Tin(II) bromide explained

Tin(II) bromide is a chemical compound of tin and bromine with a chemical formula of SnBr2. Tin is in the +2 oxidation state. The stability of tin compounds in this oxidation state is attributed to the inert pair effect.

Structure and bonding

In the gas phase SnBr2 is non-linear with a bent configuration similar to SnCl2 in the gas phase. The Br-Sn-Br angle is 95° and the Sn-Br bond length is 255pm.[1] There is evidence of dimerisation in the gaseous phase.[2] The solid state structure is related to that of SnCl2 and PbCl2 and the tin atoms have five near bromine atom neighbours in an approximately trigonal bipyramidal configuration.[3] Two polymorphs exist: a room-temperature orthorhombic polymorph, and a high-temperature hexagonal polymorph. Both contain (SnBr2) chains but the packing arrangement differs.

Preparation

Tin(II) bromide can be prepared by the reaction of metallic tin and HBr distilling off the H2O/HBr and cooling:

Sn + 2 HBr → SnBr2 + H2

However, the reaction will produce tin (IV) bromide in the presence of oxygen.

Reactions

SnBr2 is soluble in donor solvents such as acetone, pyridine and dimethylsulfoxide to give pyramidal adducts.
A number of hydrates are known, 2SnBr2·H2O, 3SnBr2·H2O & 6SnBr2·5H2O which in the solid phase have tin coordinated by a distorted trigonal prism of 6 bromine atoms with Br or H2O capping 1 or 2 faces.When dissolved in HBr the pyramidal SnBr3- ion is formed.Like SnCl2 it is a reducing agent. With a variety of alkyl bromides oxidative addition can occur to yield the alkyltin tribromide[4] e.g.

SnBr2 + RBr → RSnBr3

Tin(II) bromide can act as a Lewis acid forming adducts with donor molecules e.g. trimethylamine where it forms NMe3·SnBr2 and 2NMe3·SnBr2[5] It can also act as both donor and acceptor in, for example, the complex F3B·SnBr2·NMe3 where it is a donor to boron trifluoride and an acceptor to trimethylamine.[6]

Notes and References

  1. J.L Wardell "Tin:Inorganic Chemistry" Encyclopedia of Inorganic Chemistry Ed: R Bruce King John Wiley & Sons (1994)
  2. Thermochemistry of tetrabromoditin and bromoiodotin gaseous. K. Hilpert . M. Miller . F. Ramondo . J. Phys. Chem.. 1991. 95. 19. 7261–7266. 10.1021/j100172a031.
  3. Inert Pair Effects in Tin and Lead Dihalides: Crystal Structure of Tin(II) Bromide. Abrahams I. . Demetriou D.Z. . Journal of Solid State Chemistry. 2000. 149. 1. 28–32. 10.1006/jssc.1999.8489. 2000JSSCh.149...28A .
  4. A convenient synthesis of (C1-C18) alkyltin tribromides. Bulten E.J.. Journal of Organometallic Chemistry. 1975. 97. 1. 167–172. 10.1016/S0022-328X(00)89463-2. 1874/15985. free.
  5. Synthesis and studies of trimethylamine adducts with tin(II) halides. Chung Chun Hsu . R. A. Geanangel . amp . Inorg. Chem.. 1977. 16. 1. 2529–2534. 10.1021/ic50176a022.
  6. Donor and acceptor behavior of divalent tin compounds. Chung Chun Hsu . R. A. Geanangel . amp . Inorg. Chem.. 1980. 19. 1. 110–119. 10.1021/ic50203a024.