Heterometallic lanthanide group 12 metal iodides

Inorganic Chemistry
Louise HuebnerJohn G Brennan

Abstract

Neodymium tri-iodide reacts with Group 12 metal (M; M = Zn, Cd, Hg) iodides to form heterometallic compounds. These Lewis acidic M cleave Nd-I bonds to give either ionic ([(THF)(5)NdI(2)][MI(3)THF]; M = Zn, Cd) or charge-neutral [(THF)(5)NdI(micro(2)I)HgI(3)] compounds. Differences in structure are interpreted primarily in terms of M-L bond strengths, rather than Nd-L bond strengths. Experiments with Yb indicate that if there is any excess iodide present in these syntheses then the most readily isolated product is a triiodide salt, i.e., [(THF)(5)YbI(2)][I(3)]. In conventional solvents the presence of Lewis acid is not required for iodide displacement-from pyridine, "YbI(3)" crystallizes as [(py)(5)YbI(2)][I]. These compounds are potentially useful as heterometallic sources of lanthanide-doped iodide matrixes, they illustrate the ease with which iodides are displaced from lanthanide coordination spheres, and they underscore the complexity associated with using lanthanide iodides as Lewis acid catalysts.

References

Oct 24, 2001·Inorganic Chemistry·David W. KnoeppelSheldon G. Shore
Jan 10, 2002·Inorganic Chemistry·Anna KornienkoJohn G Brennan
Jun 13, 2002·Chemical Reviews·Jean-Claude G Bünzli, Claude Piguet
Oct 16, 2002·Inorganic Chemistry·Raquel Rodríguez-CortiñasTeresa Rodríguez-Blas
Aug 14, 2003·Journal of the American Chemical Society·Peter B GloverZoe Pikramenou
Dec 9, 2003·Inorganic Chemistry·Anna KornienkoJohn G Brennan

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Citations

Nov 17, 2006·Chemical Communications : Chem Comm·Yan-Qiong SunGuo-Yu Yang
Nov 2, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Katharina M Fromm
Nov 26, 2015·Inorganic Chemistry·Jessie L BrownAndrew J Gaunt
May 11, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Thaige P GompaHenry S La Pierre
Apr 9, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Luis M Aguirre QuintanaHenry S La Pierre
Sep 19, 2020·Nature Communications·Laura VoigtKasper S Pedersen
Aug 22, 2008·Inorganic Chemistry·Andrew J GauntMary P Neu
Sep 28, 2004·Inorganic Chemistry·Santanu BanerjeeJohn G Brennan

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