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J. S. T. Gorman et al. / Tetrahedron Letters 44 (2003) 5435–5439
10. Crystallographic data for structures 1a and 2a have been
deposited with the Cambridge Crystallographic Data
Center as supplementary publication numbers CCDC
208711 and 208712, respectively. Copies of the data can
be obtained, free of charge, on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, UK [fax: +44(0)-
1223-336033 or email: deposit@ccdc.cam.ac.uk].
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Figure 7. Additional Ru–Cp Complexes.
tripodal complexation, nor was exchange of one teth-
ered phosphine for the other at the metal center
observed. Complex 1a did react with external phosphi-
nes, and the PPh3 exchanged with (tol)3P and was
completely displaced by PBu3. These results together
suggest that a two carbon tether between the phosphine
and the Cp makes for a particularly stable complex.
In summary, hydroxymethyl substituted spiro[2.4]-
hepta-4,6-dienes were shown to be efficient precursors
for the synthesis of chiral cyclopentadienyl ruthenium
complexes with pendant phosphine donors. This
method was used to prepare several new dipodal [h5,h1-
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structures for three related complexes revealed a con-
formational trend that suggests architectural require-
ments for future ligand designs.
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Acknowledgements
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We thank the Robert A. Welch Foundation for finan-
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