaw2nd}}</ref>，它很容易被还原为锇酸盐（{{chem|OsO|2|(OH)|4|2-}}）。它和胺（路易斯碱）可以形成加合物，也能和[[氨]]反应，得到氮基锇酸盐：
:OsO<sub>4</sub> + NH<sub>3</sub> + KOH → K[Os(N)O<sub>3</sub>] + 2 H<sub>2</sub>O
[Os(N)O<sub>3</sub>]<sup>−</sup>阴离子和OsO<sub>4</sub>是同构的[[等电子体]]。OsO<sub>4</sub>易溶于[[叔丁醇]]，在溶液中，可以迅速被氢气还原为金属锇。锇的悬浮液可用于催化一系列含双键或三键的有机物的氢化反应。
:OsO<sub>4</sub> + 4 H<sub>2</sub> → Os  + 4 H<sub>2</sub>O

[[二氧化锇]]是锇的另一种氧化物，可由锇和[[氯酸钠]]、[[四氧化锇]]或[[一氧化氮]]在600&nbsp;°C反应制得。<ref>{{cite book| page = 1465| title = Inorganic chemistry|author1=A. F. Holleman  |author2=E. Wiberg |name-list-style=amp | publisher = Academic Press| year = 2001| isbn = 0-12-352651-5}}</ref><ref>{{cite journal|journal = Journal of the Less Common Metals| title = Neutronenbeugungsuntersuchungen am Osmium(IV)-oxid| doi=10.1016/0022-5088(69)90074-5  |author1=Thiele G. |author2=Woditsch P. |year = 1969|volume = 17|issue = 4|pages = 459 }}</ref>它不溶于水，可以和稀[[盐酸]]反应。<ref>{{cite journal|title = Metallic nature of osmium dioxide|author1=J. E. Greedan |author2=D. B. Willson |author3=T. E. Haas | journal = Inorg. Chem.| year = 1968 |volume = 7|issue = 11 | pages = 2461–2463| doi = 10.1021/ic50069a059}}</ref><ref>{{cite journal| title = Growth and characterization of {{chem|OsO|2}} single crystals| journal = Journal of Crystal Growth| volume = 262| issue = 1–4| year= 2004 | page = 271| doi = 10.1016/j.jcrysgro.2003.10.021| last1 = Yen| first1 = P}}</ref>

== 卤素化合物 ==

[[File:Osmium(VI)-fluorid.png|thumb|right|六氟化锇的晶胞]]

[[六氟化锇]]是17种已知的二元六氟化物之一，它可由[[锇]]和过量的[[氟气]]反应得到。它是黄色晶体，在33.4&nbsp;°C熔化，47.5&nbsp;°C沸腾。<ref name="CRC_HANDBOOK_OsF6">''[[CRC Handbook of Chemistry and Physics]]'', 90th Edition, CRC Press, Boca Raton, Florida, 2009, {{ISBN|978-1-4200-9084-0}}, Section 4, ''Physical Constants of Inorganic Compounds'', p.&nbsp;4-85.</ref>它可以部分水解，生成OsOF<sub>4</sub>。<ref>{{cite journal|last=Paine|first=R. T.|title=Partial hydrolysis of rhenium and osmium hexafluorides. An improved synthesis and characterization of rhenium oxide tetrafluoride|journal=Inorganic Chemistry|date=1 June 1973|volume=12|issue=6|pages=1457–1458|doi=10.1021/ic50124a060}}</ref> [[五氟化锇]]在固态时为四聚体（Os<sub>4</sub>F<sub>20</sub>），可由[[碘]]在[[五氟化碘]]溶液中还原[[六氟化锇]]得到：<ref>{{cite journal| author  = Holloway, John H.| author2  = Mitchell, S. J. | title= Preparation and Crystal Structure of Osmium Pentafluoride| journal= Journal of the Chemical Society  | year= 1971|pages=2789–94|doi=10.1039/J19710002789}}</ref>
:10 OsF<sub>6</sub> +  I<sub>2</sub>  →   10 OsF<sub>5</sub> +  2 IF<sub>5</sub>

[[File:OsCl4structure.jpg|thumb|right|四氯化锇的结构（绿色：氯；蓝色：锇）]]

[[四氯化锇]]存在两种晶型，可用于制备其它锇化合物，它最初于1909年通过锇的氯化反应得到：<ref>{{cite journal | title = Über das Osmium, seine analytische Bestimmung, seine Oxyde und seine Chloride | author = Otto Ruff and Ferd. Bornemann | journal = [[Zeitschrift für anorganische Chemie]] | year = 1910 | volume = 65 | pages = 429–456 | doi = 10.1002/zaac.19100650126 | url = https://zenodo.org/record/1428118 | access-date = 2023-02-10 | archive-date = 2023-01-02 | archive-url = https://web.archive.org/web/20230102153240/https://zenodo.org/record/1428118 | dead-url = no }}</ref>
这种方法得到红黑色的高温相：<ref>{{cite book | author = Cotton, S. A. | title = Chemistry of Precious Metals | publisher = Chapman and Hall | location = London | year = 1997 | isbn = 0-7514-0413-6}}</ref>
:Os  +  2 Cl<sub>2</sub>  →  OsCl<sub>4</sub>
该相属[[正交晶系]]，锇中心以八面体配位，OsCl<sub>6</sub>八面体共享对边成链。.<ref>{{cite book | author = Wells A.F. | year = 1984 | title = Structural Inorganic Chemistry | url = https://archive.org/details/structuralinorga0000well_m8i1 | edition = 5th | publisher = Oxford Science Publications | isbn = 0-19-855370-6}}</ref>棕色的立方晶型通过[[氯化亚砜]]还原[[四氧化锇]]得到：<ref>{{cite journal | author = Paul Machmer | title = On the polymorphism of osmium tetrachloride | journal = [[Chem. Commun.]] | year = 1967 | pages = 610a | doi = 10.1039/C1967000610A | issue = 12}}</ref>
:OsO<sub>4</sub> + 4 SOCl<sub>2</sub> → OsCl<sub>4</sub> + 2 Cl<sub>2</sub>  +  4 SO<sub>2</sub>

它溶于[[盐酸]]形成六氯合锇(IV)酸：
:OsO<sub>4</sub> + 10 HCl → H<sub>2</sub>OsCl<sub>6</sub> + 2 Cl<sub>2</sub>  +  4 H<sub>2</sub>O

六氯合锇(IV)酸钾（K<sub>2</sub>OsCl<sub>6</sub>）可以被[[二甲基亚砜]]还原，加热时从Os(IV)经Os(III)还原至Os(II)，产物为''cis'',''fac''-[Os<sup>II</sup>(dmso-S)<sub>3</sub>(dmso-O)Cl<sub>2</sub>]，它在室温会缓慢地异构化为''trans''-[Os<sup>II</sup>(dmso-S)<sub>4</sub>X<sub>2</sub>]。溴配合物（K<sub>2</sub>OsBr<sub>6</sub>）的反应与之类似。<ref>{{cite journal|authors=Rudnitskaya, O. V.; Kultyshkina, E. K.; Dobrokhotova, E. V.|title=Interaction of potassium hexahalogenoosmates(IV) with DMSO|journal=Vestnik MITKHT|language=ru|year=2013|volume=8|issue=2|pages=74-78|issn=1819-1487}}</ref>

[[File:Tert-butyl-chloroosmacyclopentatriene_(osmium_complex).svg|thumb|含Os=Cl的化合物<ref name=Chu />]]
锇和氯可以形成一种含Os=Cl-R特殊成键的化合物，它可以[[二氯化三(三苯基膦)合锇]]和1-乙炔基-2-叔丁基乙炔基苯为原料反应制得。<ref name=Chu>{{cite journal|journal=National Science Review|language=en|issn=2095-5138|date=2022-10-28|doi=10.1093/nsr/nwac237|url=https://academic.oup.com/nsr/advance-article/doi/10.1093/nsr/nwac237/6779694|title=Aromatic chloroosmacyclopentatrienes|accessdate=2023-02-10|author=Zhenwei Chu, Guomei He, Chuan Shi, Yuhui Hua, Yaxi Huang, Jiangxi Chen, Hujun Xie, Guochen Jia|archive-date=2022-11-06|archive-url=https://web.archive.org/web/20221106225950/https://academic.oup.com/nsr/advance-article/doi/10.1093/nsr/nwac237/6779694|dead-url=no}}</ref>

== 参考文献 ==
{{reflist|2}}

{{锇化合物}}
{{元素化合物专题}}

[[Category:锇化合物| ]]