1,3ꢀDiphenylindenyl zirconium complexes
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
1659
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Table 2. Selected bond lengths (d) and bond angles (ω) in the
structure of compound 2*
Bis(η ꢀ1,3ꢀdiphenylindenyl)dichlorozirconium (adduct with
5
one toluene molecule), (η ꢀ1,3ꢀC9H5Ph2)2ZrCl2•C6H5CH3 (1).
A mixture of ZrCl4 (300 mg, 1.29 mmol) and salt 3 (790 mg,
2.88 mmol) in toluene was heated for 16 h in a boiling water
bath. The solution was separated from the precipitate by decanꢀ
tation and concentrated to dryness. The residue was washed
with hexane and dried under high vacuum. The product was
obtained as an orange powder in a yield of 740 mg (0.94 mmol,
73%). Found (%): C, 75.01; H, 5.10. C49H38Cl2Zr. Calculated
(%): C, 74.60; H, 4.85. 1H NMR (C6D6), δ 2.10 (s, 3 H, PhCH3);
6.70 (s, 2 H, H(2)); 6.85 (m, 4 H, H(4,7) or H(5,6)); 6.99—7.12
(m, 5 H, PhCH3); 7.04 (m, 12 H, mꢀH, pꢀH); 7.44 (m, 8 H,
oꢀH); 7.82 (m, 4 H, H(5,6) or H(4),H(7)). 13C{1H} NMR, δ:
21.36 (PhCH3); 116.38 (CH(2)); 119.30 (C(1),C(3) or C(3a),
C(7a)); 125.64 (pꢀCH in PhCH3); 124.58, 127.10, 127.39
(pꢀCH, CH(4—7)); 128.51 (mꢀCH in PhCH3); 128.56, 128.73
(oꢀCH, mꢀCH); 129.28 (oꢀCH in PhCH3); 133.92 (ipsoꢀC);
137.86 (ipsoꢀC в PhCH3).
Bond
d/Å
Parameter
Value
Zr—Cl(1)
Zr—Pl(1)*
Zr—Pl(2)*
Zr—C(2)
Zr—C(3)
Zr—C(1)
Zr—C(4)
Zr—C(9)
Zr—C(34)
2.4239(16) Bond
d/Å
2.211(2)
2.264(2)
2.500(3)
2.540(6)
2.550(6)
2.630(6)
2.637(5)
2.495(5)
Zr—C(33)
2.497(5)
2.513(6)
2.519(6)
2.532(6)
Zr—C(31)
Zr—C(32)
Zr—C(35)
Angle
Zr—Cl(2)
Cl(1)—Zr—Cl(2)
ω/deg
2.4219(15)
94.80(7)
* The parameters Pl(1) and Pl(2) are the mean planes of the
fiveꢀmembered cyclopentadienyl and indenyl rings, respectively.
dienyl indenyl zirconocenes. Both ligands are planar
within 0.072(3) Å. As in most of the known indenyl comꢀ
plexes of ZrIV, the Zr—C(2) distance (2.500(3) Å) is the
shortest Zr—Cind distance.5 The geometric parameters of 2
are, on the whole, similar to those found earlier in the related
pentamethylcyclopentadienyl indenyl zirconium comꢀ
plexes (Me5C5)(Ind)ZrCl2 (see Ref. 6) and (Me5C5)ꢀ
(2ꢀPhꢀInd)ZrCl2.7
Single crystals suitable for Xꢀray diffraction were grown by
crystallization from hexane.
5
5
(η ꢀ1,3ꢀDiphenylindenyl)(η ꢀpentamethylcyclopentadienyl)ꢀ
5
5
dichlorozirconium, (η ꢀ1,3ꢀC9H5Ph2)(η ꢀC5(CH3)5)ZrCl2 (2).
A mixture of Cp*ZrCl3 (640 mg, 1.92 mmol) and salt 3 (710 mg,
2.59 mmol) in toluene was heated for 16 h in a boiling water
bath. The solution was separated from the precipitate by decanꢀ
tation and concentrated to dryness. The residue was washed
with hexane and dried under high vacuum. The product was
obtained as an orange powder in a yield of 1.03 g (1.82 mmol,
95%). Found (%): C, 66.13; H, 5.40. C31H30Cl2Zr. Calculated
(%): C, 65.94; H, 5.35. 1H NMR (THFꢀd8), δ: 1.64 (s, 15 H,
C5Me5); 7.12 (s, 1 H, H(2)); 7.30 (m, 2 H, H(4),H(7) or
Experimental
All operations, including the preparation of samples for NMR
spectroscopy, were carried out under an inert atmosphere or in
sealed evacuated Schlenkꢀtype glassware. All solvents, including
deuterated solvents, were purified according to standard procedures,8
degassed, and recondensed under high vacuum (10–3 Torr)
directly into a reaction vessel or an NMR tube. Commercial
ZrCl4 (Fluka) was used without additional purification. Magnesium
3
H(5),H(6)); 7.34 (t, 2 H, pꢀH, JH,H = 7.4 Hz); 7.47 (t, 4 H,
3
mꢀH, JH,H = 7.6 Hz); 7.95 (m, 6 H, oꢀH, H(5),H(6) or
H(4),H(7)). 13C{1H} NMR, δ: 12.25 (C5Me5); 115.20 (CH(2));
117.46, 130.53 (C(1),C(3),C(3a),C(7a)); 125.03, 126.77, 128.07
(pꢀCH, C(4)H—C(7)H); 125.86 (C5Me5); 129.16, 130.65 (oꢀCH,
mꢀCH); 134.48 (ipsoꢀC).
1H NNMR (C6D6), δ: 1.53 (s, 15 H, C5Me5); 6.58 (s, 1 H,
H(2)); 7.13 (m, 4 H, pꢀH, H(4),H(7) or H(5),H(6)); 7.27 (t,
4 H, mꢀH, 3JH,H = 7.3 Hz); 7.85 (d, 4 H, oꢀH, 3JH,H = 7.6 Hz);
8.06 (m, 2 H, H(5),H(6) or H(4),H(7)). 13C{1H} NMR, δ: 12.16
(C5Me5); 113.83 (CH(2)); 116.82 (C(1),C(3) or C(3a),C(7a));
124.54, 126.84, 127.49 (pꢀCH, C(4)HꢀC(7)H); 125.24 (C5Me5);
128.63 (mꢀCH); 130.15 (oꢀCH, C(3a),C(7a) or C(1),C(3));
133.90 (ipsoꢀC).
amalgam,9 1,3ꢀdiphenylindene,10 and Cp ZrCl3 were synthesized
according to procedures described in the literature.
*
11
The 1H and 13C NMR spectra were recorded on a Bruker
Avanceꢀ400 spectrometer (400 and 100 MHz, respectively) at
27 °C using the chemical shifts of the signals of the correspondꢀ
ing deuterated solvents (7.15 and 128.0 ppm for C6D6 and 1.73
and 25.3 ppm for THFꢀd8, respectively) as the internal standard.
The elemental analysis was carried out on an automated Carloꢀ
Erba analyzer.
Single crystals suitable for Xꢀray diffraction were grown by
crystallization from hexane.
Lithium 1,3ꢀdiphenylindenide, (1,3ꢀIndPh2)Li (3). A 2.45 M
nꢀBuLi solution in hexane (7.2 mL) was added with vigorous
stirring and strong cooling to a solution of 1,3ꢀdiphenylindene
(4.7 g, 17.5 mmol) in diethyl ether (50 mL). The yellow crystals
that precipitated were separated by decantation, washed with
diethyl ether, and dried under high vacuum. The mother liquor
was concentrated, hexane was added, and the orange precipitate
was separated, washed with a mixture of hexane and diethyl
ether, and dried under high vacuum. The total yield was 3.94 g
(14.4 mmol, 82%). 1H NMR (THFꢀd8), δ: 6.53 and 7.75 (both br.m,
2 H, H(4)—H(7)); 6.63 (br.t, 2 H, pꢀH); 7.07 (br.t, 4 H, mꢀH);
7.17 (s, 1 H, H(2)); 7.60 (br.d, 4 H, oꢀH). 13C{1H} NMR, δ:
111.77, 119.55 (C(1,3,3a,7a)); 115.19, 118.12 (C(4)H—C(7)H);
119.36 (pꢀCH); 125.14 (oꢀCH); 128.52 (mꢀCH); 131.65 (C(2)H);
144.46 (ipsoꢀC).
Reduction of complexes 1 and 2 with activated manganese.
A solution of complex 1 or 2 (~50 mg) in THFꢀd8 (0.6 mL) was
stirred with Mg/Hg (30 mg, ~15 equiv.) at 25 °C for 2 days. The
darkꢀbrown solution was separated from the precipitate and
quantitatively transferred into an NMR tube. The main signals
in the 1H and 13C NMR spectra of the reaction mixtures are
assigned to diphenylindenide anion 3.
Xꢀray diffraction study of complexes 1 and 2. The Xꢀray
diffraction data sets were collected on automated EnrafꢀNonius
CAD 4 (for 1) and Bruker SMART APEX II (for 2) diffractoꢀ
meters (MoKα radiation, λ = 0.71073 Å, graphite monochroꢀ
mator). The structures of 1 and 2 were solved by direct methods
(SHELXꢀ86).12 All nonhydrogen atoms were refined anisotroꢀ
pically by the fullꢀmatrix leastꢀsquares method based on F2