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Synthesis of new silyl-bridged bis(cyclopentadienyl) ligands and complexes

Journal Article · · Organometallics
DOI:https://doi.org/10.1021/om960132u· OSTI ID:420896
; ;  [1]
  1. Univ. of Missouri, St. Louis, MO (United States)
The new monobridged compound, [{mu}-(MePhSi)(C{sub 5}H{sub 5}){sub 2}] (2), was obtained as a mixture of five positional isomers from the reaction of MePhSiCl{sub 2} with 2 equiv of Li(C{sub 5}/H{sub 5}). Deprotonation of 2 with 2 equiv of {sup n}BuLi and subsequent reaction with 1 equiv of Me{sub 2}SiCl{sub 2} in THF resulted in an unsymmetrical dibridged (bis)cyclopentadienyl compound, [{mu},{mu}-(MePhSi)(Me{sub 2}Si)(C{sub 5}H{sub 4}){sub 2}] (3). Compound 3 was shown to be a mixture of five isomers by 1D and 2D NMR experiments. Similarly, [{mu}-(Me{sub 2}SiCH{sub 2}CH{sub 2}SiMe{sub 2})(C{sub 5}H{sub 5}){sub 2}] (4) was deprotonated with 2 equiv of {sup n}BuLi and subsequently reacted with 1 equiv of ClMe{sub 2}SiCH{sub 2}CH{sub 2}SiMe{sub 2}Cl to provide the (bis)cyclopentadienyl compound with two four-atom bridges [{mu},{mu}-(Me{sub 2}SiCH{sub 2}CH{sub 2}SiMe{sub 2}){sub 2}(C{sub 5}H{sub 4}){sub 2}] (5). X-ray diffraction studies of sublimed 5 showed the solid state structure to be the symmetrical 1,3-1,3 trans isomer, and NMR studies of 5 indicated a mixture of isomers in solution. The {sup 1}H, {sup 13}C, {sup 29}Si, and VT NMR spectra of compounds 2, 3, and 5 are described. 28 refs., 8 figs., 5 tabs.
DOE Contract Number:
FG02-92CH10499
OSTI ID:
420896
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 19 Vol. 15; ISSN ORGND7; ISSN 0276-7333
Country of Publication:
United States
Language:
English