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Solid-state structures of base-free ytterbocenes and inclusion compounds of bis(pentamethylcyclopentadienyl)ytterbium with neutral carboranes and toluene: The role of intermolecular contacts

Journal Article · · Organometallics
DOI:https://doi.org/10.1021/om990821g· OSTI ID:20017495
The base-free ytterbocenes (Me{sub 5}C{sub 5}){sub 2}Yb, (Me{sub 4}C{sub 5}H){sub 2}Yb, and [1,3-(Me{sub 3}C){sub 2}C{sub 5}H{sub 3}]{sub 2}Yb have been prepared from their diethyl ether adducts, synthesized by reaction of YbI{sub 2} and the sodium salt of the substituted cyclopentadiene anion in diethyl ether. The structures of the base-free molecules have been determined by X-ray crystallography. The molecule (Me{sub 5}C{sub 5}){sub 2}Yb has been found to crystallize in two different morphologies; the complex also forms inclusion complexes with toluene, ortho-carborane, meta-carborane, and 1,2-dimethyl-ortho-carborane. The ytterbocene molecule in all of the derivatives examined is bent in the solid state with centroid-metal-centroid angles ranging from 132{degree} to 147{degree}. A detailed examination of the structures and comparison with the reported structures of (Me{sub 5}C{sub 5}){sub 2}Eu, (Me{sub 5}C{sub 5}){sub 2}Sm, [1,3-(Me{sub 3}Si){sub 2}C{sub 5}H{sub 3}]{sub 2}Yb, and [1,3-(Me{sub 3}Si){sub 2}C{sub 5}H{sub 3}]{sub 2}Eu reveal that bending is the general structural preference. Close inter- or intramolecular contacts are observed in every case between the ytterbium atom and one or more carbon atoms other than those of the two cyclopentadienide rings of that ytterbocene fragment. The packing geometry is dictated by the substituents on the cyclopentadienide rings, the molecules arranging so as to minimize crowding in the solid state. The net result is a coordination polymer, dimer, or monomer, depending on the ring substituents.
Research Organization:
Univ. of California, Berkeley, CA (US)
Sponsoring Organization:
US Department of Energy; National Science Foundation
DOE Contract Number:
AC03-76SF00098
OSTI ID:
20017495
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 5 Vol. 19; ISSN ORGND7; ISSN 0276-7333
Country of Publication:
United States
Language:
English