ChemComm
Communication
Complexes with the ligands equipped with flexible donor
1
2
arms (L and L ) generally show better activity than those with
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4
rigid donor arms (L and L ). This is the demonstration of the
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catalytic prowess of hybrid ligands, as explained elsewhere.
1
2
Between the amine (L ) and ether (L ) pendants, the former
generally give higher catalytically productivities presumably because
of the stronger chelating support of the catalytically active nickel.
This communication describes an efficient method to prepare
a range of structurally distinctive and catalytically active Ni(II)
complexes through a clean transmetallation pathway using Na(I)
complexes containing trifunctional hybrid ligands. The isolated and
Fig. 4 X-ray structures of 8 and 9 drawn at 30% probability thermal ellipsoids.
Selected bond distances (Å) and angles (deg) for 8: Ni1–O1A 1.828(2), O1A–Ni1–O1
180.0(0), O1–Ni1–N1A 87.05(7). Atoms with the A label were generated by
symmetry operator Àx, Ày + 1, Àz + 1. For 9, Ni1–Cl1 2.4017(8), Ni1–O5 2.125(2),
Ni2–Cl2 2.4270(9), Ni2–Cl1 2.4850(9), Ni3–Cl2 2.4764(9), Ni3–O5 2.125(2), crystallographically established cubane and double-cubane frame-
O5–Ni1–Cl1 161.69(7), Cl2–Ni2–Cl1 161.50(3), O5–Ni3–Cl2 154.83(6).
works of the intermediate Na(I) complexes are reminiscent of and
yet contrasted with the structural diversity of the Ag(I) carbene
intermediates used in the transmetallation reactions for metal
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NHC carbenes. This work further suggests that many known
base-assisted (typified by NaH) preparations of metal complexes
could proceed via multinuclear Na(I) complexes instead of simplistic
+
mononuclear or even ionic Na species. We are currently exploring
the transmetallation potential of the title cubanes and double-
cubanes towards other metals.
We acknowledge the National University of Singapore,
the Ministry of Education for financial support (WBS No.
R-143-000-361-112). We thank Dr L. L. Koh, G. K. Tan and
Fig. 5 X-ray structures of 7 and 13 drawn at 30% probability thermal ellipsoids.
Selected bond distances (Å) and angles (deg) for 7: Ni1–Cl1 2.462(2), Ni1–O1 2.050(4),
Ni2–O1 2.252(4), Ni2–O3 2.207(4), Ni3–Cl1 2.488(3), Ni3–O3 2.081(5), O1–Ni1–Cl1
Y. M. Hong for X-ray diffractometry assistance.
1
62.02(13), O3–Ni3–Cl1 159.92(13). For 13: Ni1–Cl1 2.4049(7), Ni1–Cl2 2.4251(7), Ni2–
Cl1 2.4168(7), Ni2–Cl3 2.4291(7), Ni3–Cl4 2.3180(7), Ni3–Cl2 2.4127(7), Cl1–Ni1–Cl2
66.63(2), Cl1–Ni2–Cl3 165.45(2), Cl2–Ni3–Cl3 161.25(2). Only one of the two
27Cl Ni ) molecules is shown.
Notes and references
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(C
30
H
4
N
3
3 2 2
O S
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2
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(
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Fig. 6 X-ray structure of 12 drawn at 30% probability thermal ellipsoids.
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Selected bond distances (Å) and angles (deg): Ni1–O1 1.965(3), Ni1–N1
6
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and S. Brooker, Supramol. Chem., 2007, 19(1–2), 17.
2
.020(4), Ni1–O3 2.077(3), Ni1–O2 2.332(3), Ni2–O3 1.980(3), Ni2–O2 2.000(3),
Ni2–O1 2.176(3), O1–Ni1–O2 76.89(12), O3–Ni1–O2 73.77(12), O1–Ni1–O3
9.52(13), O3–Ni2–O1 76.85(12), O2–Ni2–O1 79.99(12).
7
8
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hydroxides) are available. These give the system a multitude of
flexibility that helps to stabilize both metals in different coordinative
environments, which is essential in catalytic performance.
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1
Nickel complexes with salicylaldimine based ligands show
good catalytic activities in ethylene oligomerization or poly-
(
b) A. E. Obodovskaya, L. M. Shkol’nikova, V. E. Zavodnik,
1
,7,11
merization.
In this work, all the Ni(II) complexes have been
N. V. Rannev, S. G. Kochin, V. A. Kogan and O. A. Osipov, Koord.
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evaluated for their potential in catalytic oligomerisation of
ethylene. They generally show moderate to high activities with
high selectivity to C products (Z98%) (see ESI†). Among the C
1
4
4
products, selectivity to 1-butene is up to 90%. Complex 6 shows
the highest activity and highest selectivity to C products (99%).
4
12 W. H. Zhang, S. W. Chien and T. S. A. Hor, Coord. Chem. Rev., 2011,
255, 1991.
8
Negligible C , C10 and polymer products are formed.
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994 Chem. Commun., 2013, 49, 4992--4994
This journal is c The Royal Society of Chemistry 2013