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C60H60 and C54H48 Silver Ion Extraction with New Concave Hydrocarbons.

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[lo] R. E. Cramcr. M. A. Bruck, J. W. Gilje, 0rganomP~allic.s1986. 5 . 1496.
[I I ] H . Schmidhaur. U. Deschler, B. Milewski-Mahrla. B. Zimmer-Gasser. Chrm.
Ber. 1981. 114. 612.
I121 R . E. Cramer. M. A. Bruck, J. W. Gilje. Orgunonie/ulhc.v 1988, 7. 1465.
[I31 M. G . Davidson. R. Snaith, D. Stalke, D. S. Wright. .! Org. Chc~m.1993.58.
1141 a ) H. J. Bestmann. A. .I.Kos, K. Witzgall, P. v. R. Schleyer, Chem. Brr. 1986.
119. 1331 ; b) recent review of theoretical aspects of ylides and rebated posphorus-containing molecules: D. C. Gilheany. Chem. Rev. 1994. 94, 1339-1374.
[I51 Ah initio MO calculations. 6-31G hasis set [20a] with d orbitals on P atoms at
the SCF level (monomericcomplexes), 6-31G*" basis set at the MP2 level [20b]
(dimeric complexes) using the programs GAMESS [20c] and GAUSSIAN 92.
[ X d ] All geometries were freely optimised. A manuscript for pubhcation elsewhere is in preparation in which full details of all calculations performed will
be given.
[I61 H.-J. Cristau. C'hrm. Rev. 1994, 94, 1299-1313.
[I71 H. Schinidhdur. H. Stuhler, W. Vornherger, Chem. B w . 1972. 105, 1084.
(181 G. M . Sheldrick, Acra C'rwalhgr. Sco. A 1990. 46. 467.
(191 G. M . Sheldrick. SHELXL-93. Program for crystal structure refinement, University of Ghttingen, 1993.
[20] a ) W. J Hehre. R. Ditchfield. J. A. Pople, J. Chem. Phys. 1972, 56. 2257: P. C.
Hariharan. J. A. Pople, Thror. Chim. Acru 1973. 28.213; M. J. Gordon, Cliern.
LPII.1980. 76. 163: h) C . Moller. M. S. Plesset. P i i ~ sRev.
c) M. Dupuis, D. Spangler. J. J. Wendoloski, NRCC Software Catalogue, Program No. QGZl (GAMESS): M. F. Guest, P. Fantucci. R. J. Harrison, J.
Kendrick, _1 H. van Lenthe, K. Schoeffel. P. Sherwood, GAMESS UK (CFS
Ltd., 1YY3). d) M. J. Frisch. G. W. Trucks. M. Head-Gordon. P. M. W. Gill,
M. W. Wong. J. B. Foresman, B. G . Johnson, H . B. Schleger, M. A. Robh, E. S.
Repogle, R. Gomperts, J. L. Andres, K. Raghavachari, J. S. Binkley. C. Gonzalez. R L Martin, D. Fox. D. L. Defrees. J. Baker. J. J. P. Stewart, J. A. Pople.
Gaussian Inc.. Pittsburgh PA. 1992.
C,,H,, and C,,H,,: Silver Ion Extraction
with New Concave Hydrocarbons**
Jens Gross, Gabriele Harder, Fritz Vogtle,* Holger
Stephan, and Karsten Gloe
Spherical hydrocarbons containing a cavity are of interest for
both fullerene and host-guest chemistry. Three-dimensionally
linked molecular structures made up of sixty carbon atoms may
be possible precursors for the direct synthesis of fullerenes. On
the other hand, the hydrophobic cavity of such spherical hydrocarbons, which is accessible through variable openings on the
surface of the molecule, may host metal ions like AgIL'] and
Ga',lZ1as well as chargedr3]and
organic molecules.
Some time ago we reported on a first spherical concave hydrocarbon 1 in which four benzene rings are linked by six ethano
61 C,,H,,
represents the smallest member of a family
of macropolycyclic hydrocarbons based on 1,3,5-trimethylenebenzene subunits. In Figure I (top) two further members of this
series of homologues are depicted, which fit the formula
[C,H,],,, in this case n = 2, 3, and 4.'''
In the group of compounds with only 1,3,5-substituted benzene spacers no "spheriphanes" with 60 o r 70 carbon atoms can
be realized, yet these compounds are desirable in view of possi[*I Prof. Dr. E Vogtle, Dr. J. Gross, Dipl.-Chem. G. Harder
lnstitut fur Organische Chemie und Biochemie der Universitit
Gerhard-Domagk-Strasse 1, D-53121 Bonn (Germany)
Telefax: Int. code + (228)73-5662
Prof. Dr. K. Gloe, Dr. H. Stephan
lnstitut fur Anorganische Chemie der Technischen Universitht Dresden
This work was supported by the Bundesministerium fur Forschung und Technologie (project no. 13N6070). We thank Prof. Dr. V. Boekelheide and Prof.
Dr. J. E. McMurry for providing reference compounds, and Prof. Dr. F . G .
Kllrner. DiplLChem. J. Benkhoff, and Dipl.-Chem. V. Breitkopf for conducting the high-pressure experiments.
Ang<w. Chcrn. l n t . Ed. Engl. 1995. 34, N o . 4
Fig. 1. Top: C,,H,,. C,,H,,, and C,,H,, as members of the series of spherical
hydrocarbons based on 1.3.5-trimethylenehenzene.Bottom: Some selected concave
hydrocarbons linked by other than exclusive 1.3.5-connection of the benzene rings
and different spacers.
ble conversion to fullerenes. Compounds 4-6 (Fig. 1 , bottom) indicate that other similar concave hydrocarbons are conceivable, which are constructed from benzene rings without exclusively 1,3,5-substitution o r which contain other spacers. We
report here on the syntheses of the previously unknown spherical hydrocarbons C,,H,, 4 and C,,H,, 5, which affirm the universal applicability of the strategy of the synthesis of 1.
Synthesis of C,,H,,: The cyclization compound 12 was obtained from methyl p-toluenecarboxylate (7) in eleven synthetic
steps. Bromination with N-bromosuccinimide (a in Scheme 1)
phosphorylation, and threefold Wittig reaction with 1,3,5-benzenetrialdehyde 8Is1 yielded triene 9 as a mixture of isomers.
Three-step refunctionalization (hydrogenation of the double
bonds (d), reduction of the ester and subsequent acylation (e),
and reaction with hydrobromic acid/glacial acetic acid (f)) gave
the corresponding benzyl bromide, whose phosphorylation
yielded in turn the Wittig compound 10. Threefold olefination
with dimethyl 5-formylisophthalate and application of the refunctionalization sequence (h, i, k, 1) provided cyclization compound 12. The macrotricyclic phane 13 was generated by a sulfide cyclization reactionlg1 under dilution conditions["] (m).
Subsequent oxidation to 14 (n) followed by pyrolytic desulfurization" '21 ( 0 ) afforded the new decacyclic hydrocarbon 4" 31
(total yield from 12: 2 5 % ) . Direct cyclization of 12 with
phenyllithium, which was a favorable alternative in the synthesis of C,,H,,, yielded only traces of polycycle 4.
Synthesis of C,,H,,: Phosphonium bromide 17 was obtained
by Suzuki coupling of dimethyl 5-iodoisophthalate with
dihydroxy-p-tolylborane (16, p-tolylboronic acid)['41 (a in
Scheme 2), followed by bromination with N-bromosuccinimide
(NBS, b), and phosphorylation (c). Compound 17 was converted into triene 18 by a threefold Wittig reaction with 1,3,5-benzenetrialdehyde (d) analogous to the synthesis described before.
Hydrogenation (e), reduction of the methyl ester and subsequent acetylation (f), and bromination (g) provided the cyclization compound 19, which was converted into hydrocarbon 5[15]
through sulfide cyclization reaction (h), oxidation to the sulfone
(i), and pyrolytic desulfurization reaction (k) (total yield from
12: 3.5%).
The two new macrotricycles 4 and 5 are high-melting compounds; their mass spectra display only the molecular ion peak
VCH VErlugsgese/i.schufimbH, 0.69451 Weinheim, 1995
0570-0833/95/0404-0481 3 10.00
+ .2S,'O
48 I
and no fragmentation. While 5 shows only poor solubility in
most organic solvents, 4 has good solubility properties because
of the numerous ethano bridges and thus satisfies an important
prerequisite for the investigation of host-guest interactions.
The symmetry of thecompounds is evident in their NMR spectra.[l6, *'] Due to isochronism of protons in compound 5 only
three 'H NMR signals are observed for the aromatic protons,
for 4 on the other hand, five.
By molecular modeling calculationsf' we determined the
structures and dimensions of the cavities of the macrocycles
(Fig. 2) in order to choose suitable guests for complexation
I /
13 X ==SSO 2
4 x= -
Scheme 1. a) NBS, azobisisobutyronitrile, CH,CI,, hv, reflux, 79%: PPh,. CHCI,,
2 h reflux, 99%: c ) NaiMeOH, N,N-dtmethylformamide (DMF), argon, 4 h at
50'C 24%; d) 3 bar H,, PdjC ( l o % ) , toluene, 99%; e) LiAIH,. T HE argon, 2 h
reflux, then Ac,O. 4 h reflux. 95%: f ) HBriglacial acetic acid (30%). X h at 60 'C,
88%; g) PPh,, CHCI,, 2 h reflux. 99%: h) NaiMeOH, DMF, argon, 4 h at SO C.
78%: i) 3 bar H,, PdjC (lo%), toluene, 99%; k ) LiAIH,, THE argon, 2 h reflux,
then Ac,O, 4 h reflux, 95% ; 1) HBrigldcial acetic acid (30%). 8 h at 60 'C, 93%;
m) dilution conditions. 3 equiv Na,S 9H,O, l0equiv Cs,CO,, benzene/EtOH
(1 : l ) , argon, 8 h reflux, 14%: n) 12equiv m-chloroperoxybenzoic acid, CHCI,,
24 h at room temperature, 96%; o) 10-6Torr, 580°C. 38%. Overall yield m-o:
h, i, k
Scheme 2. a) [Pd(Ph,),J, 2 N Na,CO,, toluene argon, 95 'C, 8 h. 78%: b) NBS,
azobisisobutyronitrile, CH,CI,. hv, reflux. 7 3 % : c ) PPh,, CHCI,, 3 h reflux. 96%;
d) LiiMeOH. THF. argon: 57%: e) 3 bar H,. PdjC (10%). toluene, 99%:
f) LiAIH,, THE argon, 2 h reflux, then Ac,O, 4 h reflux, 86%; g) HBr/glacial
acetic acid ( 3 3 % ) . 8 h at 60 'C, 73 %: h) dilution conditions, 3 equiv Na,S 9H,O.
10equiv Cs,CO,, benzeneiEtOH ( l : l ) , argon. 8 h reflux, 13%: i)12equiv mchloroperoxybenzoic acid, CHCI,, 24 h at room temperature. 71 %: k ) lO-'Torr.
600 'C, 38%. Overall yield h - k : 3.5%.
VCH V~riug.~ge.\rlisrhu/~
mhH. 0-69451 Wc,inhritw. 1995
Fig. 2 . The structures determined by molecular modeling [18] permit an estimation
of the dimensions of the cavities [20]. Left: C,,H,,: A-B 250pm, C-D 315 pm,
A-E 800pm. Right: C,,H,,: A-B270pm,C-D41Spm, A-E947pm.
studies. Hydrocarbon 5, for example, provides a tailored niche
for an acetonitrile molecule, whereas 4 with its larger cavity
could include molecules like adamantylamine or tert-butyla m i t ~ e . [While
crystallization experiments for the preparation
of the corresponding complexes have not been successful so far,
preliminary tests show that the complexes may be obtained under extremely high pressures.[' 91
In addition to small neutral molecules metal ions such as
silver(1) are potential guests.I2'] While the known nprismandsl'". b, '1 and n-spherandst"l form rings around Ag' o r Gal,
the concave hydrocarbons could include ions within their threedimensionally linked molecular frameworks. In extraction experiments of silver ions from aqueous solutionf2'] we determined
the extraction efficiency of hydrocarbons I , 4, and 5, the wellknown n-prismand 20, and z-spherand 21, as well as the reference compounds 22 and 23[23]q ~ a n t i t a t i v e 1 y .Aqueous
f ~ ~ ~ silver
nitrate/picric acid solutions were extracted with a chloroform
phase containing the hydrocarbon ligand in different concentrations (Fig. 3). The determination of the silver ion content in
both phases with the radiotracer method[25]permits a comparison of the extraction efficiency and gives information about the
stoichiometry of the complex.
As expected, reference compounds 22 and 23, whose cavities
are too small, d o not extract Ag' ions (Fig. 4). C,,H,, 1 and
tetraene 20 form I : 1 complexes in the organic phase, but show
relatively poor extraction efficiency. C,,H48 5 extracts silver(])
in a comparable magnitude. The [2.2.2]paracyclophane 21 is
able to extract efficiently over a wide range of concentrations
because of its good solubility (at a ligand concentration of
5 x lo-' M, 67 YOof the Ag' is extracted) forming an 1 : 1 complex
also. However, the best silver ion extraction is possible with
O570-OR33195!'0404-0482JF 10.00f .25;0
Angew. Chrm. Int. Ed. EngI. 1995, 34. No. 4
I -'
'g 'A,
' 4
CaII, Znll
H p
Fig. 5. Comparison of the extractabilities E of selected cations by the hydrocarbons
1. 21, 4 ([ligand] = 1 x lo-' M in CHCI,. The extractabilities of Na'. Ca" and Zn"
were investigated in separate experiments).
lg [Ligand(org)]---+
Fig. 3. The dependence of the distribution proportion D,, (DAs= [Ag] in chloroform);[Ag] in water) on the concentration of the ligand in chloroform gives information about theextraction capacity and thecomposition of thecomplex. (Conditions:
M. [picric acid] = 1 x lo-' M: organic phase:
aqueous phase [AgNO,] = 2.7 x
~5 x lo-' M in CHCI,).
[ligand] = S x
mercury and thallium the values are slightly higher with 0.5 and
0.8 Oh, respectively (Fig. 5). Relative to other hydrocarbons
C,,H,, shows the highest extraction efficiency for silver observed to date and high selectivity. These results indicate that
concave hydrocarbons not only form a new family of structurally appealing molecules but may also be of interest as selective
host molecules.
Received: August 10.1994 [Z 7226 IE]
German version: A n g r i ~Chem. 1995. 107, 523
Keywords: host-guest chemistry . hydrocarbons . silver compounds spherands
Fig. 4 Comparison of the extractabilities of Ag' by selected hydrocarbons; [ligand]=lxIO~'~inCHCI~.
C,,H,, 4, which extracts more than twice as much Agl in
comparison to 21 at low ligand concentrations (up to
1 x 10- M) .[261 At higher concentrations the complex precipitates, and further investigations are not possible with this extraction system. Because of the few measured quantities, definite
determination of the complex composition for both 4 and 5 is
not possible.[271
In comparison to complex ligands containing heteroatoms
such as thiacrowns, which bind metal ions through their free
electron pairs, we expect a more selective extraction of silver
ions with the new concave hydrocarbons. Therefore, we investigated the extraction efficiency of the hydrocarbons 1,21, and 4,
which were available in sufficient amounts, for different alkali,
alkaline earth, and transition metal ions (Fig. 5 ) . While 21 does
not extract detectable amounts of either alkali metal ions or TI'
and Hg", which have ionic radii comparable to that of Ag', an
extractability of 0.1 YOfor TI' is found with C,,H,, (for Na',
Ca". Zn". Hg" < 0.1 %). In the case of C,,H,, the extractabilities for sodium, calcium, and zinc are also below 0.1 %; for
Aiigeiv. Chrm. I n t .
Ed. En,$ 1995, 34, N o . 4
[l] Examples of silver rr-prismands and rr-spherands: a ) H. C. Kang, A. W. Hanson. B. Eaton. V. Boekelheide, J Am. Chm. Soc. 1985. 107, 1979-198s; b)
J.-L. Pierre, P. Baret, P. Chautemps, M. Armand, iliid. 1981, 103. 2986-2988;
C. Cohen-Addad. P. Baret, P. Chautemps, JLL. Pierre. Acta Cr,wfallogr.
Secf. C 1983. 39, 1346-1349; c) J. E. McMurry, G. J. Harley, J. R. Matz, 1. C.
Clardy, J. Mitchell, J. Am. Chem. Soc. 1986, f08,515-516: d) H. Schmidbaur,
W. Bublak, B. Huber, G. Reber, G. Muller, Angeir.. C/irm. 1986, 98, 11081109; Angew. Chern. I n t . Ed. Engl. 1986.25, 1089-1090; e) for further examples of x-donor contributions in the complexation of silver ions see: A. Ikeda.
S. Shinkai, J. Am. Chem. SOC.1994. 116. 3102-3110: R. Leppkes. F. Vogtle.
Chem. Brr. 1983, 116. 215-219.
[2] a) H. Schmidbaur, R. Hager, B. Huber. G. Muller. Angru-. Chem. 1987, 99,
354-356; A n p i ' . Chenr. 1111.Ed. Enxl. 1987.26,33X -340: h) C . Elschenbroich,
J. Schneider. M. Wunsch, J.-L. Pierre. P. Baret, P. Chautemps. Chem. Ber.
1988, 121. 177- 183.
[3] For cation-n interactions ofquaternary ammonia salts with electron-rich host
compounds see P. C. Kearney, L. S. Mizoue. R. A. Kumpf. J. E. Forman, A.
McCurdy, D. A. Dougherty, J. Am. Cheni. Soc. 1993. 115.Y907-991Y; M. A.
Petti, T. J. Shepodd, R. E. Barrans, Jr., D. A. Dougherty. ;bid. 1988,110,68256840.
[4] For the inclusion of uncharged molecules in cage compounds see: T.A.
Robbins, C. B. Knobler. D. R. Bellew, D. J. Cram. 1 Am. Chrm. SOC.
1994, 116. 111 -122; review: D. J. Cram, Nufun, (Lond(in) 1992, 356.
[S] a j F. Vogtle, J. Gross. C. Seel, M. Nieger. An,syw. Cheni. 1992, 104.
1112-1113; Angew. C h m . I n t . Ed. Eiigl. 1992, 31. 1069-1070; F. Vogtle,
C. Seel, R. Berscheid, J. GroO, P.-M. Windscheif in Computational Approaches in Supramolecular Cheniisfry (Ed.: G. Wipffj ( N A T O AS1 Ser.
Ser. C 1994. 426, 311-317): b) L. F. Lindoy, Nurirre (London) 1992. 359,
[6] The analogue ofC,,H,, with etheno bridges (C,6H2,,) has been calculated with
conjugation considerations: 0. Wennerstrom, U. Noriander, J P h w Chem.
1985,89. 3233-3237; electronic structures of conjugated "spheriphanes" have
C/irm In/:Compuf. Scr.
been discussed recently: P. W. Fowler, S. J. Austin, .l
1994. 34. 264-269.
VCH Verlug.\ges~~llschuft
m h H , 0-69451 Weinheim. 199s
0570-083319510404-0483 $ 10.00 . 3 / 0
If one considers the benzene spacers as corners and the ethano bridges as edges
of polyhedra. C,,H,, is a tetrahedron. CjnHtra prism, and C,,H,, a cube. The
faces of the polyhedra correspond to the openings on the surface of the molecule. an area suri-ounded by n corners corresponding to a [2.] metacyclophane
window (71.
W. Ried, F.-J. Konigstein. Chem. Ber. 1959. 92. 2532-2545; H.-E. Hogberg. 0.
Bernhard Geissler, Stefan Barth, Uwe Bergstrasser,
Wennerstriim, Arlu Chem. Scund. Ser. B 1982, 36, 661 --667.
Michael Slany, Julie Durkin, Peter B. Hitchcock,
F. Vogtle, Cyrlophan-Chemie, Teubner. Stuttgart. 1990; Chmistry,
Wiley, Chichester. 1993.
Matthias Hofmann, Paul Binger,* John F. Nixon,*
P. Knops, N. Sendhoff, H.-€3. Mekelburger. F. Vogtle. Tip. Curr. Chem. 1992,
Paul von Ragut Schleyer," and Manfred Regitz*
Ihi, 1 36.
A. Dohm, F. Vogtle, Tup. Cuvr. Chem. 1991, 161, 69-106.
Dedicated fo Profbssor Rolf Huisgen
We thank Prof. Dr. M. Jansen, Institut fur Anorganische Chemie der Univeron the occasion of' his 75th birthday
sit& Bonn, for providing the high-vacuum pump and DipLChem. H. Seyeda
for his help.
In the cyclooligomerization of alkynes there is a special interest
R, = 0.48(petroleum ether40-60/CH2CI, 1:l);ni.p. > 340°C; IUPACname:
33.36243.461.3.391 .12.161 19.231,Z6.30]hexa.
in their cyclotetramers as also is the case in the series of phos12.14,16(58),19.21,23(59),26,28,30(60).33.35,39,43.45.49,phaalkynes (RC=P). Following the original thermal cyclote53. 55-heneicosaene.
tramerization of tBuC-P with low selectivity to the tetraphosPreparation analogous to that described by R. T. Hawkins, W. J. Lennarz,
phacubane 1,[11specific high-yield syntheses['] enable a detailed
H. R. Snyder, J. Am. Chem. Soc. 1960,82, 3053-3059.
R, = 0.43 (silica gel; eluent: petroleum ether 40-60/CH,C12 1 : l ) ;
study to be made of the reactivity of this p e n t a c y ~ l e . [ ~ ' ~ ~
m.p. 1 340-C; IUPAC name: decacyclo[
1 3 . 3 s . 1 J0~~4.~.'7~2'~.24~28]tetrapentdconta-l,~(5~),6,X,l~.i2,l4(52).~~,l~,2l(53),24,26,28(54).29.31,35,39,41,43,47,49-heneicosaene.
Spectroscopic data of 4: 'H NMR (400 MHz, CDCI,): 6 = 6.80 (d,
'J(H,H) = 8 Hz. 6 H ; ArH), 6.77 (t. 'J(H,H) =1.5 Hr, 3H; ArH). 6.67 (d,
'J(H,H) = 8 Hz, 6H ; ArH). 6.63 (d, 3J(H,H) =1.5 Hz. 6 H ; ArH). 6.42 (s.
3 H; ArH). 3.0 (m, 12H; CH,), 2.70 (m, 12H; CH,), 2.61 (s, 12H; CH,);
I3CNMR (100 MHz, CDCI,): d =140.81 ( 3 C : Cq), 140.34 (3C; C J , 139.60
(6C; C J , 138.94 (3C; CJ. 138.25 (3C; C J . 128.73 (6C; CH), 127.94 (6C;
CH), 126.97(3C; CH), 126.92 (3C;CH). 126.34(6C;CH),38.15 (3C;CH,).
37.82 (3C; CH,), 36.31 ( 3 C ; CH,), 36.25 ( 3 C ; CH,), 34.08 (3C; CH,); MS
(DEI): mi: ( O h ) : 780.4(100) [ M ' ] .
Utilizing a stepwise route, the polycyclic isomers 2 and 3 conSpectroscopicdataof5: ' H NMR (250 MHz,CDCI,): 6 = 6.95(s, 3 H ; ArH).
taining phosphaalkene units are now accessible151which, on
6.73 (d, 'J(H,H) =1.5 Hz, 6 H ; ArH), 6.64 (s, 15H;ArH). 3.07 (m, 12H;
CH,), 3.04 (s, 12H); CH,); I3C NMR (62.89 MHz. CDCI,): 6 ~ 1 4 0 . 4 (3C,
heating, quantitatively transform to the more thermodynamiC,),139.91 (3C,C,), 139.36(6C,C,). 139.25(3C,C J , 139.07(3C,C,). 128.83
cally stable compound 4, which only contains L3a3-phosphorus
(6C. CH), 127.89 (3C, CH), 126.76 (6C. CH), 126.39 (6C. CH), 126.32 (3C.
CH), 35.12 (3C. CH,), 33.45 (6C. CH,), 32.71 (3C. CH,); MS (70 eV). m/z
We now report the syntheses of the tetraphosphacyclooctadi( Y O )696.3770(100)
[M'], calcd: 696.3756.
The geometries were fully optimized with PM3 (Mopac 6.0, QCPE 455) at the
enes 7 and 13, which represent a new type of phosphaalkyne
RHF SCF level.
cyclotetramer, and also present results of a b initio calculations
Solutions of hydrocarbon 5 in chloroform were treated with acetonitrile and
on H C = P cyclooligomers.
warmed to 60' C and 10 kbar for 24 h in a sealed Teflon tube in an autoclave.
Treatment of the tricyclic zirconium compound 512. with
The samples were examined by NMR spectroscopy afterwards.
Points B, D, and E mark the centers of the benzene rings, A and C the centers
[(PPh,),NiCI,] leads to the removal of the ZrCp, fragment and
between these points.
to a dimerization resulting in the formation of the phosphaalkyne
For ah initio calculations of endo- and exohedral complexation of alkali metal
cyclotetramer 7 in 70 O/' yield.
ions by 1 see: J. Cioslowski, Q. Lin, J. Am. Chem. Soc., submitted.
Treatment of the dihydrophosphete 6,which is readily accesK. Gloe. P. Miihl. J. Beger, 2. Chem. 1988, 28. 1-14,
I The [3,3](2,6)naphthaIenophane23 was kindly supplied by DipL-Chem. F. Ott.
sible from the reaction of 5 with iodine and whose structure has
Its preparation will be reported elsewhere.
been established,[g1with [(PPh,),Pt(C,H,)] followed by iodine
The silver complex of the deltaphane (cf. [la]) is insoluble in chloroform, and
elimination and a further dimerization leads to the same product
therefore cannot be studied in more detail.
K. Gloe, P. Miihl, 1sofopenpru.xis 1983, 19, 257-260.
It is possible to recover silver as an amine complex without damaging the
[*] Prof. Dr. M. Regitz. Dr. B. Geissler, Dr. S . Barth, Dr. U. Bergstrasser.
hydrocarbon ligand by washing with ammonia solution.
Dr. M. Slany
Fachbereich Chemie der Universitdt
I If the straight line in Fig. 4 has a gradient of one, an 1: 1 complex is
Erwin-Schrodinger-Strasse,D-67663 Kaiserslautern (Germany)
Telefax: Int. code + (631)205-3921
Prof. Dr. P. Binger
Max-Pldnck-Institut fur Kohlenforschung
Kaiser-Wilhelm-Platz 1. D-45470 Miilheim an der Ruhr (Germany)
Telefax:Int. code + (208)1306-2980
Prof. Dr. J. F. Nixon, J. Durkin, Dr. P. B. Hitchcock
School of Chemistry and Molecular Sciences, University of Sussex
GB-Brighton BNl YQJ (UK)
Telefax: Int. code + (273)677196
Prof. Dr. P. von R. Schleyer, Dip1.-Chem. M. Hofmann
Computer-Chemie-Centrum des lnstituts fur Organische Chemie
der Universitit Erlangen-Nurnberg
Nigelsbachstrasse 25. D-91052 Erlangen (Germany)
Telefax: Int. code + (9131)85-9132
[**I Phosphorus Compounds Part 91. This work was supported by the Volkswagen
Foundation. the Deutsche Forschungsgemeinschaft (Graduiertenkolleg,
"Phosphor als Bindeglied verschiedener chemischer Disziplinen"), the Fonds
der Chemischen Industrie and the Landesregierung von Rheinland-Pfalz.
Part 90: K. K . Laali. B. Geissler, 0. Wagner, J. Hoffmann. R. Armbrust, W.
Eisfeld, M. Regitz, L Am. Chem. Sor. 1994, 116, 9407-9408.
New Phosphaalkyne Cyclotetramers Derived
from h3a2-Diphosphetes**
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concave, silver, ion, hydrocarbonic, extraction, c60h60, new, c54h48
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