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Anionic Host Molecules with Bicyclic Carbon SkeletonsЧSynthesis and Guest Inclusion in Aqueous Solution.

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calculations with inclusion of electron correlations confirm the T,, symmetry for Li4C4.~i21
Received: February 11, 1986;
supplemented: March 19, 1986 [Z 1667 IE]
German version: Angew. Chem. 58 (1986) 558
CAS Registry numbers:
K,LiSi,. 102210-64-0; K,Li(Si,)>, 102210-65-1; Si, 7440-21-3; Li, 7439-93-2;
[ I ] P. von R. Schleyer, Pure Appl. Chem. SO (1984) 151; G . Rauscher, T.
Clark, D. Poppinger, P. von R. Schleyer, Angew. Chem. 90 (1978) 306;
Angew Chem. l n i . Ed. Engl. 17 (1978) 276.
[2] H. G. von Schnering, R. Nesper, K.-F Tebbe, J. Curda, Z . Merallkd. 71
(1980) 357.
(31 E. Menges, V. Hopf, H. Schafer, A. Weiss, Naturforsch. 5 2 4 (1969)
1351 : A Gruttner, Disserloiion. Universitat Stuttgart 1982.
141 E. Busmann, No/urwissenschafren 47 (1960) 82.
[5] J. Witte, H. G. von Schnering, Z . Anorg. Allg. Chem. 327 (1964) 260.
161 R. E. Marsh. 1). P. Shoemaker, Acra Crysrallogr. 6 (1953) 197.
171 J. Llanos, R. Nesper, H. G . von Schnering, Angew. Chem. 95 (1983)
1026: Angew. Chem. lnr. Ed. Engl. 22 (1983) 998.
[XI J . Llanos, R. Nesper, H. G . von Schnering, Acra Crysrallogr. A 4 0 (1984)
Suppl. ('-228, Abstr. 08.2-40.
191 H. G. \'on Schnering, R. Nesper, T. Chattopadhyay, D. Stoilova, unpublished refinement of the NaSi structure (cf. IS]).
[lo] A. Savin, K. Vogel, H. Preuss, H. Stoll, R. Nesper, H. G . von Schnering,
[ I I ] J. P. Ritchie, J. Am. Chem. Sor. 105 (1983) 2083: R. L. Disch, J. Schulman, J . P. Ritchie, ibid. 106 (1984) 6246.
[ 121 K. Raghavachari, P. von R. Schleyer, private communication (1986).
A Stable 1,2,4-Thiadiphosphole
("2,4-Diphosphathiophene")* *
By RolfAppel* and Rainer Moors
Dedicated to Professor Marianne BaudIer
on the occasion of her 65th birthday
Investigations carried out in the past few years have revealed that there is a definite and, in some cases, amazing
relationship between the P=C and C=C double bond.[IJ
This relationship manifests itself in the reaction behavior
of the phosphaalkenes and alkenes as well as in the synthesis of phosphabenzene,'21 p h o ~ p h a a z u l e n e s , 'and
~ ~ various phospholes containing heteroatoms. Among these,
only one incompletely characterized thiadiphosphole has
been described as reactive intermediate[51aside from aza-,
oxaza-, and thiazapho~pholes.[~~
We have now been able to synthesize the stable thiadiphosphole derivative 4 containing a conjugated
P=C-P=C sequence by reaction of carbon disulfide 1
with lithium bis(trimethylsilyl)phosphide 2 and chlorotrimethylsilane 3.
5-Trimethylsilyl-3-trimethylsilylthio-l,2,4-thiadiphosphole 4 is a yellow liquid that can be distilled under high
2 CS,
2 LiP(SiMe,),
2 Me3SiCL
vacuum (b.p. 75-78 "C/lO-' torr). Its composition has
been confirmed by an elemental analysis and a molar mass
determination; its constitution by an analysis of the spectroscopic data.
The 31P-NMR spectrum shows an AB system at
6=309.8 and 304.3 in the characteristic PC double bond
region with a PP coupling constant of 59.1 Hz. In the I3CN M R spectrum, the ring C-atoms appear as a doublet of
doublets at 6= 194.84 ( 'JCP=82.4 Hz, ' J C p = 1.0 Hz) and
189.96 ('J0=88.5
Hz, 'JCp=87.5 Hz) in the region for
sp2-hybridized carbon atoms. The signal at 6 = 1.54 (d,
3Jc,=5.3 Hz) is assigned to the trimethylsilyl carbon
atoms. Due to very similar coupling constants, the carbon
atoms of the trimethylsilylthio group appear with the
chemically different phosphorus atoms as a pseudo-triplet
at 6=0.66 with a coupling constant 4Jcp= 1.4 Hz.
A double-doublet with two small Si-P coupling constants of 5.8 and 3.0 Hz is observed at 6 = 18.32 in the "SiN M R spectrum. On the basis of the characteristic value of
the shift, this signal can be assigned to the trimethylsilylthio-silicon atom. The silicon atom of the trimethylsilyl
group bound to the carbon appears as a double doublet at
6= -2.03 (2Jsjp=25.8 Hz, 3Js,p=3.2 Hz).
All operations were carried out under inert gas using anhydrous solvents
A solution of 2 . 2 T H F (12 g, 37 mmol) in diethyl ether (80 mL) was slowly
added dropwise to a solution of CS2 (2.5 mL, 41 mmol) in 80 m L diethyl
ether cooled with methanol/dry ice. After I 5 minutes' stirring the dark-red
mixture was treated with 3 (5.2 mL, 41 mmol) and allowed to warm to room
temperature. The solvent was then removed and the residue was taken up in
50 mL of pentane, filtered, and the LiCl washed several times with pentane.
After removal of the pentane under vacuum, the crude product 4 was distilled under vacuum (mercury diffusion pump): yield 2.5 g (45"/,1referred to
2); MS (70 eV 90°C (selection)): m/z 296 (M', 47.7%). 281 ( M a - C H , ,
15.2%), 233 ( M @ - P S , 6.0%), 73 (CH3)& 100%).
The thioether 6 was collected in a cold trap, distilled (b.p. 65'C/I5 torr), and
identified 'H-NMR spectroscopically by comparison with authentic samples.
Received: February 13, 1986 [Z 1668 IE]
German version: Angew. Chem. 58 (1986) 570
[ I ] R. Appel, F. Knoll, I. Ruppert, Angew. Chem. 93 (I98 I ) 77 I : Anyen'.
Chern. lnt. Ed. Etigl. 20 (1981) 731.
[2] A. J. Ashe, J. Am. Chem. Soc. 93 (1971) 3293.
[3] G . Markl, E. Seidl, Angew. Chem. 95 (1983) 58; Angew. Chem. I n / . Ed
Engl. 22 (1983) 57; Angew. Chem. Suppl. 1983. 75; G. Mlrkl, E. Seidl. 1 .
Trotsch, Angew. Chem. 95 (1983) 891: Angew. Chem. I n / . Ed. Engl. 22
(1983) 879.
[4] A. Schmidpeter, K. Karaghiosoff, Nachr. Chem. Tech. Lab. 33 (1985) 793
(review of azaphospholes), and references cited therein.
[ S ] Y . Kobayashi, S. Fujino, 1. Kumadaki, J . Am. Chem. Soc 103 (1981)
Anionic Host Molecules
with Bicyclic Carbon SkeletonsSynthesis and Guest Inclusion in Aqueous Solution**
- 7PC
By Thomas Merz, Herbert Wirtz. and Fritz Vogtle*
Macrobicyclic molecules with carbon skeletons that can
act as water-soluble host molecules, such as 1, were unknown up to now.['I The corresponding monocyclic carbon
Prof. Dr. R. Appel, R. Moors
Anorganisch-chemisches lnstitut der Universitat
Gerhard-Domagk-Str. I , D-5300 Bonn I (FRG)
Lower Coordinated Phosphorus Compounds, Part %-Part
pel, F. Knoch, C. Porz, Chem. Ber.. in press.
Angew Chem. Inr. Ed. Engl 25 (1586) No 6
49: R. Ap
Prof. DJ. F. Vogtle, DipLChem. T. Merz, Dr. H. Wirtz
lnstitut fur Organische Chemie und Biochemie der Universitat
Gerhard-Domagk-Strasse 1, D-5300 Bonn 1 (FRG)
[**I We thank Prof. F. W . R6llgen and DipLChem. S . S. Wong (Bonn), Prof.
H . Egge (Bonn), and Dr. G. Eckhardr (Bonn) for the mass spectra, and
Dr. B Steffm and Mr. C . Schmidt (Bonn) for the 400-MHz 'H-NMR
0 VCH Verlagsgesellschaft mhH. 0.6940 Wernheim, 1986
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compounds, such as 2, have become known only recently.[’] The investigation of guest inclusion in molecules such
as 1, which has a disk-shaped cavity (Fig. I), offers promise of progress in the preparation of artificial receptors and
membrane channels and-by selection of appropriate
functional groups-in the development of synthetic catalysts.“]
R = C O ~ N ~
We have now prepared the first example of this type of
molecule, the dodecaester l a (m.p. = 285 0C),[31from simple starting materials-the trifunctional bromo compound
3 and the tetraethyl carboxylate 4[‘]--in a single synthetic
step under dilution conditions (sixfold bond formation;
0.6% yield).
(m.p. > 320°C), obtained from l a by hydrolysis with KOH
in ethanol, is particularly soluble in water at p H > 7 . In
aqueous NaOH, l c is formed.
therefore binds this guest with an association constant
(Ig K,,, = 2.0 at pH 7) similar to that of 2c (Ig K,,, = 2.3 at
p H 7). Examination of models provides an explanation for
this finding; namely, neither cavity offers sufficient space
for the entire ANS molecule. Only the anilino moiety of
ANS fits into the cavity of lc. Presumably, the charges of
the peripheral carboxylate groups have less effect on the
guest ANS than on positively charged guest molecules.
Taking into consideration these results, we expanded the
search for guests that fit into the cavity of l c to electrically
uncharged guest molecules that, moreover, d o not exhibit
high-field shifts on association with the monocyclic host
2c.[?l In fact, after addition of benzene to an aqueous solution of l c (and ultrasonication over several hours), we observed in the ‘H-NMR spectrum, in addition to the usual
benzene absorption at 6= 7.34, a strongly high-field shifted
signal (A6=0.65 ppm!), which we assign to benzene enclosed in the cavity of l c . Evaporation to dryness and
pumping at 50°C removes all traces of benzene; subsequent addition of toluene and ultrasonication leads to inclusion of this guest, the aromatic and aliphatic protons of
which appear at very high field besides in the usual region
(AS(H,,,,,, ) = 0.5, AS(CH3) = 0.6 ppm). Mesitylene also
undergoes inclusion in l c in aqueous solution upon ultrasonication, as was demonstrated analogously (S= 6.2 and
1.8; A6(H,,,,,,)=0.6
ppm, A6(CH3)=0.5 ppm).
Fig. I . Space-lilling model of the host Ib: a) empty; b ) w l t h enclosed benzene.
On account of the macrobicyclic effect,[5]it was of interest to compare the strength and selectivity of the binding
of guest substances by the new bicyclic host l b (as the sodium salt lc) with those of the monocyclic host 2b (as the
sodium salt 2c).”] In contrast to the findings for 2c,[’I the
doubly charged guest compound 5, which, according to
examination of molecular models, should fit into the cavity
of l b , does not exhibit ‘H-NMR high-field shifts in aqueous solution. This points to an unexpected and significant
difference in the recognition of guests by the macrobicyclic
host l c compared with the macromonocycle 2c. We propose that the guest dication is already “trapped” at the anionic periphery@]of the sodium salt l c (cf. Fig. 1) and, owing to the formation of strong ion pairs as well as the relatively rigid skeleton, does not enter the cavity. In contrast,
the conformationally more flexible host 2c offers the same
guest 5 both the possibility of analogous ion-pair formation and access to a directly neighboring cavity, which results in high-field shifts for the enclosed guest compound
on account of anisotropy effects.
In view of these findings, it was at first surprising that an
association constant of Ig K,,, = 2.1 (pH 11) was found by
fluorescence spectroscopy for the reaction of l c (concenmol/L) with 1,S-ANS (1,S-anitration between 0 and
linonaphthalenesulfonate)in aqueous solution, since l c
0 VCH Verlagsgesellsch~fimbH. D-6940 Weinheim, 1986
Thus, whereas the monocycle 2c does not bind uncharged guest molecules to a significant extent, l c does,
owing to its ability to enclose the guest on all sides in a
preformed cavity.
As demonstrated by the preparation of the analogous
host compound 6a (0.8% yield),”] which contains a modified cavity, the one-step synthesis strategy chosen for l a is
also applicable to other building blocks.
The differences observed in the binding of cationic, anionic, and uncharged guests by the bicyclic guest l c opens
u p possibilities for influencing the complexation in cavi-
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6b R = C O ~ H
6c R=co,@N~@
Angew. Chem. Int. Ed. Engl. 28 (1986) No. 6
ties by the use of pH-dependent charged groups on the periphery. Moreover, on account of their relevance for the
control of the passage of molecules through membrane
openings,lxlthe host compounds described here appear to
us to be of great interest with respect to guest selection.t91
Received: February 18, 1986;
revised: March 14, 1986 [Z 1672 IE]
German version: Angew. Chem. 98 (1986) 549
[ I ] F. Vogtle, W. M. Muller, J. lnclusion Phenom. 2 (1984) 369; D. OKrongly,
S . R. Denmeade, M. Y . Chiang, R. Breslow, J . Am. Chem. Soc. 107 (1985)
5544: F. Diederich, K. Dick, ibid. 106 (1984) 8024; J. R. Moran, S . Karbach, D. J. Cram, b i d . 104 (1982) 5826, M. Dhaenens, L. Lacombe, J. M.
Lehn. J.-P. Vigneron, 3. Cbem. SOC.Cbem. Commun. 1984. 1098; J. Rebek, Jr., B. Askew, N. Islam, M. Killoran, D. Nemeth, R. Wolak, J. Am.
Chem. Soc. 107 (1985) 6736; H. Schrage, J. Franke, F. Vogtle, E. Steckhan, Angew. Chem. 98 (1986) 335; Angew. Chem. Int. Ed. Engl. 25 (1986)
336, and references cited therein.
[2) F. Vogtle, T. M e n , H. Wirtz. Angew. Chem. 97 (1985) 226; .4ngew. Chem.
Int. Ed. Engl. 24 (1985) 221. In the meantime, an X-ray structure analysis
of 2a has been carried out. The dimensions of the cavity plausibly account for the inclusion of a benzene ring.
[3] l a : 'H-NMR (CDCIJTMS int.): 6= 1.29 (t. 36H. CH,), 1.80 (s, 12 aliphat. H), 3.24 (s, 12 benzyl. H), 4.25 (m, ABX, 24 OCHz), 6.78, 6.82,7.08,
7.12 (AA'BB', 24 aromat. H), 7.26 (s, 6 aromat. H).-"C-NMR (CD2C12):
6 = 171.4, 141.9, 139.7, 131.6, 129.3, 127.3, 124.8, 61.6, 58.1, 36.5, 25.2,
14.1.-FAB-MS: m / z 1723 [ M + HIa.
[4j l b : 'H-NMR ( D 2 0 standard): 6= 1.65 (s, 12 aliphat. H), 3.15 (s, 12 benzyl. H), 6.9, 7.05 (AA'BB', 24 aromat. H), 7.3 (s, 6 aromat. H).
IS] A. Caron, J. Guilhelm, C. Riche, C. Pascarol, B. Alpha, J. M. Lehn, J. C.
Rodriguez-Ubis, Helu. Chim. Acta 68 (1985) 1577.
[6] Compare the open-chain hexanoic acids: a) F. M. Menger, M. Takeshita,
J. F. Chow, J. Am. Chem. SOC.103 (1981) 5939; b) S. Shinkai, S . Mori, T.
Tsubaki, T. Sone, 0. Manabe, Tetrahedron Leu. 2s (1984) 5315; highfield shifts were not reported in this case.
171 6a: 'H-NMR (CDCIJTMS int.): 6=1.25 (t, 36H, CH,), 1.89 (s, 12 aliphat. H),2.05 (s, 6 H , bridgehead CH,), 3.33 (s, 12 benzyl. H), 4.22 (4. 24
OCH2), 7.24, 7.64 (24 aromat. H).-ELMS: m / z 1622.
[8] Review: D. W. Urry, Top. Curr. Cbem. IZS(1985) 175.
[9j For transport of molecules with o r against a pH gradient, see [8].
-a Novel Polyanion in the Compound
Fig. 1. Structure and arrangement of the anion [ C U ~ ~ I , , ]in~ the
~ @crystal.
In the system pyridinium iodide/CuI, it has now been
possible to isolate the largest discrete iodocuprate(1) ion to
date. The structural determination of a compound having
the composition ( P Y H ) ~ [ C U ~revealed
that the correct
formulation was (pyH)24([Cu36156]14).[31
In addition to isolated I Q ions at the positions 8b and 24d of the cubic space
group Fm3c, eight iodocuprate(1) ions [cu&6]200 are
present in the unit cell (Fig. 1). 36 Cul, tetrahedrons joined
by two or three common edges form a structure having the
extremely rare molecule symmetry 432 (=O). The 56 I
atoms of the anion can be regarded ideally as a section of a
cubic close-packing of spheres (Fig. 2a); eight cubes, facecentered on all sides, combine to form a larger cube, which
lacks the I atoms in the middle of the faces and in the center. The Cu atoms occupy 36 tetrahedral gaps of the iodine
partial lattice in such a way that 24 Cu atoms occupy the
corners of a cube with octahedral habit, i.e., the positions
formed by cutting off the corners of a cube. The 12 remaining Cu atoms lie at the middle of the edges of this cube;
the centers of the faces and of the cube itself are unoccupied (Fig. 2b). If a van der Waals radius ofa 2.2 A is assumed for 1°, a diameter of approximately 7 A is obtained
for the cavity in the center of the anion. The holes in the
centers of the faces have a diameter of about 1.5 A and are
therefore too small to allow guest molecules or cations to
enter the cavity of the cube; the compound crystallizes
without molecules of solvent.
By Hans H a d " and Joachim Fuchs
Dedicated to Professor Georg Manecke on the occasion
of his 70th birthday
In iodocuprates(1) [CU,I,]("-"')~, trigonal-planar and
tetrahedrally coordinated Cu atoms are present; the Cu13
units may be joined by common edges and the CuI, tetrahedrons by common corners, edges, and faces (!) to form
higher condensed iodocuprate(1) ions. This results in a surprisingly wide range of possibilities in the structural chemistry of iodocuprates( I), from low-molecular-weight units
such as [ C U I ~ ] ~ ' [ or
I ~ the binuclear ions [ C U ~ I ~ ] ~ ~ ,
[ C U ~ I and
~ ] ~[ ~C ,U ~ I ~and
] " ~higher condensed units such
or [Cu81r3]5"
as [cu416]2Q,[ C U ~ I ~[ C] U
~ ~ I, , ][Cu611
to polymeric anions such as L[cuI?], k[cu2e], '[Cu3I?],
or ~ [ C U , I ~Such
] . ~a~ variety
of structures is not encountered for other iodometalates. The structure and degree of
condensation of the iodocuprates(1) is determined by the
size, form, and charge distribution of the cations involved.
Prof. Dr. H. Hartl, Prof. Dr. J. Fuchs
lnstitut fur Anorganische und Analytische Chemie
der Freien Universitat
Fabeckstrasse 34/36, D-1000 Berlin 33 (FRG)
[**I Synthesis and Structural Investigation of lodocuprates(i), Part 7. This
work was supported by the Fonds der Chemischen 1ndustrie.-Part 6:
Angen. Chem. Int. Ed. Engl. 25 (1986) No. 6
Fig. 2. a) View along an axis perpendicular to a face of the cube, showing the
anion [Cu3a1,6]20e;large circles, I ; small circles, C u ; distances [pm]: Cu-I
264.9(5)-270.8(5), C u . . . C u 278.9(5)-285.4(7); angle ["I: I-Cu-I 103.6(2)I13.7(1). b) Cu partial structure of the anion [ C U , ~ ~ ~(cube
, ] ~ "with
~ octahedral habit). Hatched triangles: front side; black triangles: rear side.
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solutions, bicyclic, anionic, inclusion, molecules, skeletonsчsynthesis, aqueous, carbon, host, guest
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