Supporting Information
© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2006
Mechanistic Insights into Stereoselective Catalysis – The Effects of
Counterions in a Cu(II)Bis(sulfoximine) Catalyzed Diels-Alder Reaction
Carsten Bolm,*,[a] Marc Martin, [a] Georg Gescheidt,*, [b] Cornelia Palivan, [c] Tsvetanka
Stanoeva, [b] Helmut Bertagnolli,*, [d] Martin Feth, [d] Arthur Schweiger, ,%, [e] George Mitrikas,
[e]
and Jeffrey Harmer*,[e]
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Table 1: Structural parameters of Cu(II) reference compounds according to X-ray diffraction
experiments (N: coordination number, r: distance, A: Absorber, Bs: Backscatterer)
A-Bs
r [Å]
N
Cu-Br
2.40
4
[(Phen)CuCl2]a
Cu-N
2.05
2
XRD [2]
Cu-Cl
2.30
2
[(Phen)CuIIBr2]a
Cu-N
2.04
2
Cu-Br
2.40
2
CuBr2
XRD [1]
XRD
a
[3]
Phen: 1,10-Phenanthroline
[1] L. Helmholz, J. Am. Chem. Soc. 1949, 69, 886.
[2] D. Boys, C. Escobar, S. Martinez-Carrera, Acta Cryst. 1981, B37, 351.
[3] M.T. Garland, D. Grandjean, E. Spodine, A.M. Atria, J. Manzur, Acta Cryst. 1988, C44,
1547.
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Figure 1: Experimental (solid line) and calculated (dotted line) k³ χ(k) functions (a) and their
Fourier transforms (b) of solid CuBr2 at the Cu K-edge.
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Figure 2: Comparison of the experimental k³χ(k) functions (a) their Fourier transforms of
solid CuBr2 + 1 eq. (S,S)-1 und CuBr2 + 2 eq. (S,S)-1 (isolated from CH2Cl2) at the Br K-edge.
Figure 3: Comparison of the experimental k³χ(k) functions (a) their Fourier transforms of
solid CuBr2 and CuBr2 + 1 eq. (S,S)-1 (isolated from CH2Cl2) at the Br K-edge.
.
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A
B
Figure 4: EPR spectra of (S,S)–1 + CuCl2 + 2 in the g = 2 region. A) FID-detected EPR
spectrum and simulation (c1). (B) CW-EPR spectrum and simulations which comprise the
FID-detected EPR spectrum
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(c1: 75%) and a quasi-isotropic component (c2: 25%) that is associated with the half-field
signal.
Red – experimental, c1 – cyan, c2 – dark blue, black – (c1+c2).
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A
B
Figure 5: EPR spectra of (S,S)–1 + CuBr2 in the g = 2 region. A) FID-detected EPR spectrum
and simulation (c1 + a small c2 component). (B) CW-EPR spectrum and simulations which
comprise the FID-detected EPR spectrum (c1: 15%) and a quasi-isotropic component (c2:
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85%) that is associated with the half-field signal. Red – experimental, c1 – cyan, c2 – dark
blue, black – (c1+c2).
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Figure 6: CW EPR spectra of (S,S)–1 + CuBr2 + 2 in the g = 2 region and simulations which
comprise the FID-detected EPR spectrum (c1: 30%) and a quasi-isotropic component (c2:
70%) that is associated with the half-field signal. Red – experimental, c1 – cyan, c2 – dark
blue, black – (c1+c2).