2500
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 11, November, 2005
Sizov et al.
C H AlCl Zr (1a•C H ). Calculated (%): Al, 4.35; Cl, 11.41;
had, along with signals of C H (δ 128.91, s) and residual 1a
2
6
29
2
2
1
6
6
6
6
Zr, 29.36. The H NMR spectra of the product are identical to
those published in the literature3 (300 MHz, δ, 20 °C), toluꢀ
eneꢀd : 7.13 (s, 6 H, C H ); 5.57 (s, 20 H, Cp); ≈–2 (br.s, 2 H,
(δ 103.85, s, Cp), signals at δ 195.43 (C(5)); 148.93 (C(7));
142.83 (C(6)); 142.29 (C(8)); 131.53 (C(9)); 127.99 (C(10),
C(12)); 126.93 (C(13)); 124.75 (C(11)); 123.22 (C(14));
112.9 (Cp). The 27Al NMR spectrum (130.32 MHz, 60 °C)
contained, along with the signal of residual 1a (δ 199.08, br.s),
8
6
6
Al—H—Zr); –8.34 (s, 1 H, Zr—H—Zr); THFꢀd : 7.31 (s, 6 H,
8
C H ); 6.04 (s, 20 H, Cp); ≈–2 (br.s, 2 H, Al—H—Zr); –7.96
6
6
1
1
27
(
s, 1H, Zr—H—Zr). H NMR (500 MHz, pyridineꢀd , 20 °C),
signals at δ 47.0 (s); 223.8 (br.s). H{ Al} NMR (500.13 MHz,
60 °C), δ: –3.55({223.8}, s). The assignment of the signals in the
spectra was made based on comparison with the intensities of
5
δ: 7.34 (s, 6 H, C H ); 6.15 (s, 20 H, Cp); ≈ –1.7 (br.s, 2 H,
6
6
1
3
1
Al—H—Zr); –7.77 (s, 1 H, Zr—H—Zr). C{ H} NMR
7
,8,10
(
(
75.5 MHz, pyridineꢀd , 20 °C), δ: 128.75 (s, C H ); 103.74
peaks published in the literature
and C—H correlations.
5
6
6
s, Cp). 27Al NMR (130.32 MHz, pyridineꢀd , 20 °C), δ:
[(µꢀChloro){di[bis(η ꢀcyclopentadienyl)]zirconium(III)}]di(µꢀ
hydrido)di(chloro)aluminum(III), [(Cp Zr) (µꢀCl)](µꢀH) AlCl
2
5
5
1
92.44 (br.s).
2
2
2
After isolation of the first portion of crystals, the mother
(4). Complex 1a•C H (0.30 g, 0.48 mmol), which was preꢀ
6 6
liquor was again concentrated to oneꢀhalf of the initial volume
and kept at ~20 °C for 16 h, after which an additional amount
pared as described above, was dissolved in warm 1,4ꢀdioxane
(40 mL). The solution was cooled to 20 °C, and gaseous HCl
(0.48 mmol) was added with vigorous stirring to the gas phase
over the solution through septum using a syringe for 30 min. The
reaction mixture was stirred at room temperature for 20 min and
at 50 °C for 1 h and then concentrated in vacuo to ∼ 8 mL.
Benzene (30 mL) was added to the resulting red oil and the
mixture was allowed to stand for 16 h. The needleꢀlike orange
crystals that precipitated (0.09 g, 30%) were separated, washed
with the cold solvent recondensed from the mother liquor, and
dried in vacuo. Found (%): Al, 4.21; Cl, 17.22; Zr, 30.01.
C H AlCl OZr (4•0.5C H O ). Calculated (%): Al, 4.34;
(
0.14 g, 14%) of crystals of 1a•C H was obtained.
6 6
5
[
(µ ꢀHydrido){di[bis](η ꢀcyclopentadienyl)]zircoꢀ
nium(III)}]di(µꢀhydrido)di(bromo)aluminum(III), [(Cp Zr) (µꢀ
2
2
H)](µꢀH) AlBr2 (1b) was prepared analogously to 1a. Darkꢀred
2
crystals were obtained in a yield of 0.39 g (45%) from a solution
1
6
of Cp ZrBr2 (0.92 g, 2.41 mmol), tolane (0.22 g, 1.21 mmol),
2
CoBr (17 mg), and LiAlH (2.41 mmol, a solution in 11 mL
2
4
of Et O) in a mixture of diethyl ether (40 mL) and benꢀ
2
zene (150 mL). Found (%): Al, 3.90; Br, 21.93; Zr, 25.99.
C H AlBr Zr (1b•C H ). Calculated (%): Al, 3.80; Br, 22.50;
2
6
29
2
2
6
6
22 26
3
2
4
8
2
1
1
Zr, 25.68. H NMR (300 MHz, THFꢀd , 20 °C), δ: 7.31 (s, 6 H,
Cl, 17.09; Zr, 29.32. H NMR (300 MHz, 20 °C, benzeneꢀd ),
8
6
C H ); 6.08 (s, 20 H, Cp); –1.58 (br.s, 2 H, Al—H—Zr); –7.71
δ: 5.25 (s, 20 H, Cp); 3.34 (s, 4 H, dioxane). 27Al NMR
6
6
2
7
(
s, 1 H, Zr—H—Zr). Al NMR (130.32 MHz, THFꢀd , 20 °C),
δ: 192.19 (br.s). H NMR (300 MHz, tolueneꢀd , 20 °C), δ:
(130.32 MHz, 20 °C, benzeneꢀd ), δ: 223.89 (br.s).
8
6
1
1
27
H{ Al} NMR (500 MHz, 20 °C, benzeneꢀd ), δ: –3.24{223.89}
8
6
1
7
.08 (s, 6 H, C H ); 5.52 (s, 20 H, Cp); –7.93 (s, 1 H,
(s). H NMR (300 MHz, 20 °C, THFꢀd ), δ: 5.69 (s, 20 H, Cp);
6
6
8
2
7
27
Zr—H—Zr). Al NMR (130.32 MHz, tolueneꢀd , 60 °C), δ:
1
3.56 (s, 4 H, dioxane). Al NMR (130.32 MHz, 20 °C, THFꢀd ),
δ: 223.27 (br.s). H{ Al} NMR (500 MHz, 20 °C, THFꢀd ), δ:
8
8
91.90 (br.s); 221.6 (s). 1H{ Al} NMR (500.13 MHz, toluꢀ
27
1
27
8
eneꢀd , 60 °C), δ: –1.40 ({191.90}, s, Al—H—Zr); –3.28
–3.41{223.27} (s). One crystal was chosen for Xꢀray diffraction
study.
8
(
{221.6}, s).
An additional amount of crystals of 1b•C H (0.13 g, 15%)
Xꢀray diffraction characterization of complex 4•0.5C H O .
6
6
4
8
2
was obtained by concentrating the mother liquor once again.
Orange needleꢀlike crystals of complex 4•0.5C H O
(C H AlCl OZr , M = 622.20, the dioxane molecule lies on
22 26 3 2
4 8 2
5
[
(µ ꢀHydrido){di[bis(η ꢀcyclopentadienyl)]zircoꢀ
nium(III)}]di(µꢀhydrido)di(iodo)aluminum(III), [(Cp Zr) (µꢀ
an inversion center) are monoclinic, at 120 K a = 16.473(5) Å,
2
2
3
H)](µꢀH) AlI2 (1c) was prepared (as 1c•C H ) according to a
b = 9.347(3) Å, c = 16.739(5) Å, β = 116.821(6)°, V = 2300(1) Å ,
2
6
6
3
1
–3
known procedure. H NMR (300 MHz, tolueneꢀd , 20 °C), δ:
space group P2 /c, Z = 4, D
= 1.797 g cm . Xꢀray diffracꢀ
8
1
calc
7
.08 (s, 6 H, C H ); 5.53 (s, 20 H, Cp); –7.93 (s, 1 H,
tion data (17343 reflections) were collected on a Bruker
SMART CCD diffractometer at 120 K (λMoꢀKα radiation,
6
1
6
13
Zr—H—Zr). C{ H} NMR (75.5 MHz, tolueneꢀd , 20 °C), δ:
8
1
03.74 (s, Cp); C H6 overlaps with the signal of the solvent.
2θmax
= 58.00°) from a single crystal of dimensions
6
2
7
Al NMR (130.32 MHz, tolueneꢀd , 60 °C), δ: 221.2 (s);
0.2×0.2×0.5 mm sealed in a capillary. The Xꢀray data were
processed using the SMART and SAINTPlus programs. Afꢀ
ter merging of equivalent reflections, the data set consisted of
8
1
7
18
2
14.6 (s); 200.3 (s); 185.7 (s); 181.1 (s); 167.5 (br.s).
1
27
H{ Al} NMR (500.13 MHz, tolueneꢀd , 60 °C), δ: –3.57
8
(
–
{221.2, 214.6}, s); –3.48({200.3}, s); –3.71 ({185.7, 181.1}, s);
0.94({167.5}, s, Al—H—Zr).
5867 independent reflections (R = 0.1047). An absorption
int
–
1
correction (µ = 1.305 mm ) was applied using the SADABS
1
9
The reaction of complex 1a with tolane was studied in a
program (Tmax and Tmin are 0.695 and 0.147, respectively).
The structure was solved by direct methods. All nonhydrogen
atoms were located from difference electron density maps and
sealed NMR tube. The spectra of a mixture of tolane (10.7 mg,
.06 mmol) and complex 1a•C H6 (37.3 mg, 0.06 mmol) in
0
6
2
THFꢀd8 (0.6 mL) were recorded before and after heating
to 65 °C. The H NMR spectrum measured before heating
(
tra of 1a•C H (δ): 7.31 (s, 6 H, C H ); 6.04 (s, 20 H, Cp);
∼
tolane (δ): 7.50 (m, 4 H); 7.35 (m, 6 H). After heating, the
1
refined anisotropically by the leastꢀsquares method against F hkl.
1
The hydride hydrogen atoms were located from difference maps
and refined isotropically. The H atoms in the Cp groups were
placed in geometrically calculated positions and refined using a
riding model with U(H) = 1.2U(C), where U(C) are the equivaꢀ
lent displacement parameters of their parent carbon atoms. The
final reliability factors were R1 = 0.0567 (based on Fhkl for
300 MHz, 20 °C) corresponded to a superposition of the specꢀ
6
6
6
6
–2 (br.s, 2 H, Al—H—Zr); –7.96 (s, 1 H, Zr—H—Zr) and free
H NMR spectrum (300 MHz, 20 °C) contained, along with
2
signals of C H and residual 1a, signals at δ 6.97 (t, 4 H, C(10),
2983 reflections with I > 2σ(I) ), wR = 0.1258 (based on F
6
6
2
hkl
J = 7.8 Hz); 6.65 (m, 16 H, C(9) and C(11)—C(14)); 6.33 (s,
1
for a total of 5867 reflections), GOOF = 0.839, 270 parameters
were refined.
0 H, Cp). The 13C{ H} NMR spectrum (75.5 MHz, 20 °C)
1