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Revision as of 13:36, 6 December 2011 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 450270097 of page Samarium(II)_iodide for the Chem/Drugbox validation project (updated: '').		Latest revision as of 20:35, 17 September 2024 edit 169.229.250.214 (talk) fixing paragraph formattingTag: Visual edit: Switched
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	{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}}
	{{chembox		{{chembox
			| Watchedfields = changed
	| verifiedrevid = 435311244		| verifiedrevid = 464386740
	| ImageFile = Diiodopenta(THF)samarium(II)-3D-balls.png
	| ImageSize = 200px		| ImageFile = EuI2.png
			| ImageSize =
	| ImageCaption = Samarium(II) iodide complex with ]
			| ImageCaption =
	| ImageName = Ball-and-stick model of a samarium(II) iodide-THF complex		| ImageName = Ball-and-stick model of a samarium(II) iodide-THF complex
	| IUPACName =		| IUPACName = samarium(II) iodide
	| OtherNames = Samarium diiodide		| OtherNames = samarium diiodide
	| Section1 = {{Chembox Identifiers		|Section1={{Chembox Identifiers
	| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}		| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
	| ChemSpiderID = 125002		| ChemSpiderID = 125002
	| PubChem = 141689		| PubChem = 141689
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	| StdInChIKey = UAWABSHMGXMCRK-UHFFFAOYSA-L		| StdInChIKey = UAWABSHMGXMCRK-UHFFFAOYSA-L
	| CASNo = 32248-43-4		| CASNo = 32248-43-4
	| CASNo_Ref = {{cascite|correct|CAS}}		| CASNo_Ref = {{cascite|correct|CAS}}
			| UNII_Ref = {{fdacite|correct|FDA}}
			| UNII = L15T8U41LC
	}}		}}
	| Section2 = {{Chembox Properties		|Section2={{Chembox Properties
	| Formula = SmI<sub>2</sub>		| Formula = SmI<sub>2</sub>
	| MolarMass = 404.16 g/mol		| MolarMass = 404.16 g/mol
	| Appearance = green solid		| Appearance = green solid
	| Density =		| Density =
	| Solubility =		| Solubility =
	| MeltingPt = 520 °C		| MeltingPtC = 520
	| BoilingPt =		| BoilingPt =
	}}		}}
	| Section4 = {{Chembox Thermochemistry		|Section4={{Chembox Thermochemistry
	| DeltaHf =		| DeltaHf =
	| Entropy =		| Entropy =
	}}		}}
	| Section7 = {{Chembox Hazards		|Section7={{Chembox Hazards
	| ExternalMSDS =		| ExternalSDS =
	| EUIndex = Not listed		| HPhrases =
	| EUClass =		| PPhrases =
	| RPhrases =		| GHS_ref =
	| SPhrases =		| NFPA-H =
	| NFPA-H =		| NFPA-F =
	| NFPA-F =		| NFPA-R =
	| NFPA-R =		| NFPA-S =
		⚫	| FlashPt = Non-flammable
	| NFPA-O =
⚫	| FlashPt = Non-flammable
	}}		}}
	| Section8 = {{Chembox Related		|Section8={{Chembox Related
	| OtherAnions = ]<br/>]		| OtherAnions = ]<br />]
	| OtherCations = ]<br/>]		| OtherCations = ]<br />]
	}}		}}
	}}		}}
			]
			'''Samarium(II) iodide''' is an ] with the formula SmI<sub>2</sub>. When employed as a solution for ], it is known as ''']'s reagent'''. SmI<sub>2</sub> is a green solid and forms a dark blue solution in ].<ref>https://www.sigmaaldrich.com/GB/en/sds/aldrich/347116?userType=anonymous {{Bare URL inline|date=August 2024}}</ref> It is a strong one-electron ] that is used in ].
			==Structure==
			In solid samarium(II) iodide, the metal centers are seven-coordinate with a face-capped ].<ref name = "Greenwood">{{Greenwood&Earnshaw}}</ref>
			] complex]]
			In its ], samarium remains heptacoordinate with five ether and two terminal iodide ligands.<ref>{{cite journal |author1=William J. Evans |author2=Tammy S. Gummersheimer |author3=Joseph W. Ziller |name-list-style=amp | year = 1995 | title = Coordination Chemistry of Samarium Diiodide with Ethers Including the Crystal Structure of Tetrahydrofuran-Solvated Samarium Diiodide, SmI<sub>2</sub>(THF)<sub>5</sub> | journal = ] | volume = 117 | issue = 35 | pages = 8999–9002 | doi = 10.1021/ja00140a016}}</ref>
			==Preparation==
			Samarium iodide is easily prepared in nearly quantitative yields from samarium metal and either ] or ].<ref>{{cite journal | author = P. Girard, J. L. Namy and H. B. Kagan | title = Divalent Lanthanide Derivatives in Organic Synthesis. 1. Mild Preparation of SmI<sub>2</sub> and YbI<sub>2</sub> and Their Use as Reducing or Coupling Agents | year = 1980 | journal = ] | volume = 102 | issue = 8 | pages = 2693–2698 | doi = 10.1021/ja00528a029}}</ref> When prepared in this way, its solutions is most often used without purification of the inorganic reagent.
			{{NumBlk|:|<math chem>\begin{array}{cl}{}\\
			\ce{{Sm} + ICH2I -> SmI2} + 0.5\ce{H2C=CH2} \\
			\ce{{Sm} + I(CH2)2I -> {SmI2} + H2C=CH2} \\
			{}\end{array}</math>|}}
			Solid, solvent-free SmI<sub>2</sub> forms by high temperature ] of ] (SmI<sub>3</sub>).<ref name="SM_1930">G. Jantsch, N. Skalla: "Zur Kenntnis der Halogenide der seltenen Erden. IV. – Über Samarium(II)jodid und den thermischen Abbau des Samarium(III)jodids", '']'', '''1930''', ''193'', 391–405; {{doi|10.1002/zaac.19301930132}}.</ref><ref>G. Jantsch: "Thermischer Abbau von seltenen Erd(III)halogeniden", '']'', '''1930''', ''18&nbsp;(7)'', 155–155; {{doi|10.1007/BF01501667}}.</ref><ref name="GMELIN">'']'', System Nr. 39, Band C 6, p. 192–194.</ref>
			== Reactions ==
			Samarium(II) iodide is a powerful ] – for example it rapidly reduces ] to ].<ref name = "Greenwood"/> It is available commercially as a dark blue 0.1 ] solution in THF. Although used typically in superstoichiometric amounts, catalytic applications have been described.<ref>{{cite journal |doi=10.1038/s41929-018-0219-x|title=SmI2-catalysed cyclization cascades by radical relay|year=2019|last1=Huang|first1=Huan-Ming|last2=McDouall|first2=Joseph J. W.|last3=Procter|first3=David J.|journal=Nature Catalysis|volume=2|issue=3|pages=211–218|s2cid=104423773|url=https://www.research.manchester.ac.uk/portal/en/publications/smi2catalyzed-cyclization-cascades-by-radical-relay(d64241b6-d89c-4ee2-b1a1-0eec1827ac0a).html}}</ref>
			===Organic chemistry===
			{{Main|Reductions with samarium(II) iodide}}
			Samarium(II) iodide is a reagent for ] formation, for example in a ] (similar to the ]) between a ] and an alkyl iodide to form a ]:<ref>{{cite journal | journal = ] | year = 1996 | pages = 633–634 |author1=Machrouhi, Fouzia |author2=Hamann, Béatrice |author3=Namy, Jean-Louis |author4=Kagan, Henri B. | title = Improved Reactivity of Diiodosamarium by Catalysis with Transition Metal Salts | doi = 10.1055/s-1996-5547 | volume = 1996 | issue = 7| s2cid = 196761752 }}</ref>
			:R<sup>1</sup>I + R<sup>2</sup>COR<sup>3</sup> → R<sup>1</sup>R<sup>2</sup>C(OH)R<sup>3</sup>
			]
			Typical reaction conditions use SmI<sub>2</sub> in THF in the presence of catalytic NiI<sub>2</sub>.
			]s react similarly (adding two R groups), but ]s give by-products. The reaction is convenient in that it is often very rapid (5 minutes or less in the cold). Although samarium(II) iodide is considered a powerful single-electron reducing agent, it does display remarkable ] among functional groups. For example, ]s and ]s can be reduced to the corresponding ] in the presence of a variety of ]-containing functionalities (such as ]s, ]s, ]s, ]s, etc.). This is presumably due to the considerably slower reaction with ]s as compared to ]s and ]s. Furthermore, hydrodehalogenation of halogenated ] to the corresponding ] compound can be achieved using samarium(II) iodide. Also, it can be monitored by the color change that occurs as the dark blue color of SmI<sub>2</sub> in THF discharges to a light yellow once the reaction has occurred. The picture shows the dark colour disappearing immediately upon contact with the ] mixture.
			Work-up is with dilute ], and the samarium is removed as aqueous Sm<sup>3+</sup>.
			Carbonyl compounds can also be coupled with simple alkenes to form five, six or eight membered rings.<ref>{{cite journal |author1=Molander, G. A. |author2=McKiie, J. A. | journal = ] | year = 1992 | volume = 57 | pages = 3132–3139 | doi = 10.1021/jo00037a033 | title = Samarium(II) iodide-induced reductive cyclization of unactivated olefinic ketones. Sequential radical cyclization/intermolecular nucleophilic addition and substitution reactions | issue = 11}}</ref>
			] groups can be removed from ''N''-tosylamides almost instantaneously, using SmI<sub>2</sub> in conjunction with distilled water and an amine base. The reaction is even effective for deprotection of sensitive substrates such as ]:<ref name="Ankner2009">{{cite journal|last=Ankner|first=Tobias|author2=Göran Hilmersson |year=2009|title=Instantaneous Deprotection of Tosylamides and Esters with SmI2/Amine/Water|journal=Organic Letters|publisher=American Chemical Society|volume=11|pages=503–506|doi=10.1021/ol802243d|pmid=19123840|issue=3}}</ref>
			:] {{clear left}}
			In the ], an alcohol could be almost instantaneously deoxygenated by reducing their toluate ester in presence of SmI<sub>2</sub>.
			:] {{clear left}}
			SmI<sub>2</sub> can also be used in the ] of ]. An example is the SmI<sub>2</sub> induced ] - ] ] of 5-methylenecyclooctanone which proceeds through a ] intermediate:
			:]
			:
			The applications of SmI<sub>2</sub> have been reviewed.<ref>{{cite journal | journal = ] | year = 2001 | pages = 2727–2751 | title =Recent developments in lanthanide mediated organic synthesis | author = Patrick G. Steel | doi = 10.1039/a908189e | issue = 21}}</ref><ref>{{cite journal |author1=Molander, G. A. |author2=Harris, C. R. | journal = ] | year = 1996 | volume = 96 | pages = 307–338 | doi = 10.1021/cr950019y | title = Sequencing Reactions with Samarium(II) Iodide | pmid=11848755 | issue = 1}}</ref><ref>{{cite journal |author1=K. C. Nicolaou |author2=Shelby P. Ellery |author3=Jason S. Chen | journal = ] | year = 2009 | volume = 48 | issue = 39 |pages = 7140–7165 | doi = 10.1002/anie.200902151 | title = Samarium Diiodide Mediated Reactions in Total Synthesis | pmid = 19714695 | pmc = 2771673}}</ref> The book ''Organic Synthesis Using Samarium Diiodide'', published in 2009, gives a detailed overview of reactions mediated by SmI<sub>2</sub>.<ref>{{cite book |last1=Procter |first1=David J. |last2=Flowers,II |first2=Robert A. |last3=Skydstrup |first3=Troels |year=2009 |title=Organic Synthesis Using Samarium Diiodide |publisher=Royal Society of Chemistry |isbn= 978-1-84755-110-8 }}</ref>
			== References ==
			{{reflist}}
			{{Samarium compounds}}
			{{Iodides}}
			{{Lanthanide halides}}
			]
			]
			]
			]
			]