COMMUNICATIONS
dichloromethane (10/1). Phosphirene complex 4 was isolated as yellow
crystals (2 g, 66%). 31P NMR (81 MHz, CDCl3): d 201.0 (1J(P,W)
Steam-Stable MSU-S Aluminosilicate
Mesostructures Assembled from Zeolite
ZSM-5 and Zeolite Beta Seeds**
294.9 Hz); 13C NMR (50 MHz, CDCl3): d 89.3 (d, 1J(C,P) 18.8 Hz;
2
ꢀ
ꢀ
ꢀ
P-C C), 93.9 (d, J(C,P) 5.8 Hz; P-C C), 120.9 (s; C C-Ph, Cipso), 195.9
2
2
(d, J(C,P) 9.1 Hz; cis-CO), 198.4 (d, J(C,P) 34.8 Hz; trans-CO); MS:
Yu Liu, Wenzhong Zhang, and Thomas J. Pinnavaia*
m/z (%): 634 (6) [M ], 494 (100) [M
5CO]; elemental analysis (%) calcd
for C27H15O5PW: C 51.10, H 2.36; found: C 51.48, H, 2.42.
The structural integrity of Al-MCM-41 and related meso-
porous aluminosilicate molecular sieves has been significantly
improved in recent years through direct assembly and post-
synthesis treatment methods.[1] Nevertheless, the hydrother-
mal instability and mild acidity remain inferior to conven-
tional zeolites and limit potential applications in petroleum
refining and fine chemicals synthesis.[2] One might expect to
improve both the stability and acidity of these materials if
zeolite-like order could be introduced into the pore walls. One
approach, first introduced by van Bekkum and co-workers,[3]
is to transform the preassembled walls of Al-MCM-41 into
zeolitic structures by post-assembly treatment with a micro-
porous zeolite structure director, such as tetrapropylammo-
nium cations. More recent studies have shown that the walls of
the mesostructure can indeed be converted to a zeolitic
product, but the microporous zeolite phase (ZSM-5) is
segregated from the mesostructure, giving rise to ZSM-5/
MCM-41 composites.[4] These composites exhibited an en-
hancement in acidity for hydrocarbon cracking in comparison
to mechanical mixtures of ZSM-5 and MCM-41 and an
improvement in steam stability for purely siliceous composi-
tes.[4c]
6: Biphosphirene 6 was isolated as light yellow crystals by chromatography
with hexane/dichloromethane (4/1). 13C NMR (50 MHz, CDCl3): d 137.4
2
(d, 1J(C,P) 5.4 Hz; Cipso, Ph-P), 143.2 (pseudo t, 1J(C,P) ꢁ J(C,P)
13.6 Hz; Ph-C(P) C-P); MS: highest mass 785 [M
10CO H].
7: Biphosphirene 7 was isolated as a yellow powder by chromatography
with hexane/dichloromethane (10/1). 13C NMR (50 MHz, CDCl3): d 89.5
1
2
ꢀ
ꢀ
(d, J(C,P) 23.6 Hz; P-C C), 95.2 (d, J(C,P) 6.5 Hz, P-C C), 120.5 (s;
1
2
ꢀ
C C-Ph, Cipso), 144.6 (pseudo t, J(C,P) ꢁ J(C,P) 15 Hz; PhC(P) C-P);
MS: highest mass 632; elemental analysis (%) calcd for C40H20O10P2W2: C
44.07, H 1.85; found: C 44.03, H 1.75.
8: Triphosphirene 8 was isolated as light yellow crystals by chromatography
with hexane/dichloromethane (4/1); elemental analysis calcd (%) calcd for
C51H25O15P3W3: C 40.24, H 1.66; found: C 39.98, H 1.56.
Received: November 9, 2000 [Z16063]
[1] Reviews: F. Mathey, Chem. Rev. 1990, 90, 997 ± 1025; F. Mathey, M.
Regitz in Comprehensive Heterocyclic Chemistry II, Vol. 1 (Eds.:
A. R. Katritzky, C. W. Rees, E. F. V. Scriven), Pergamon, Oxford,
1996, pp. 277 ± 304; K. B. Dillon, F. Mathey, J. F. Nixon, Phosphorus:
The Carbon Copy, Wiley, Chichester, 1998, pp. 183 ± 203.
[2] M. Link, E. Niecke, M. Nieger, Chem. Ber. 1994, 127, 313 ± 319; N. H.
Tran Huy, L. Ricard, F. Mathey, J. Chem. Soc. Dalton Trans. 1999,
2409 ± 2410.
[3] M. J. M. Vlaar, A. W. Ehlers, F. J. J. de Kanter, M. Schakel, A. L.
Spek, K. Lammertsma, Angew. Chem. 2000, 112, 3071 ± 3074; Angew.
Chem. Int. Ed. 2000, 39, 2943 ± 2945.
[4] S. Holand, F. Mathey, Organometallics 1988, 7, 1796 ± 1801.
[5] A. Marinetti, F. Mathey, J. Fischer, A. Mitschler, J. Chem. Soc. Chem.
Commun. 1982, 667 ± 668.
We recently reported an alternative approach to more
acidic and hydrothermally stable mesostructures based on the
direct assembly of nanoclustered aluminosilicate precursors
that normally nucleate zeolite type Y crystallization.[5] These
protozeolitic species, known as ªzeolite seedsº, promote
zeolite nucleation by adopting AlO4 and SiO4 connectivities
that resemble the secondary building units of a crystalline
[6] A. Marinetti, F. Mathey, J. Fischer, A. Mitschler, J. Am. Chem. Soc.
1982, 104, 4484 ± 4485.
[7] N. H. Tran Huy, L. Ricard, F. Mathey, Organometallics 1997, 16, 4501 ±
4504; B. Wang, K. A. Nguyen, G. N. Srinivas, C. L. Watkins, S. Menzer,
A. L. Spek, K. Lammertsma, Organometallics 1999, 18, 796 ± 799.
[8] X-ray structure data for 8a: crystal dimensions 0.40 Â 0.16 Â 0.16,
zeolite.[6] The assembly of the Na -nucleated zeolite type Y
(faujasitic) seeds under hydrothermal conditions in the
presence of cetyltrimethylammonium ions afforded hexago-
nal MSU-S mesostructures with Si/Al ratios in the range 1.6:1
monoclinic, P21/n, a 12.467(5), b 18.565(5), c 22.346(5) , b
1
91.220(5)8, V 5171(3) 3, Z 4, 1calcd 1.955 gcm 3, m 6.817 cm
,
to 10:1. The replacement of Na by NH4 ions in the as-made
mesostructure, followed by calcination in the presence of the
surfactant, afforded exceptionally acidic and steam-stable
mesostructures. However, the steam stability was enhanced
by structure-stabilizing occlusions of carbon that formed
during the calcination process. That is, the steam stability at
8008C was in part a consequence of the exceptional acidity of
a framework that formed structure-stabilizing carbon, and not
entirely a result of an intrinsically stable framework.
F(000) 2872, qmax 30.038, hkl ranges: 13 ± 17; 21 ± 26; 31 ± 25,
33543 data collected, 15050 unique data (Rint 0.0699), 12185 data
with I > 2s(I), 649 parameters refined, GOF(F 2) 1.008, final R
indices: R1 0.0414, wR2 0.1095; max/min residual electron density
2.082(.251)/ 3.219(.251) eA 3. Data collection was with a Nonius
Kappa CCD diffractometer, f and w scans, MoKa radiation (l
0.71073 ), graphite monochromator, T 150 K, structure solution
with SIR97,refinement against F2 (SHELXL97) with anisotropic
thermal parameters for all non-hydrogen atoms, calculated hydrogen
positions with riding isotropic thermal parameters. 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-151986. 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).
Here we also make use of protozeolitic nanoclusters to
form exceptionally acidic and steam-stable aluminosilicate
[*] Prof. T. J. Pinnavaia, Y. Liu, W. Zhang
Department of Chemistry and
[9] Review: E. Roskamp, C. Roskamp in Comprehensive Heterocyclic
Chemistry II, Vol. 1 (Eds: A. R. Katritzky, C. W. Rees, E. F. V.
Scriven), Pergamon, Oxford, 1996, pp. 305 ± 331.
Center for Fundamental Materials Research
Michigan State University
[10] A. Marinetti, F. Mathey, J. Fischer, A. Mitschler, J. Chem. Soc. Chem.
Commun. 1984, 45 ± 46; B. Deschamps, F. Mathey, Synthesis 1995,
941 ± 943.
East Lansing, Michigan 48824 (USA)
Fax : (1)517-432-1225
[**] The partial support of this research by the National Science
Foundation through CRG grant 99-03706 is gratefully acknowledged.
Angew. Chem. Int. Ed. 2001, 40, No. 7
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
1433-7851/01/4007-1255 $ 17.50+.50/0
1255