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lished by an nOe experiment; the presence of thf in this
complex (but its absence in the related
[Sc(N2NNpy)(CH2SiMe3)]) testifies to the apparently
less sterically crowding nature of the O2NNpy ligand in
comparison to the related N2NNpy. We were unable to
obtain diffraction-quality crystals of the dialkyl com-
plex [Sc(OArN3)(CH2SiMe3)2] (8), and so to establish
further its identity we treated it with two equivalents of
p-cresol (HOꢀ4-C6H4Me). This protonolysis reaction
yielded two equivalents of SiMe4 (observed by 1H-
NMR spectroscopy) and the bis(aryloxide) complex
[Sc(OArN3)(OAr)2] (10, OAr=Oꢀ4-C6H4Me). The
OArN3 ligand sub-spectra of 10 are comparable to those
of the precursor 8. The molecular structure of 10 as
determined by X-ray crystallography is illustrated in
Fig. 4 together with selected bond lengths. Fig. 4
confirms the proposed molecular structure and lends
support to that also proposed for [Sc(OArN3)-
(CH2SiMe3)2] (8).
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In conclusion, we have described new organoscan-
dium and related complexes of three new ligand envi-
ronments for the organometallic chemistry of this
element. Work is in progress to probe and define the
reaction chemistry of the new complexes and their
heavier Group 3 congeners and homologues.
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Organometallics (2001) to be submitted;
3. Supplementary material
Crystallographic data have been depoisited with the
Cambride Crystallographic Data Centre, deposition
numbers for compounds 5·C6H6, 7 and 10·C6H6:
CCDC 170226, CCDC 170227 and CCDC 170228,
respectively. Copies of this information may be ob-
tained free of charge from The Director, CCDC, 12
Union Road, Cambridge CB2 1EK, UK (fax: +44-
(b) B.R. Tyrrell, T. Toupance, P. Mountford, unpublished
results.
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[14] NMR, IR and mass spectroscopic data are fully consistent with
the proposed structures. Satisfactory C, H and N combustion
analyses have been obtained for all of the new compounds except
for the spectroscopically pure OArN3-supported compounds 8
and 10, despite repeated recrystallisations. The EI-mass spectrum
Acknowledgements
of
8 showed an isotope envelope corresponding to [M−
CH2SiMe3]+; that of 10 showed the expected molecular ion. In
addition, the X-ray structure of 10 is fully consistent with the
proposed structure. The 1H- and 13C-NMR data for 8 are
analogous to those of a fully characterised yttrium analogue [17].
[15] The corresponding reaction with YCl3 gives the binuclear, seven-
coordinate yttrium complex [Y(O2NNpy)2(m-Cl)2(py)2] as estab-
lished by X-ray crystallography. B.R. Tyrrell, P. Mountford,
unpublished results.
We thank the University of Oxford, EPSRC and
Leverhulme Trust for support of this work. We also
thank Dr G.A. Vaughan (Exxon Chemical Co.) for a
generous gifts of ScCl3, and Dr T. Toupance for helpful
discussions.
[16] X-ray data: For [Sc(O2NNpy)Cl(py)]·C6H6 (5·C6H6): C47H61
-
References
ClN3O2Sc, M=780.43, monolinic, spacegroup C2/c, a=
,
27.0551(8), b=17.8450(5), c=19.0419(8) A, i=95.537(1)°,
3
U=9150.5(5) A , Z=8, T=150 K, v=0.26 mm−1, 10 384
,
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D.R. Aris, G.R. Willey, Coord. Chem. Rev. 181 (1999) 121;
(b) S.A. Cotton, Polyhedron, 18 (1999) 1691;
independent reflections (Rmerge=0.11) with 2577 having I\
3|(I) and 4820 having I\|(I) and used in refinement of 457
parameters, final R indices: R=0.0667 [I\3|(I)] and Rw=
(c) F.T. Edelmann, in: E.W. Abel, F.G.A. Stone, G. Wilkinson
(Eds.), Comprehensive Organometallic Chemistry, 2nd ed., vol.
4, 1995, p. 10;
0.0882
[I\|(I)].
For
[Sc(N2NNpy)(CH2SiMe3)]
(7):
C20H43N4ScSi3, M=468.81, T=175 K, orthorhombic, space-