Compound 6 is well soluble in toluene but sparingly soluble in n-hexane and was purified by crystallization from toluene at low temperature. Compound 6 is stable in the solid state for several months in inert gas atmosphere in the dark. 1H-NMR, mass spectrometry, and elemental analysis data are consistent with the formulation of 6. The mass spectrum (EI) shows the peak of highest intensity at 793 ((M+ - I), 100 %) and one peak at 905 ((M+ - Me), 3 %). The 1H-NMR (C6D6) reveals two resonances (
δ
1.51 and 6.42 ppm), assignable to resonances of tBu and C-H protons, respectively. The 27 Al-NMR (C6D6) spectrum exhibits only one sharp signal atδ
62.3 ppm, indicating coordination number four at the Al-atoms.42cResults and Discussion 22 Interestingly, in a manner analogous to the preparation of 3, the reaction of K(3,5-tBu2pz) with AlCl3 in a ratio of 3:1 in toluene gave the homoleptic compound [(
η
2 -3,5-tBu2pz)3Al] (7) in good yield, well soluble in hexane and thermally quite stable.Sometimes 7 will crystallize together with compound 3. Therefore a modified synthetic approach for 7 was elaborated by treatment of the compound [(
η
1,η
1-3,5-tBu2 pz)(µ-AlH2)]2 (8, vide infra) with 4 equivalents of H(3,5-tBu2pz).41 This method directly led to the pure product (7) in nearly quantitative yield at room temperature in toluene with elimination of hydrogen.The data of mass spectrum and elemental analysis are in agreement with the formulation of 7 (M+ (m/z) = 564, 100 %). The 1H-NMR shows only one set of resonances (
δ
1.35 ppm for the protons of the tBu group and 6.13 ppm for the CH proton), indicating a symmetric molecule. The 27Al-NMR signal is too broad to be observed. Compound 7 is the first example of a homoleptic compound with pyrazolato ligands and therefore it might be employed as a precursor in developing aluminum nitride films (AlN), although several transition metal complexes with this ligand have already been employed to prepare such as TiN films.21b2.1.4. Molecular structures of complexes 3 and 7
Single crystals suitable for Xray diffraction studies were obtained from nhexane at -26 °C. Figure 2 shows a perspective view of compound 3 along with the atom-labeling scheme. 3 crystallizes in the orthorhombic crystal system, space group Pbcn. The similar cell parameters of [(
η
1,η
1-3,5-tBu2pz)(µ
-AlCl2)]2 (3) and [(η
1,η
1-3,5-tBu2pz)(µ
-AlMe2)]2 (1) indicate structural similarities between these two compounds (Figures 1 and 2). Both compounds contain a six-membered ring with pyrazolato groups asResults and Discussion 23 bridging ligands. As in compound 1, the six-membered ring in compound 3 adopts a distorted conformation due to steric effects. The Al(1)-N(1) bond length (1.904(2) Å) is slightly shorter than that in compound 1 (Al(1)-N(1), 1.9638(13)) Å) due to the higher electron withdrawing properties of the chlorine atoms. In 3, the N(1A)-Al(1)-N(1) angle (104.86(12)°) is somewhat larger than that of compound 1 (N(1)-Al(1)-N(2), 99.77(6)°).
Figure 2. Perspective view of the complex [(
η
1,η
1-3,5-tBu2pz)(µ-AlCl2)]2 3, showing the numbering scheme and the thermal ellipsoids at the 50 % probability level. Selected bond lengths [Å] and angles [°]: Al(1)-N(1) 1.904(2), Al(2)-N(2) 1.903(2), Al(1)-Cl(1) 2.1181(9); Cl(1)-Al(1)-N(1) 114.36(6), Cl(1)-Al(1)-Cl(1A) 112.22(6), Cl(2A)-Al(2)-N(2A) 112.52(6), N(1)-Al(1)-N(1A) 104.86(12), N(2)-Al(2)-Cl(2A)-Al(2)-N(2A) 105.02(12).Compound 7 has a monomeric structure with three chelating pyrazolato ligands resulting in a formally six-coordinated aluminum atom. Both N-atoms of each pyrazolato ligand coordinate to the Al-atom in a
η
2-mode, constituting the first example of a aluminumη
2-pyrazolato complex.Results and Discussion 24 The Al-N distances (1.916(3) Å) in 7 are comparable with those found in the four coordinated [(
η
1,η
1-3,5-tBu2pz)(µ
-AlCl2)]2 (3, 1.904(2) Å) but are significantly shorter than those in 1 (Al(1)-N(1), 1.9638(13) Å).
Figure 3. Perspective view of the complex [(
η
2-3,5-tBu2pz)3Al] (7), showing the numbering scheme and the thermal ellipsoids at the 50 % probability level. Selected bond lengths [Å] and angles [°]: Al(1)-N(1) 1.916(3), Al(1)-N(2), 1.916(3); N(1)-Al(1)-N(2) 107.82(9), N(1)-Al(1)-N(1)-Al(1)-N(2) 43.02(10).2.2. Preparation of the aluminum hydride complex [(
η
1,η
1–3,5-tBu2pz)(µ
-AlH2)]2(8)43
Recently, aluminum hydrides with bulky substitutents attracted interest due to their suitability as starting materials for several other aluminum compounds either unavailable or difficult to prepare by other routes.44,45 In the case of group 13 element hydride compounds the pyrazabole [pz(
µ
-BH2)]240g is commercially available and the pyrazolato gallane [pz(µ
-GaH2)]240a,h was prepared nearly three decades ago, an aluminum hydride with an ancillary pyrazolato ligand was yet unknown. Most likely, the pyrazolato alane [pz(µ
-AlH2)]2 is rather poorly soluble in organic solvents.Results and Discussion 25 Accordingly, it was assumed that the use of bulky pyrazolato ligands might overcome this problem, furthermore, such compounds were expected as ideal precursors for the preparation of other aluminum complexes.
The aluminum dihydride dimer [(
η
1-3,5-tBu2pz)(µ
-AlH2)]2 (8) was successfully synthesized by the reaction of AlH3xNMe346 with H(3,5-tBu2pz)41 (Scheme 15) in nearly quantitative yield (91 %), after the reaction excess H3Al⋅NMe3 was removed in vacuo for at least 6 hours to afford the pure product. 8 could also be purified by recrystallization from toluene at -26 °C in fair yield (76 %). Compound 8 can be conveniently prepared in larger scales (over 50 mmol) in the laboratory and is thermally quite stable, but very sensitive to oxygen and water. No decomposition occurred when 8 was stored in a glove-box for at least two months at ambient temperature or refluxed for 4 days in toluene. However, a metallic aluminum film formed on the wall of the flask within several days if the excess of H3Al⋅NMe3 was not completely removed. Actually, 8 does not dissolve readily in toluene at ambient temperature and consequently warm toluene (ca. 50 °C) was often employed to increase its solubility before 8 was reacted with other reagents in solution at room temperature.Compound 8 was fully characterized by 1H-NMR, elemental analysis, and MS(EI). In the 1H-NMR spectrum it exhibits a broad Al-H signal at
δ
5.3 ppm (W1/2 = 144 Hz) and in addition, typical asymmetric and symmetric absorptions for υAl-H at 1869 and 1920 cm-1 in the IR spectrum indicate terminal Al-H bonds in the solid state.47 However, the27Al-NMR signal is too broad to be observed. High quality crystals of 8 were readily obtained by recrystallization from the crude product in toluene at ambient temperature;
X-ray studies revealed 8 as a dimer.
2 H(3,5-tBu2pz) + 2 H3Al⋅NMe3
Results and Discussion 26 [
η
1,η
1-3,5-tBu2pz(µ
-AlH2)]2 + 2 H2 + 2 NMe38 Scheme 15. Synthesis of compound 8
2.3. Aluminum group 16 compounds
2.3.1. Preparation of an aluminoxane hydride [(
η
1,η
1-tBu2pz)4(µ
3-O)2(µ
-AlH)4] (9) and the aluminum chalcogenide hydrides [{η
1,η
1-3,5-tBupz(µ-AlH)}2E] (E = S (10);Se (11); Te (12))48
Recently several aluminoxanes (tBuAlO)n (n = 6 - 9) as well as aluminum hydroxides or oxide hydroxides were prepared by the reactions of R3Al (R = tBu, Me, Mes, Ph) with water or anhydrous lithium hydroxide.31,49,50b In contrast, it has been shown that aluminum hydride compounds can be used as precursors for the synthesis of organoaluminum chalcogenides with the formula (RAlE)n (R = organic group; E = O, S, Se, Te) by reactions with species such as (Me2SiO)3,51 S(SiMe3)2,52 Se, or Te.53,54
Herein described are the syntheses of compounds [{
η
1,η
1-3,5-tBu2pz(µ-AlH)}2E]n (E= O (9) (n = 2), S (10), Se (11), Te (12) (n = 1)).
When a solution of compound 8 in dry dioxane was stirred at room temperature for several days complex 9 was formed in low yield (Scheme 16).
Results and Discussion 27