of TMS cyanide with one equivalent of benzaldehyde in the
presence of 1 mol% of 4 at room temperature resulted in the
quantitative formation of the addition product 6 (Scheme 3).
Interestingly, the titanium dichloro complex of a ‘‘regular’’
calixarene ligand, 1,3-dimethylcalixarene,14 showed only
minimal catalytic activity in the same reaction, demonstrating
the advantages of the new ligand design for catalysis.
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In summary, we prepared a new oxygen-depleted calixarene
ligand with triazole groups attached to the lower rim. The ligand
can be used to prepare a titanium(IV) complex which showed
catalytic activity superior to that of the unmodified calixarene
Ti(IV) complex. We are currently studying the catalytic activity
of the new complexes in various organic reactions as well as
working on the asymmetric version of the new ligand.
We acknowledge the support from Israel Science Foundation.
Notes and references
z Crystal structure data: for 3: C62H70N6O2, M = 931.24, 0.6 ꢁ 0.3 ꢁ
0.03 mm3, monoclinic, space group P21/c,
a = 11.6844(5),
b = 41.4198(15), c = 10.9193(4) A, b = 98.280(2)1, V = 5229.5(4) A3,
Z = 4, Dc = 1.183 g cmꢂ3, 2ymax = 25.061, Nonius KappaCCD,
Mo-Ka radiation (l
= 0.71073 A), graphite monochromator,
T = 110(2) K, 6705 collected reflections, 4505 unique reflections
(Rint = 0.0720). R1 = 0.0771, wR2 = 0.1661 for data with
I 4 2s(I), and R1 = 0.1232, wR2 = 0.1923 for all unique data. The
crystals are characterized by high mosaicity and very poor diffraction.
Some of the tert-butyl groups exhibit partial orientational disorder,
which could not be resolved. The low resolution of the dataset
affects the reliability of the parameters calculated from the structure
determination. The structure is used to show connectivity.
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For 4: C62H68Cl2N6O2Tiꢃ1.721(CHCl3), M = 1253.44, 0.45 ꢁ 0.35 ꢁ
3
0.10 mm , triclinic, space group P1, a = 12.3623(4), b = 16.3201(4),
ꢀ
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c
=
19.1318(7) A,
g = 71.1954(17)1, V = 3528.9(2) A3, Z = 2, Dc = 1.181 g cmꢂ3
2ymax = 27.481, Nonius KappaCCD, Mo-Ka radiation (l = 0.71073 A),
graphite monochromator, 110(2) K, 15 836 collected
reflections, 10 522 unique reflections (Rint = 0.0440). R1 = 0.0753,
wR2 0.2135 for data with 2s(I), and R1 0.1111,
a
=
83.9380(19),
b
=
75.0364(13),
,
T
=
=
I
4
=
wR2 = 0.2349 for all unique data. The crystal contains molecules of
partly disordered chloroform solvent. It also contains additional
crystallization solvent, which could not be modeled by discrete atoms.
Two of the tert-butyl substituents also exhibit rotational disorder.
Distance constraints were used in their crystallographic refinement.
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ꢀc
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