Lightest Member Of The Basic Carboxylate Structural Pattern: (Al (Μ -O) (Μ-O Ccf) (Thf) ) ( (Me Si) Cal (O Ccf) ) ‚C H
Lightest Member Of The Basic Carboxylate Structural Pattern: (Al (Μ -O) (Μ-O Ccf) (Thf) ) ( (Me Si) Cal (O Ccf) ) ‚C H
Lightest Member Of The Basic Carboxylate Structural Pattern: (Al (Μ -O) (Μ-O Ccf) (Thf) ) ( (Me Si) Cal (O Ccf) ) ‚C H
Introduction Scheme 1
Basic chromium acetate1 plays an important role in the
history of coordination chemistry. Its µ3-oxo-trinuclear
pattern appears as a distinguished structural prototype of the
polynuclear complexes,2 being encountered in innumerable
systems of Cr,3 Mn,4 and Fe5 and also with the heavier metals
(Ru,6 Ir,7 W8). Various mixed valent species with Mn or Fe
are well-known examples for the special magnetic and optical
problems related with the localized versus the delocalized
* Author to whom correspondence should be addressed. E-mail: hroesky
@gwdg.de.
† Institut für Anorganische Chemie der Universität Göttingen.
‡ Permanent address: University of Bucharest, Faculty of Chemistry, character of itinerant electrons.9 The µ3-oxo-trinuclear pro-
Inorganic Chemistry Department, Dumbrava Rosie 23, Bucharest 70254, totype appears within a certain variety of ligands, but the
Romania. E-mail: [email protected].
§ Institute of Physical Chemistry. carboxylates seem to be the symbiotic companions of the
| Dedicated to Professor Gottfried Huttner on the occasion of his 65th
central oxygen, bridging the equatorial positions of the metal
birthday.
(1) Chang, S. C.; Jeffrey, G. A. Acta Crystallogr. Sect. B 1970, 26, 673- ions with the central µ3-O atom. The reaction of (Me3Si)3-
674. CAlMe2‚THF with one, two, or three equivalents of CF3-
(2) (a) Cannon, R. D.; White, R. P. Prog. Inorg. Chem. 1988, 36, 195-
298. (b) Anson, C. E.; Bourke, J. P.; Cannon, R. D.; Jayasooriya, U.
COOH yielded [(Me3Si)3CAlMe(O2CCF3)]2 (1), [(Me3Si)3-
A.; Molinier, M.; Powell, A. K. Inorg. Chem. 1997, 36, 1265-1266. CAl(O2CCF3)2]2 (2), and [Al3(µ3-O)(µ-O2CCF3)6(THF)3]-
(3) (a) Schenk, K. J.; Güdel, H. U. Inorg. Chem. 1982, 21, 2253-2256. [(Me3Si)3CAl(O2CCF3)3]‚C7H8 (3), respectively (Scheme 1).
(b) Anson, C. E.; Chai-Saard, N.; Bourke, J. P.; Cannon, R. D.;
Jayasooriya, U. A.; Powell, A. K. Inorg. Chem. 1993, 32, 1502-1507. The cation [Al3(µ3-O)(µ-O2CCF3)6(THF)3]+ of 3 is so far
(c) Bourke, J. P.; Karu, E.; Cannon, R. D. Inorg. Chem. 1996, 35, the lightest member of the oxo-centered trinuclear class of
1577-1581. (d) Cannon, R. D.; Jayasooriya, U. A.; Sowrey, F. E.;
Tilford, C.; Little, A.; Bourke, J. P.; Rogers, R. D.; Vincent, J. B.; complexes, although within the main group metal ions, a
Kearley, G. J. Inorg. Chem. 1998, 37, 5675-5676. (e) Lieberman, R. gallium analogue is known, [Ga3(µ3-O)(µ-O2CC6H5)6(4-
L.; Bino, A.; Mirsky, N.; Summers, D. A.; Thompson, R. C. Inorg. MePy)3]+.10 Up to now, an Al3O core was obtained only in
Chim. Acta 2000, 297, 1-5.
(4) (a) Baikie, A. R. E.; Hursthouse, M. B.; New, L.; Thornton, P.; White, asymmetrical patterns,11 involving aza-indole ligands and
R. G. J. Chem. Soc., Chem. Commun. 1980, 684-685. (b) Ribas, J.; aluminum centers with different coordination numbers. Com-
Albela, B.; Stoeckli-Evans, H.; Christou, G. Inorg. Chem. 1997, 36,
2352-2360. (c) Li, J.; Yang, S. M.; Zhang, F. X.; Tang, Z. X.; Ma, pound 3 is the first symmetrical example that confirms a
S. L.; Shi, Q. Z.; Wu, Q. J.; Huang, Z. X. Inorg. Chim. Acta 1999,
294, 109-113. (9) (a) Wrobleski, J. T.; Dziobkowski, C. T.; Brown, D. B. Inorg Chem.
(5) Lippard, S. J. Angew. Chem., Int. Ed. Engl. 1988, 27, 344-361. (b) 1981, 20, 684-686. (b) McCusker, J. K.; Jang, H. G.; Wang, S.;
Wu, G.; Zhang, Y.; Ribaud, L.; Coppens, P.; Wilson, C.; Iversen, B. Christou, G.; Hendrickson, D. N. Inorg. Chem. 1992, 31, 1874-1880.
B.; Larsen, F. K. Inorg. Chem. 1998, 37, 6078-6083. (c) Jayasooriya, (c) Wu, R. W.; Poyraz, M.; Sowrey, F. E.; Anson, C. E.; Wocadlo,
U. A.; Cannon, R. D.; Anson, C. E.; Arapkoske, S. K.; White, R. P.; S.; Powell, A. K.; Jayasooriya, U. A.; Cannon, R. D.; Nakamoto, T.;
Kearley, G. J. J. Chem. Soc., Chem. Commun. 1992, 379-381. (d) Katada, M.; Sano, H. Inorg. Chem. 1998, 37, 1913-1921. (d) Wilson,
Fu, D. G.; Wang, G. X.; Tang, W. X. Polyhedron 1993, 12, 2459- C.; Iversen, B. B.; Overgaard, J.; Larsen, F. K.; Wu, G.; Palii, S. P.;
2463. Timco, G. A.; Gerbeleu, N. V. J. Am. Chem. Soc. 2000, 122, 11370-
(6) (a) Abe, M.; Sasaki, Y.; Yamaguchi, T.; Ito, T. Bull. Chem. Soc. Jpn. 11379. (e) Wu, C. C.; Hunt, S. A.; Gantzel, P. K.; Gütlich P.;
1992, 65, 1585-1590. (b) Powell, G.; Richens, D. T.; Bino, A. Inorg. Hendrickson, D. N. Inorg. Chem. 1997, 36, 4717-4733.
Chim. Acta 1995, 232, 167-170. (10) Andras, M. T.; Duraj, S. A.; Hepp, A. F.; Fanwick, P. E.; Bodnar, M.
(7) Almog, O.; Bino, A.; Garfinkel-Shweky, D. Inorg. Chim. Acta 1993, M. J. Am. Chem. Soc. 1992, 114, 786-787.
213, 99-102. (11) (a) Gao, S.; Wu, Q.; Wu, G.; Wang, S. Organometallics 1998, 17,
(8) Ardon, M.; Cotton, F. A.; Dori, Z.; Fang, A.; Kapon, M.; Reisner, G. 4666-4674. (b) Liu, W.; Hassan, A.; Wang, S. Organometallics 1997,
M.; Shaia, M. J. Am. Chem. Soc. 1982, 104, 5394-5398. 16, 4257-4259.
1022 Inorganic Chemistry, Vol. 41, No. 4, 2002 10.1021/ic010880y CCC: $22.00 © 2002 American Chemical Society
Published on Web 01/23/2002
NOTE
long-standing unproved assumption that the basic aluminum Table 1. Crystal Data and Structure Refinement for 3
acetates, well-known as chemical reagents,12 possess a struc- empirical formula C47H59Al4F27O22Si3
tural variety analogous to the chromium one.13 The synthesis fw 1681.13
of 3 by using the organometallic precursor (Me3Si)3CAlMe2‚ temp (K)
cryst size (mm3)
200(2)
1.0 × 0.7 × 0.5
THF offered a valid option for generating basic carboxylates, cryst syst rhombohedral
as compared to the synthesis in water, where probably col- space group R3h
a ) b ) c (Å) 18.313(2)
loidal hydroxo species are precluding formation of crystal R ) β ) γ(deg) 53.472(17)
phases. V (Å3) 3679.3(7)
Z 2
Experimental Section Fcalcd (g mm-3) 1.517
General Data. All experiments were carried out using standard µ (mm-1) 0.246
Schlenk techniques under a dry nitrogen atmosphere because of F(000) 1708
2θ range (deg) 7-50
the sensitivity of the reactants and products toward air and moisture. index ranges -14 e h e 21, -21 e k e 21,
A Braun MB 150-GI box was used to store the compounds and to -12 e l e 18
prepare the samples for spectroscopic characterization. All solvents reflns collected 4633
were distilled from sodium/benzophenone and degassed prior to independent reflections 4341 (Rint ) 0.1241)
data/restraints/parameters 4341/599/368
use. (Me3Si)3CAlMe2‚THF was prepared as described in the
GOF F2 1.013
literature.14 Elemental analyses were performed at the Analytisches R,awR2b (I > 2σ(I)) 0.0712, 0.1918
Labor des Instituts für Anorganische Chemie der Universität R, wR2 (all data) 0.0889, 0.2112
Göttingen. NMR spectra were recorded on a Bruker Avance 200 largest diff peak and hole (e Å-3) 1.284 and -0.698
or Bruker Avance 500 spectrometer, and chemical shifts were a R ) ∑||Fo|| - |Fc||/∑|Fo|. b wR2 ) [∑w(Fo2 - Fc2)2]/[∑w(Fo2)2]1/2.
referenced to Me4Si and C6F6, respectively. FT-IR spectra were
measured on a Bio-Rad FTS-7 as CsI or KBr pellets in the range crystallized for one week at -20 °C. Compound 3 was obtained in
4000-400 cm-1. Mass spectra were obtained on Finnigan MAT 10% yield (0.18 g, 0.11 mmol) (decomposing at 135 °C). 1H NMR
8230 and Varian MAT CH 5 instruments by EI- and FAB-MS (200 MHz, THF-d8, ppm): δ 0.26 (s). 19F NMR (188 MHz, THF-
techniques. Decomposing points were measured in sealed glass d8, ppm): δ -77.4 (s, 1 F), -75.9 (s, 1 F), -75.8 (s, 1 F). 29Si
tubes on a Büchi 540 instrument. NMR (99 MHz, THF-d8, ppm): δ -3.0 (s). MS (FABpos): m/z
Synthesis of [(Me3Si)3CAlMe(O2CCF3)]2 (1). CF3COOH (0.335 991 (10%, [Mcation+]), 919 (100%, [Mcation+ - THF]). MS (FAB-
- -1
g, 2.94 mmol) was added to a solution of (Me3Si)3CAlMe2‚THF neg): m/z, 597 (100%, [Manion ]). IR (CsI, cm ): 2962, 1763, 1735,
(1.06 g, 2.94 mmol) in toluene (20 mL). The cloudy liquid was 1521, 1236, 1179, 1008, 860, 803, 735, 663, 566, 452, 410, 369.
stirred for 1 day. An insoluble residue was filtered off and Anal. Calcd for C47H59Al4F27O22Si3: C, 33.58; H, 3.54. Found: C,
recrystallized at -20 °C from THF. Small amounts of adherent 34.3; H, 3.8.
solvent were removed in vacuo. Compound 1 (0.42 g, 0.54 mmol, X-ray Structure Determination of 3. A suitable single crystal
37%) was obtained as a colorless solid (decomposing at 210 °C). for an X-ray structural analysis of 3 was obtained from a saturated
1H NMR (200 MHz, THF-d , ppm): δ -0.47 (s, 3 H, AlCH ),
8 3 toluene/THF solution (8:1) at -20 °C. Diffraction data were
0.23 (s, 27 H, SiCH3). 19F NMR (188 MHz, THF-d8, ppm): δ -74.7 collected on a Siemens-Stoe AED diffractometer (at -70 °C) with
(s). 29Si NMR (99 MHz, THF-d8, ppm): δ -4.1 (s). MS (EI): m/z graphite-monochromated Mo KR radiation (λ ) 0.710 73 Å). The
757 (30%, M - Me), 371 (100%, M/2 - Me). IR (KBr, cm-1): structure was solved by direct methods15 and refined against F2 on
2959, 1736, 1700, 1503, 1428, 1261, 1210, 1178, 1050, 851, 724, all data by full-matrix least squares with SHELXL-93.16 All non-
673. Anal. Calcd for C26H60Al2F6O4Si6: C, 40.39; H, 7.82. Found: hydrogen atoms were refined anisotropically and included at
C, 41.1; H, 7.8. geometrically calculated positions and refined using a riding model.
Synthesis of [(Me3Si)3CAl(O2CCF3)2]2 (2). CF3COOH (0.860 Other details of the data collection, structure solution, and the
g, 7.54 mmol) was added to a solution of (Me3Si)3CAlMe2‚THF refinement are listed in Table 1. The crystallographic data reveal a
(1.36 g, 3.77 mmol) in toluene (20 mL) and stirred for 1 day. All disorder on the CF3-groups.
solvents were removed in vacuo. The remaining solid was treated
with n-hexane (20 mL) and filtered. Crystallization in toluene at Results and Discussion
-20 °C afforded 2 (1.66 g, 1.71 mmol, 45%) as a colorless solid The stepwise formation of compounds 1-3 can be
(decomposing at 170 °C). 1H NMR (200 MHz, THF-d8, ppm): δ rationalized as follows: The first step is the exchange of a
0.23 (s). 19F NMR (188 MHz, THF-d8, ppm): δ -74.8 (s). 29Si methyl group at (Me3Si)3CAlMe2‚THF by CF3COO- fol-
NMR (99 MHz, THF-d8, ppm): δ -3.1 (s). MS (EI): m/z 953 lowed by replacement of the second one by a CF3COO-.
(100%, M - Me). IR (KBr, cm-1): 2960, 1762, 1749, 1417, 1265,
Inadvertently present water or water generated from con-
1217, 1192, 1162, 854, 836, 723, 676. Anal. Calcd for C28H54-
Al2F12O8Si6: C, 34.70; H, 5.62. Found: C, 35.0; H, 5.7.
densation of CF3COOH in this strongly acidic solution then
Synthesis of [Al3(µ3-O)(µ-O2CCF3)6(THF)3][(Me3Si)3CAl- accounts for the cleavage of the remaining Al-C bonds
(O2CCF3)3]‚C7H8 (3). CF3COOH (1.99 g, 16.5 mmol) was added under formation of the cation. The anion of 3 results from
to a solution of (Me3Si)3CAlMe2‚THF (2.00 g, 5.50 mmol) in addition of CF3COO- to 2 (Scheme 1).
toluene (20 mL) and stirred for 1 day. All volatile substances were According to the numerically computed vibrational spec-
pumped off. The residue was dissolved in toluene/THF (5:1) and trum,18 which identified intense A2′′ modes at 643 and 736
(12) Basic aluminum acetates: CASRN 142-03-0. (15) Sheldrick, G. M. Acta Crystallogr. Sect. A 1990, 46, 467.
(13) (a) Spacu, G.; Popper, E. Kolloid-Z. 1943, 103, 19-21. (b) Starke, (16) Sheldrick, G. M. SHELXL-93, Program for Crystal Structure Refine-
K. J. Inorg. Nucl. Chem. 1960, 13, 254-257. ment; University of Göttingen: Göttingen, Germany, 1993.
(14) Schnitter, C.; Roesky, H. W.; Albers, T.; Schmidt, H.-G.; Röpken, (17) Pandey, A.; Gupta, V. D.; Nöth, H. Eur. J. Inorg. Chem. 1999, 1291.
C.; Parisini, E.; Sheldrick, G. M. Chem.sEur. J. 1997, 3, 1783. (18) Koide, Y.; Barron, A. R. Organometallics 1995, 14, 4026.