TY - JOUR
T1 - Eight-coordinate fluoride in a silicate double-four-ring
AU - Goesten, M.G.
AU - Hoffmann, R.
AU - Bickelhaupt, F.M.
AU - Hensen, E.J.M.
PY - 2017
Y1 - 2017
N2 - Fluoride, nature’s smallest anion, is capable of covalently coordinating to eight silicon atoms. The setting is a simple and common motif in zeolite chemistry: the box-shaped silicate double-four-ring (D4R). Fluoride seeks its center. It is the strain of box deformation that keeps fluoride in the middle of the box, and freezes what would be a transition state in its absence. Hypervalent bonding ensues. Fluoride’s compactness works to its advantage in stabilizing the cage; chloride, bromide, and iodide do not bring about stabilization due to greater steric repulsion with the box frame. The combination of strain and hypervalent bonding, and the way they work in concert to yield this unusual case of multiple hypervalence, has potential for extension to a broader range of solid-state compounds.
AB - Fluoride, nature’s smallest anion, is capable of covalently coordinating to eight silicon atoms. The setting is a simple and common motif in zeolite chemistry: the box-shaped silicate double-four-ring (D4R). Fluoride seeks its center. It is the strain of box deformation that keeps fluoride in the middle of the box, and freezes what would be a transition state in its absence. Hypervalent bonding ensues. Fluoride’s compactness works to its advantage in stabilizing the cage; chloride, bromide, and iodide do not bring about stabilization due to greater steric repulsion with the box frame. The combination of strain and hypervalent bonding, and the way they work in concert to yield this unusual case of multiple hypervalence, has potential for extension to a broader range of solid-state compounds.
KW - Chemical bonding
KW - Hypervalence
KW - Main-group chemistry
KW - Zeolite chemistry
UR - http://www.scopus.com/inward/record.url?scp=85011295542&partnerID=8YFLogxK
U2 - 10.1073/pnas.1615742114
DO - 10.1073/pnas.1615742114
M3 - Article
C2 - 28096342
SN - 0027-8424
VL - 114
SP - 828
EP - 833
JO - Proceedings of the National Academy of Sciences of the United States of America (PNAS)
JF - Proceedings of the National Academy of Sciences of the United States of America (PNAS)
IS - 5
ER -