Heterometallic lanthanide group 12 metal iodides.
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.
Huebner
Louise
L
Department of Chemistry and Chemical Biology, Rutgers, the State University of New Jersey, 610 Taylor Road, Piscataway, NJ 08854-8087, USA.
Kornienko
Anna
A
Emge
Thomas J
TJ
Brennan
John G
JG
D007455:Iodine / Q000737:chemistry*; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D019216:Metals, Heavy / Q000737:chemistry*; D008956:Models, Chemical; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D028581:Lanthanoid Series Elements; D019216:Metals, Heavy; D009942:Organometallic Compounds; D007455:Iodine