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influence on the metal-ligand bonding mode, resulting in complexes having a diverse array of
both coordination number and number of chelating or bridging ligands. The thermal reactivity of
1, i.e., the loss of (NMe2BH2)2 to yield the 14- coordinate [Th(H3BNMe2BH3)2(BH4)2] (2),
suggests that even the 15 coordinate structure of 1 seen in the solid state is still sufficiently
crowded to promote conversion to a geometry with a lower coordination geometry. However,
with a judicious choice of large metal and small ligands, complexes with stable 16-coordinate
geometries do not seem implausible.
ACKNOWLEDGEMENTS
Work at Argonne National Laboratory was supported by the US Department of Energy, BESMaterials Science, under contract DEAC02-06CH11357. Work at the University of Illinois was
supported by the U.S. National Science Foundation (CHE 07-50422) and the PG Research
Foundation. We thank Scott R. Wilson and Teresa Prussak-Wieckowska for collecting the XRD
data.
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