Samarium(II) bromide explained

Samarium(II) bromide is an inorganic compound with the chemical formula .[1] It is a brown solid that is insoluble in most solvents but degrades readily in air.

Structure

In the gas phase, is a bent molecule with Sm–Br distance 274.5 pm and bond angle 131±6°.[2]

History

Samarium(II) bromide was first synthesized in 1934 by P. W. Selwood, when he reduced samarium tribromide (SmBr3) with hydrogen (H2). Kagan also synthesized it by converting samarium(III) oxide (Sm2O3) to SmBr3 and then reducing with a lithium dispersion in THF. Robert A. Flowers synthesized it by adding two equivalent of lithium bromide (LiBr) to samarium diiodide (SmI2) in tetrahydrofuran. Namy managed to synthesize it by mixing tetrabromoethane (C2H2Br4) with samarium metal, and Hilmerson found that heating the tetrabromoethane or samarium greatly improved the production of samarium(II) bromide.[3]

Reactions

Samarium(II) bromide has reducing properties reminiscent of the more commonly used samarium diiodide.[4] It is an effective for pinacol homocouplings of aldehydes, ketones, and cross-coupling carbonyl compounds. Reports have shown that samarium(II) bromide is capable of selectively reducing ketones if it is in the presence of an alkyl halide.[3]

Samarium(II) bromide forms soluble adducts with hexamethylphosphoramide. This species reduces imines to amines and alkyl chlorides to hydrocarbons.[5] For example, SmBr2(hmpa)x converts cyclohexyl chloride to cyclohexane.[6]

Samarium(II) bromide will reduce ketones in tetrahydrofuran if an activator is absent.[7]

Notes and References

  1. Web site: Elements. American. Samarium Bromide SmBr2. American Elements. 20 December 2016.
  2. Ezhov . Yu. S. . Sevast'yanov . V. G. . Molecular Structure of Samarium Dibromide . Journal of Structural Chemistry . January 2004 . 45 . 1 . 160–164 . 10.1023/B:JORY.0000041516.14569.9c. 96049918 .
  3. Book: Skrydstrup. David J. Procter, Robert A. Flowers, Troels. Organic synthesis using samarium diiodide a practical guide. limited. 2009. Royal Society of Chemistry. Cambridge. 9781847551108. 157.
  4. Book: Ho. Tse-Lok. Fiesers' Reagents for Organic Synthesis Volume 28. 2016. John Wiley & Sons. 9781118942819. 486.
  5. Book: Pecharsky. Vitalij K.. Bünzli. Jean-Claude G.. Gschneidner. Karl A.. Handbook on the physics and chemistry of rare earths. 2006. North Holland Pub. Co.. Amsterdam. 9780080466729. 431.
  6. Book: Couty. Sylvain. Baird. Mark S.. Meijere. Armin de. Chessum. Nicola. Dzielendziak. Adam. Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 48: Alkanes. 2014. Georg Thieme Verlag. 9783131722911. 153.
  7. Book: Brown. Richard. Cox. Liam. Eames. Jason. Fader. Lee. Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 36: Alcohols. 2014. Georg Thieme Verlag. 9783131721310. 129.