Inorganic Chemistry
Communication
Notes
(μ-O)}2] is unusually acute because of both the size of the
bridging atoms and the high steric requirement of the iPrL
ligand. In our case, the lower steric bulk of MeL may also play a
role in the shortening of the Al−O bond lengths, thus resulting
in a more obtuse Al−O−Al angle, which, in turn, relieves the
ring strain to some extent.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We thank DGAPA UNAM (Grant IN210710) for financial
support and DGTIC UNAM for computer time.
■
In order to gain further insight into the bonding properties of
the inorganic cores in 4 and 7, the local and integrated
properties15 of the electron density in these compounds were
calculated together with those in the related compounds
[{MeLAl(EH)}2(μ-O)] (E = O, S, Te).16 A comparison of the
data obtained from the calculated structure of [MeLAl-
(TeH)}2(μ-O)] and that of 7 allowed a better understanding
of the influence of the ring strain on the electronic properties of
the latter.
From the molecular graphs of 4 and 7 (Figures S4 and S5 in
SI), it is possible to observe the set of bond paths
corresponding to the Se−Al−O−Al−Se fragment and the
Al2OTe ring. In both cases, several C−H···O, C−H···E (E =
Te, Se), and C−H···π interactions were observed, which help to
stabilize the structure. On the basis of the properties of the
bond critical points,17,18 it is possible to determine the ionic
order in the Al−E bonds: Al−O ≫ Al−Te(cyclic) > Al−S >
Al−Se > Al−Te(acyclic) (Table S4 in the SI).
REFERENCES
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(1) (a) Sinn, H.; Kaminsky, W. Adv. Organomet. Chem. 1980, 18, 99.
(b) Feng, T. L.; Gurian, P. L.; Healy, M. D.; Barron, A. R. Inorg. Chem.
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The atomic charges (q) in the E−Al−O−Al−E fragment of
these compounds show tendencies related to the chalcogen
atom E, as well as to the cyclic or acyclic nature of the
compounds (Table S5 in the SI). The positive atomic charge of
the aluminum atom decreases with an increase of the atomic
number of E, as opposed to an increase of the negative charge
of the bridging oxygen atom. On the other hand, the q(Te) in
[{MeLAl(TeH)}2(μ-O)] corresponds to −0.57, while that for
the cyclic tellurium alumoxane 7 corresponds to −1.3, more
than twice the value of that in the former. This can be
rationalized in terms of the difference in the connectivity of the
tellurium atoms in these compounds, specifically to the
electronic demand that the two aluminum atoms in 7 exert
on the tellurium atom.
́
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A.; Moya-Cabrera, M. Angew. Chem., Int. Ed. 2007, 46, 2895.
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Angew. Chem. 2003, 115, 5660; Angew. Chem., Int. Ed. 2003, 42, 5502.
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Power, P. P. J. Am. Chem. Soc. 2005, 127, 10170.
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Inorg. Chem. 2004, 3508.
In summary, a facile method was developed for preparation
of the molecular hydrogenselenide 3 and the unique
alumoxanes 4 and 7. Furthermore, 3 and 4 can by useful
synthons for the preparation of unusual heterobimetallic ring
systems.
(10) Cui, C.; Roesky, H. W.; Noltemeyer, M.; Schmidt, H.-G.
Organometallics 1999, 18, 5120.
(11) Keith, T. A. AIMAll, version 11.12.19; TK Gristmill Software:
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reference, see the SI.
ASSOCIATED CONTENT
■
S
* Supporting Information
(15) Bader, R. F. W. Atoms in Molecules, a Quantum Theory;
Clarendon Press: Oxford, U.K., 1990.
X-ray crystallographic procedure details for compounds 4, 5,
and 7 (Table S1), details on the refinement of 5 (Table S2),
space group assignment for 7 (Table S3), CIF format files for 4,
5, and 7, detailed experimental procedures for compounds 3, 4,
and 7 (Figures S1−S5), further details of the DFT computa-
tional studies (Tables S4 and S5), and the full ref 14. This
material is available free of charge via the Internet at http://
(16) Compounds [{MeLAl(EH)}2(μ-O)] (E = O, S) were prepared
by our research group (see ref 3), while [{MeLAl(TeH)}2(μ-O)] in
unknown to date; thus, its structure was calculated in order to have
comparable data with the former compounds as well as with 4 and 7.
(17) Macchi, P.; Sironi, A. Coord. Chem. Rev. 2003, 238−383.
(18) Koch, U.; Popelier, P. L. A. J. Phys. Chem. 1995, 99, 9747−9754.
AUTHOR INFORMATION
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Corresponding Author
Present Address
‡S.G.-G.: Institute of Inorganic Chemistry, Karlsruhe Institute
of Technology, Engesserstrasse 15, Gebaude 30, 76131
̈
Karlsruhe, Germany.
2795
dx.doi.org/10.1021/ic302588f | Inorg. Chem. 2013, 52, 2793−2795