The azide-nitrilimine analogy in aluminum chemistry

Article abstract of DOI:10.1002/(SICI)1521-3773(19980420)37:7<989::AID-ANIE989>3.0.CO;2-1

Tetracoordinate aluminum derivatives featuring an AINNCR fragment are stable and possess a rich structural diversity, as exemplified by the nitrilimines 1 and 2, similar to that observed for the related azides. Compound 1 is the first structurally characterized six-membered AIN heterocycle in which the nitrogen and aluminum centers exhibit different coordination numbers. R=P(NiPr₂)₂; R'=iBu; E=N, CR.

Full text of DOI:10.1002/(SICI)1521-3773(19980420)37:7<989::AID-ANIE989>3.0.CO;2-1

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[14] Crystals were grown by slow diffusion of n-pentane into a solution of 4
in 1% C5H5N/CHCl3, over two weeks. Crystal structure analysis for 4 ´
indicating strong porphyrin ± porphyrin conjugation. Compar-
ing 13, 15 and 16 shows that the thiophene unit leads to more
conjugation than phenylene, but less than anthracene. It is
remarkable that the 9,10-diethynylanthracene bridge allows
even more electronic communication than the simple buta-
diyne link in 14. This implies that longer oligomers of type 2/3
should have strong third-order NLO behavior.
Å
2C5H5N: Mr ˆ 1667.66, triclinic, space group P1, a ˆ 11.052(2), b ˆ
13.110(2), c ˆ 16.970(4) Š, a ˆ 81.88(2), b ˆ 89.68(2), g ˆ 77.20(2)8,
1
Vˆ 2372.9(8) Š3, Z ˆ 1, T ˆ 293; 1calc ˆ 1.167 g cm 3; m ˆ 0.987 mm
,
crystal dimensions 0.25 Â 0.35 Â 0.45 mm; diffractometer: Enraf-Non-
ius MACH3; radiation CuKa (l ˆ 1.54184 Š); scan mode: w/2q; range:
3.5 < q < 74.6; measured reflections: 10156; independent reflections:
9712 (Rint ˆ 0.0186); corrections applied: Lorentz polarization and
experimental absorption correction (psi-scans, A. C. T. North, D. C.
Phillips, F. S. Mathews, Acta Crystallogr. A 1968, 24, 351 ± 359) Tmin
/
Experimental Section
Tmax 0.7302/0.7839; R values (I > 2sI): R1 ˆ 0.0847, wR2 ˆ 0.2492, all
data: R1 ˆ 0.1344, wR2 ˆ 0.2784. Structure solution with direct
methods (SHELXS-86, G. Sheldrick, 1990). Structure refinement
(SHELXL-93, G. Sheldrick, 1993): Full-matrix least squares methods
against F 2; 548 parameters, 28 constraints, max/min residual electron
density 0.662/ 0.825 eŠ 3. All non-hydrogen atoms were refined
anisotropically and hydrogen atoms were placed in calculated positions.
Crystallographic data (excluding structure factors) for the structure
reported in this paper have been deposited with the Cambridge
Crystallographic Data Center as supplementary publication no.
CCDC-100671. Copies of the data can be obtained free of charge
on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK
(fax: (‡44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
13: A solution of 12[9] (54 mg, 50 mmol) in THF (8 mL) and pyridine (80 mL)
was treated with dimethylaminotrimethyltin (41 mL, 250 mmol) at 508C for
2 h, then evaporated. To the resulting waxy residue was added THF (8 mL),
8[11] (11 mg, 25 mmol), tris(dibenzylideneacetone)dipalladium(0) (2.7 mg,
3 mmol), and triphenylphosphane (3.1 mg, 12 mmol) under argon. The
mixture was stirred at 508C for 24 h. Purification by chromatography on
silica (eluting with 50/2/1 petroleum ether (60 ± 808C)/ethyl acetate/
pyridine) and recrystallization from CH2Cl2/methanol yielded 13 as a
brown solid (27 mg, 46%).
Received: September 5, 1997
Revised version: December 15, 1997 [Z10894IE]
German version: Angew. Chem. 1998, 110, 1033 ± 1037
[15] Crystal structures of other 5,15-dialkynyl porphyrins have been
reported: S. M. LeCours, S. G. DiMagno, M. J. Therien, J. Am. Chem.
Soc. 1996, 118, 11854 ± 11864; S.-P. J. Huuskonen, G. S. Wilson, H. L.
Anderson, Acta Crystallogr., in press.
[16] D. P. Arnold, D. A. James, J. Org. Chem. 1997, 62, 3460 ± 3469; P. J.
Angiolillo, V. S.-Y. Lin, J. M. Vanderkooi, M. J. Therien, J. Am. Chem.
Soc. 1995, 117, 12514 ± 12527; V. S.-Y. Lin, M. J. Therien, Chem. Eur. J.
1995, 1, 645 ± 651; V. S.-Y. Lin, S. G. DiMagno, M. J. Therien, Science
1994, 264, 1105 ± 1111; H. L. Anderson, Inorg. Chem. 1994, 33, 972 ±
981; D. P. Arnold, D. A. James, C. H. L. Kennard, G. Smith, J. Chem.
Soc. Chem. Commun. 1994, 2131 ± 2132; D. P. Arnold, L. J. Nitschinsk,
Tetrahedron Lett. 1993, 34, 693 ± 696.
Keywords: alkynes ´ anthracene ´ conjugation ´ nonlinear
optics ´ porphyrinoids
[1] H. L. Anderson, S. J. Martin, D. D. C. Bradley, Angew. Chem. 1994,
106, 711 ± 713; Angew. Chem. Int. Ed. Engl. 1994, 33, 655 ± 657; Adv.
Mater. Opt. Electron. 1994, 4, 277 ± 283; D. Beljonne, G. E. OꢁKeefe,
Â
P. J. Hamer, R. H. Friend, H. L. Anderson, J. L. Bredas, J. Chem. Phys.
1997, 106, 9439 ± 9460. Second-order NLO materials with this type of
structure have also been developed: S. M. LeCours, H.-W. Guan, S. G.
DiMagno, C. H. Wang, M. J. Therien, J. Am. Chem. Soc. 1996, 118,
1497 ± 1503; S. Priyadarshy, M. J. Therien, D. N. Beratan, ibid. 1996,
118, 1504 ± 1510.
[2] R. O. Garay, H. Naarmann, K. Müllen, Macromolecules 1994, 27,
1922 ± 1927; U. Scherf, K. Müllen, Synthesis 1992, 23-38.
[3] T. M. Swager, C. J. Gil, M. S. Wrighton, J. Phys. Chem. 1995, 99, 4886 ±
4893; D. Ofer, T. M. Swager, M. S. Wrighton, Chem. Mater. 1995, 7,
418 ± 425; M. S. Khan, A. K. Kakkar, N. J. Long, J. Lewis, P. Raithby, P.
Nguyen, T. B. Marder, F. Wittmann, R. H. Friend, J. Mater. Chem.
1994, 4, 1227 ± 1232; K. Sonogashira, K. Asami, N. Takeuchi, J. Mat.
Sci. Lett. 1985, 4, 737 ± 740; K. Sanechika, T. Yamamoto, A.
Yamamoto, Bull. Chem. Soc. Jpn. 1984, 57, 752 ± 755.
The Azide-Nitrilimine Analogy in Aluminum
Chemistry**
Norbert Emig, François P. Gabbaï, Harald
Â
Â
Krautscheid, Regis Reau, and Guy Bertrand*
[4] J.-M. Cense, R.-M. Le Quan, Tetrahedron Lett. 1979, 3725 ± 3728; S.
Nakajima, A. Osuka, ibid. 1995, 36, 8457 ± 8460.
[5] M. Sirish, R. Kache, B. G. Maiya, J. Photochem. Photobiol. A 1996, 93,
129 ± 136.
[6] F. Effenberger, H. Schlosser, P. Bäuerle, S. Maier, H. Port, H. C. Wolf,
Angew. Chem. 1988, 100, 274 ± 277; Angew. Chem. Int. Ed. Engl. 1988,
27, 281 ± 284.
Covalent azides of type A are well-known 1,3-dipoles that
have found widespread application in organic synthesis,[1] and
that are also of increasing importance in inorganic chem-
istry.[2] Aluminum azides possess a rich structural diversity
(derivatives C ± G[3]) and constitute valuable single-source
[7] F. Würthner, M. S. Vollmer, F. Effenberger, P. Emele, D. U. Meyer, H.
Port, H. C. Wolf, J. Am. Chem. Soc. 1995, 117, 8090 ± 8099; S.
Kawabata, I. Yamazaki, Y. Nishimura, Bull. Chem. Soc. Jpn. 1997,
70, 1125 ± 1133.
[8] T. Marx, E. Breitmaier, Liebigs Ann. Chem. 1994, 857 ± 858.
[9] The synthesis of 5, 12, and 14 will be detailed elsewhere.
[10] G. S. Wilson, H. L. Anderson, Synlett 1996, 1039 ± 1040; H. L.
Anderson, Tetrahedron Lett. 1992, 33, 1101 ± 1104.
Â
[*] Dr. G. Bertrand, Dr. N. Emig, Dr. R. Reau
Laboratoire de Chimie de Coordination du CNRS
205, route de Narbonne, 31077 Toulouse Cedex (France)
Â
Fax : (‡ 33)561553003
E-mail: gbertran@lcctoul.lcc-toulouse.fr
Dr. F. P. Gabbaï
Anorganisch-chemisches Institut
der Technischen Universität München
Lichtenbergstrasse 4, D-85747 Garching (Germany)
Fax : (‡ 49)89-289-13125
[11] B. F. Duerr, Y.-S. Chung, A. W. Czarnik, J. Org. Chem. 1988, 53, 2120 ±
2122.
„
[12] The oscillator strength f is defined as: f ˆ (4.319  10 9n 1) ednÄ,
where n is the refractive index (1.42 for CH2Cl2), e is the extinction
coefficient (m 1 cm 1) and nÄ is the frequency in wavenumbers (cm 1).
[13] Fluorescence quantum yields were measured relative to 9,10-bi-
s(phenylethynyl)anthracene (Ff ˆ 0.58); S. Nakatsuji, K. Matsuda, Y.
Uesugi, K. Nakashima, S. Akiyama, W. Fabian, J. Chem. Soc. Perkin
Trans. 1 1992, 755 ± 758.
Dr. H. Krautscheid
Institut für Anorganische Chemie der Universität
Engesserstrasse, Geb. 30.45, D-76138 Karlsruhe (Germany)
Fax : (‡ 49)721-661-921
[**] We thank the CNRS for financial support of this work, and the
Gottlieb Daimler- and Karl Benz-Foundation for a grant to N. E.
Angew. Chem. Int. Ed. 1998, 37, No. 7
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Scheme 1. Reactions of the lithium salt 1 with various aluminum chlorides.
precursors to AlN semiconducting phases.[4] For many years,
the development of the chemistry of the isolobal nitrilimines
of type B was hampered because of their potential instability
and the lack of suitable preparative methods. In recent years,
efficient routes have been established for preparing stable
nitrilimines[5] and, just as for the azides, the Na ± Nb bond can
be cleaved.[6] Here we report the synthesis of various
aluminum ± nitrogen derivatives featuring the nitrilimine
skeleton.
Figure 1. Molecular structure of 2b in the solid state. Hydrogen atoms
have been omitted for clarity. Selected bond lengths [Š] and angles [8]: P1 ±
C25 1.804(7), C25 ± N2 1.144(7), N2 ± N1 1.287(6), N1 ± Al1 1.918(5), N1 ±
Al2 1.893(5); P1-C25-N2 163.1(6), C25-N2-N1 177.9(6), N2-N1-Al1
114.5(4), N2-N1-Al2 119.2(4), Al1-N1-Al2 123.6(3), N1-Al1-N9 98.2(2).
The lithium salt of the [bis(diisopropylamino)phosphanyl]-
diazomethane 1[7] was allowed to react in THF, at 788C, with
one equivalent of ClAlEt2 and ClAl(iBu)2. After workup at
room temperature, compound 2a and 2b were isolated in 85
and 90% yield,[8] respectively (Scheme 1). The IR absorption
of 2a also reveals a six-membered Al ± N core). The central
six-membered (AlNa)3 heterocycle features a twisted con-
formation, in contrast to the planar geometry postulated from
IR and Raman data for the analogous azide derivative C.[3a]
The mean endocyclic ring angles at the Na (119.68) and Al
(109.68) atoms reflect the sp2 and sp3 hybridization, respec-
tively. The Al ± Na bond lengths (1.89 ± 1.93 Š) are much
longer than those observed for the only known aromatic
alumazene H (1.78 Š),[11] which contains three-coordinate Al
and N centers, but are comparable to those of tris(amino-
alanes) I (1.95 Š),[12] which contain four-coordinate Al and N
centers. The N-N-C fragments are almost linear (177.5 ±
179.78), as are the P-C-N angles (163.1 ± 169.18), reflecting
the sp hybridization of the C and Nb atoms. The Na ± Nb bond
1
at 2140 cm , the 14N chemical shift of the Nb center (2a: 203
(n1/2 ˆ 147 Hz); 2b: 203 (n1/2 ˆ 118 Hz)), and the observation
of doublet for the PC carbon atom (2a: 62.89 (JP,C ˆ 74.3 Hz);
2b:63.21 (JP,C ˆ 62.5 Hz)) in the 13C NMR spectrum were
consistent with nitrilimine structures 3a, b. However, deriv-
atives 2a, b are inert toward the Lawessonꢁs reagent, one of
the most effective 1,3-dipolarophiles.[9] Single crystals of 2b
suitable for an X-ray analysis[10] were grown from a solution in
pentane at 308C (Figure 1). Compound 2b is a trimer of
nitrilimine 3b, and is the first structurally characterized six-
membered Al ± N heterocycle in which the nitrogen and
aluminum atoms possess different coordination numbers[11]
(an X-ray diffraction study performed of poor quality crystals
990
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31P (48.51) and 13C (61.17 (d, JP,C ˆ 83.5 Hz)) NMR signals for
the P-C-N-N skeleton are comparable to those observed for
compounds 2a, b, but the IR absorption is shifted to lower
1
frequency (nÄ ˆ 2076 cm 1; DnÄ ˆ 64 cm /2a, b). The simplicity
of the NMR spectra for the diamidoamine part is in agree-
ment with a monomeric structure.[15] Interestingly, in contrast
to derivatives 2, compound 6 reacted with the Lawessonꢁs
reagent,[9] affording the expected [3‡2] adduct 6 as an orange
oil in 63% yield.
The only example of four-coordinate ªmonomericº alumi-
num azide features intermolecular hydrogen bonding involv-
ing the Na and Ng atoms in the solid state.[3d] In contrast, the
azide 8,[8] which is analogous to nitrilimine 6, prepared in 85%
yield by treatment of the aluminum chloride 5 with NaN3, is
monomeric as proved by a single-crystal X-ray diffraction
study[10] (Figure 3). These results clearly show that nitrilimines
of type B can indeed exhibit a comparable coordination
behavior to that of covalent azides A.
lengths (1.26 ± 1.29 Š) are half way between those for a double
and a single N ± N bond, and the Nb ± C bond lengths (1.14 ±
1.16 Š) are typical for a C ± N triple bond. Taken together,
these data support a heteropropargylic canonical structure for
the C-N-N fragment, in contrast to most of the known
nitrilimines, which feature a cumulenic structure.[13]
The same reaction was carried out with the more sterically
hindered ClAl(tBu)2 in the hope of stabilizing a monomeric
nitrilimine. After workup at below 308C, highly air- and
moisture-sensitive crystals of 4 (Scheme 1) suitable for an X-
ray crystallographic study were obtained from the pentane
solution at 308C (Scheme 1; Figure 2).[10] Compound 4 is a
Figure 3. Molecular structure of 8 in the solid state. Hydrogen atoms have
been omitted for clarity. Selected bond lengths [Š] and angles [8] Al1 ± N1
1.805(4), Al1 ± N2 1.807(4), Al1 ± N3 1.970(4), Al1 ± N4 1.837(5), N4 ± N5
1.212(6), N5 ± N6 1.137(6); Al1-N4-N5 129.9(4), N4-N5-N6 176.6(5).
Figure 2. Molecular structure of the anion of 4 in the solid state. Hydrogen
atoms have been omitted for clarity. Selected bond lengths [Š] and angles
[8]: P1 ± C1 1.800(3), C1 ± N1 1.161(3), N1 ± N2 1.293(3), N2 ± Al1 1.954(3),
N2 ± Al2 1.958(3); P1-C1-N1 168.9(3), C1-N1-N2 178.9(3), N1-N2-Al1
107.8(2), N1-N2-Al2 114.5(2), Al1-N2-Al2 137.7(1).
Experimental Section
nitrilimine analogue of the azido complex D,[3b] featuring a
1,1-m-Na bridging mode. In both cases, the Al2N2E (E ˆ C or
N) fragment is planar (maximum deviation: 4: 0.006 Š; C:
0.01 Š), indicating an sp2 hybridization for the bridging Na
nitrogen, while the Nb atom is sp-hybridized (4: C-N-N:
178.98; C: N-N-N: 1788). The Al ± N distances lie in the same
range (4: 1.96 and 1.95 Š; C: 2.03 Š], the N ± N bond length
(1.29 Š) lies between the values for a double and a single
bond, and the C ± N bond length (1.16 Š) is typical for a C ± N
triple bond. The P-C-N fragment is almost linear (168.98).
Again these data as a whole support a heteropropargylic
canonical structure for the C-N-N fragment. Compound 4 is
one of the very rare examples of a lithium salt featuring an
Al ± Cl bond;[14] at temperatures above 208C, it decomposes
rapidly leading to a complicated mixture of products.
In a typical experiment a solution of Et2AlCl (1m, 1.9 mL) in hexane was
added dropwise at 788C to a solution (10 mL) of 1 (prepared by addition
at 788C of a solution of BuLi (1.9 mmol) in hexane to the bis(diisopro-
pylamino)phosphanyldiazomethane (0.52 g, 1.9 mmol)) in THF. The sol-
ution was allowed to warm to room temperature, stirred for 1 h, and the
solvent was removed under vacuum. The residue was treated with pentane
and filtered (10 mL). Compound 2a was obtained from a pentane solution
at 308C as colorless crystals (0.64 g).
Received: October 17, 1997 [Z11045IE]
German version: Angew. Chem. 1998, 110, 1037 ± 1040
Keywords: aluminum ´ azides ´ diazo compounds ´ hetero-
cycles ´ lithium ´ nitrilimines
[1] Reviews: a) R. Huisgen, Angew. Chem. 1963, 75, 604; Angew. Chem.
Int. Ed. Engl. 1963, 2, 565; ibid. 1963, 75, 741 and 1963, 2, 633; b) P.
Caramella, P. Grünanger in 1,3-Dipolar Cycloaddition Chemistry
(Ed.: A. Padwa), Wiley, New York, 1984, p. 559.
[2] a) I. C. Tornieporth-Oetting, T. M. Klapötke, Angew. Chem. 1995, 107,
559; Angew. Chem. Int. Ed. Engl. 1995, 34, 511; b) T. M. Klapötke,
Chem. Ber. 1997, 130, 443; representative recent contributions: c) H.
Hennig, K. Hofbauer, K. Handke, R. Stich, Angew. Chem. 1997, 109,
We have recently shown that the tridentate diamidoamine
ligand [(Me3SiNCH2CH2)2NR]2 allows the preparation of a
variety of monomeric aluminum(iii) derivatives.[15] Therefore,
the lithium salt of 1 was allowed to react with the aluminum
chloride 5. After workup at room temperature, nitrilimine 6[8]
was isolated as an orange oil in 91% yield (Scheme 1). The
Angew. Chem. Int. Ed. 1998, 37, No. 7
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373; Angew. Chem. Int. Ed. Engl. 1997, 36, 408; d) G. De Munno, T.
Poerio, G. Viau, M. Julve, F. Lloret, ibid. 1997, 109, 1531 and 1997, 36,
1459; e) C. J. Carmalt, A. H. Cowley, R. D. Culp, R. A. Jones, Y.-M.
Sun, B. Fitts, S. Whaley, H. W. Roesky, Inorg. Chem. 1997, 36, 3108.
[3] a) J. Müller, K. Dehnicke, J. Organomet. Chem. 1968, 12, 37; b) J. L.
Atwood, W. R. Newberry, ibid. 1974, 65, 145; c) W. Uhl, R. Gerding, S.
Pohl, W. Saak, Chem. Ber. 1995, 128, 81; d) R. A. Fischer, A. Miehr, H.
Sussek, H. Pritzkow, E. Herdtweck, J. Müller, O. Ambacher, T.
Metzger, Chem. Commun. 1996, 2685.
[4] a) D. C. Boyd, R. T. Haasch, D. R. Mantell, R. K. Schulze, J. F. Evans,
W. L. Gladfelter, Chem. Mater. 1989, 1, 119; see also: b) A. Miehr,
M. R. Mattner, R. A. Fischer, Organometallics 1996, 15, 2053; c) A.
Miehr, O. Ambacher, T. Metzger, E. Born, R. A. Fischer, Chem. Vap.
Deposition 1996, 2, 51; d) R. A. Fischer, A. Miehr, E. Herdtweck,
M. R. Mattner, O. Ambacher, T. Metzger, E. Born, S. Weinkauf, C. R.
Pulham, S. Parsons, Chem. Eur. J. 1996, 2, 101; e) C. J. Carmalt, A. H.
Cowley, R. D. Culp, R. A. Jones, Chem. Commun. 1996, 1453.
[5] G. Bertrand, C. Wentrup, Angew. Chem. 1994, 106, 549; Angew. Chem.
Int. Ed. Engl. 1994, 33, 527.
Direct Observation of Radical Intermediates
While Investigating the Redox Behavior of
Thiamin Coenzyme Models**
Ikuo Nakanishi, Shinobu Itoh, Tomoyoshi Suenobu,
and Shunichi Fukuzumi*
Thiamin diphosphate (ThDP) is the coenzyme for a number
of important biochemical reactions, including the decarboxyl-
ation of pyruvic acid to acetaldehyde. The conjugate base of 2-
hydroxyethyl-ThDP, which is an acyl carbanion equivalent
and called an ªactive aldehydeº, plays a key role in the
catalysis of ThDP-dependent enzymes.[1] The active aldehyde
is able to reduce various physiological electron acceptors, for
example the lipoamide in the pyruvate dehydrogenase multi-
enzyme complex,[2] the flavin adenine dinucleotide (FAD) in
pyruvate oxidase,[3] and the Fe4S4 cluster in pyruvate-ferre-
doxin oxidoreductase.[4] Simple thiazolium ions have been
studied extensively as models of the thiamin coenzyme, and
valuable information about the elementary step of ThDP-
dependent enzymatic reactions was provided.[5±10] The active
aldehyde, however, readily undergoes acyloin-type condensa-
tion with a second pyruvate or aldehyde molecule in the
absence of oxidizing agents.[1, 11] Such instability of the active
aldehydes has precluded the direct determination of the most
fundamental properties of the intermediates, such as oxida-
tion potentials.[12] Therefore, no direct observation of the
radical intermediates derived from thiamin coenzyme models
has been described so far. Here we report the direct
observation of radical intermediates of active aldehydes 2
with low-temperature cyclic voltammetry and EPR spectros-
copy. Active aldehydes 2 are derived from 3-benzylthiazo-
lium salts 1 and simple aldehydes such as acetaldehyde and
benzaldehyde in the presence of 1,8-diazabicylco[5.4.0]undec-
7-ene (DBU).
[6] M. Granier, A. Bacereido, Y. Dartiguenave, M. Dartiguenave, M. J.
Menu, G. Bertrand, J. Am. Chem. Soc. 1990, 112, 6277.
[7] G. Sicard, A. Baceiredo, G. Bertrand, J. Am. Chem. Soc. 1988, 110,
2663.
[8] Selected spectroscopic data: 2a: M.p. 988C; 31P NMR (C6D6): d ˆ
43.2(s); 2b: M.p. 1428C; 31P NMR (C6D6): d ˆ 44.4 (s); 6: 1H NMR
(C6D6): d ˆ 0.37 (s; SiMe3), 1.16 (d, J ˆ 6.7 Hz; CHCH3), 1.29 (d, J ˆ
6.7 Hz; CHCH3), 1.87 (dt, J ˆ 11.5, 5.6 Hz; CH2), 1.94 (s; NCH3), 2.20
(dt, J ˆ 11.5, 5.8 Hz; CH2), 2.79 (dd, J ˆ 5.6, 5.8 Hz; 2CH2), 3.46
(septd, J ˆ 6.7, 6.7 Hz; CHCH3), 3.52 (septd, J ˆ 6.7, 6.7 Hz; CHCH3);
7: 31P NMR (C6D6): d ˆ 49.1 (d, J ˆ 4.3 Hz), 104.7 (d, J ˆ 4.3 Hz);
13C{1H} NMR (C6D6): d ˆ 134.5 (dd, J ˆ 59.4, 13.4 Hz; PCSP); IR
(pentane): nÄ ˆ 1594 cm 1; 8: 1H NMR (C6D6): d ˆ 0.48 (s; SiCH3), 1.96
(s; NCH3), 1.99 (dt, J ˆ 11.7, 5.8 Hz; CH2), 2.34 (dt, J ˆ 11.7, 5.7 Hz;
CH2), 2.91 (dd, J ˆ 5.7, 5.8 Hz; 2 CH2); 27Al NMR (C6D6): d ˆ ‡118
(n1/2 ˆ 3800 Hz); 14N NMR (C6D6): d ˆ 138.9 (n1/2 ˆ 70 Hz), 202.9
1
(n1/2 ˆ 15 Hz), 224.5 (n1/2 ˆ 25 Hz); IR (THF): nÄ ˆ 2125 cm
.
[9] N. Dubau-Assibat, A. Baceiredo, G. Bertrand, J. Org. Chem. 1995, 60,
3904.
[10] Crystal data: 2b: C63H138Al3N12P3, orthorhombic, P212121, a ˆ
13.701(7), b ˆ 14.354(7), c ˆ 41.008(15) Š, Vˆ 8065(6) Š3, Z ˆ 4, with
665 parameters refined on 11282 reflections with F > 2s(Fo)], R1 ˆ
0.063 and wR2 ˆ 0.196; 4: C45H87Al2Cl2LiN4O4P, monoclinic, P21/c,
a ˆ 17.490(5), b ˆ 11.458(2), c ˆ 28.904(7) Š, b ˆ 92.67(2)8, Vˆ
5786.1(24) Š3, Z ˆ 4, with 584 parameters refined on 9514 reflections
with F > 2s(Fo)], R1 ˆ 0.065 and wR2 ˆ 0.200; 8: C11H29AlN6Si2,
monoclinic, P21/n, a ˆ 9.366(1), b ˆ 8.123(1), c ˆ 25.794(3) Š, b ˆ
93.76(1)8, Vˆ 1958.1(4) Š3, Z ˆ 4, with 217 parameters refined on
2490 reflections with F > 2s(Fo)], R1 ˆ 0.078 and wR2 ˆ 0.185. The
structures were solved by direct methods[16a] and refined by full-matrix
least squares on F2 [16b].Crystallographic data (excluding structure
factors) for the structures reported in this paper have been deposited
with the Cambridge Crystallographic Data Centre as supplementary
publication no. CCDC-100758. Copies of the data can be obtained free
of charge on application to CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (fax: (‡44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
[11] K. M. Waggoner, H. Hope, P. P. Power, Angew. Chem. 1988, 100, 1765;
Angew. Chem. Int. Ed. Engl. 1988, 27, 1699.
A cyclic voltammogram (CV) of the active aldehyde 2a Ð
which is prepared in situ by adding neat DBU (1.0 Â 10 2 m) to
a deaerated solution of 3-benzylthiazolium ion 1a (5.0 Â
R1
N
R1
N
R1
N
R2
R3
R2
R3
R2
R3
O–
R
RCHO
DBU
H
DBU
S
S
S
1
1–
2–
a
R
R
R
R
R
R
R
R
1 = PhCH2, R2 = Me, R3 = H, R = Me
1 = PhCH2, R2 = R3 =Me, R = Me
1 = PhCH2, R2 = R3 = H, R = Me
1 = PhCH2, R2 = Me, R3 = H, R = Ph
1 = PhCH2, R2 = R3 =Me, R = Ph
1 = PhCH2, R2 = R3 = H, R = Ph
1 = PhCD2, R2 = Me, R3 = H, R = Me
1 = PhCH2, R2 = Me, R3 = H, R = CD3
b
c
d
e
f
[12] L. V. Interrante, G. A. Sigel, M. Garbauskas, C. Hejna, G. A. Slack,
Inorg. Chem. 1989, 28, 252.
Â
[13] a) J. L. Faure, R. Reau, M. W. Wong, R. Koch, C. Wentrup, G.
g
h
i
Bertrand, J. Am. Chem. Soc. 1997, 119, 2819; b) M. W. Wong, C.
Wentrup, ibid. 1993, 115, 7743; c) G. Maier, J. Eckwert, H. P.
Reisenauer, A. Bothur, C. Schmidt, Liebigs Ann. 1996, 1041.
[14] a) A. Heine, D. Stalke, Angew. Chem. 1993, 105, 90; Angew. Chem. Int.
Ed. Engl. 1993, 32, 121; b) M. T. Reetz, B. M. Johnson, K. Harms,
Tetrahedron Lett. 1994, 35, 2525.
R1 = PhCD2, R2 = Me, R3 = H, R = Ph
[*] Prof. Dr. S. Fukuzumi, I. Nakanishi, Dr. S. Itoh, Dr. T. Suenobu
Department of Applied Chemistry, Faculty of Engineering
Osaka University
Â
[15] a) N. Emig, R. Reau, H. Krautscheid, D. Fenske, G. Bertrand, J. Am.
2-1 Yamada-oka Suita Osaka 565-0871 (Japan)
Fax: (‡81)6-879-7370
Chem. Soc. 1996, 118, 5822; b) N. Emig, H. Nguyen, H. Krautscheid,
Â
R. Reau, G. Bertrand, unpublished results.
E-mail: fukuzumi@chem.eng.osaka-u.ac.jp
[16] a) G. M. Sheldrick, Acta Crystallogr. Sect.
A 1990, 46, 467;
b) SHELXL-97, Program crystal structure refinement, Universität
Göttingen, 1997.
[**] This work was partially supported by a Grant-in-Aid from the
Ministry of Education, Science, Sports, and Culture, Japan.
992
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Angew. Chem. Int. Ed. 1998, 37, No. 7