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OctaleneЧBicyclo[6.2.0]decapentaene Conversion Mediated by Transition-Metal Complexes

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(51 Procedure: A mixture (45 g) consisting of approximately 60% PpiPrs. 20%
an X-ray structure analysis. Because of the common mode
P,iPr,, 5% P7iPr3, as well as further isopropylphosphanes (obtained by
of formation with 1 and PlliPrtlClas well as of the analogy
reaction of iPrPClZ and PCI3 (5:4) with magnesium in boiling THF) is
of the 31P('H}-NMR spectrum with that of 1 and of
thermolyzed for 7 h at 230 "C. The yellow-brown, highly viscous product
it is highly probable that 2 is a 3,4,7,10,11-penis taken up in 30 mL cyclohexane and chromatographed portionwise on
taisopropylpentacycl0[']tridecaphosphane. A1203(dried by heating in uacuo) using n-hexane and cyclohexane; the
chromatographic process is monitored using "P-NMR and mass spectroscopy. The fractions having the highest amount of 2 are combined, the
solvent is evaporated off, and the more soluble portions are removed
from the residue by extraction with n-pentane (3 x 5 mL). Several recrystallizations from THF/pentane (3: 1) yields 0.18 g pure 2 (not optimized);
pure 1 is obtained from the mothor liquor.
Octalene-Bicycld6.2.0ldecapentaene Conversion
Mediated by Transition-Metal Complexes
By Dieter Kawka, Peter Mues, and Emanuel Vogel*
Dedicated to Professor Ernst Otto Fischer on the occasion
of his 65th birthday
The naphthalene- and azulene-isomer bicyclo[6.2.0Jdecapentaene is a molecule of current interest, both from the
synthetic['] and theoretical[" point of view, due to the question of whether the fusion of two antiaromatic [4n]annulenes leads to an aromatic bicycle with a peripheral
(4n 2)n-electron system. After Schriider et aZ.flb,
succeeded in opening an entry to substituted bicyclo[6.2.0]decapentaenes,Oda et al.["]were able in 1980 to
prepare the parent compound 2 for the first time starting
from bicyclo[4.2.0]octa-3,7-diene-2,5-dione.
Fig. 1. Molecular structure of 1 in the crystal [2]; top: ORTEP representation; bottom: projection of the molecule parallel to the C1 axis with average
bond lengths in pm (050.7 pm) and selected average angles in degrees
( ~ 5 0 . 6 " exceptions:
110.72 1.2" and 96.221.4").
Some time ago we were ablec3]to detect mass spectroscopically the phosphorus hydrides PI2H, and PI3H5,respectively, among the products of hydrolysis of calcium
phosphide and in the products of thermolysis of diphosphane; however, their structures were not yet amenable to
experimental investigations. Since in 1 and 2 significant
steric influences of the substituents on the constitution of
the phosphorus frameworks can be ruled outr1b1,the hydrides can be considered to be the parent compounds of 1
and 2, respectively.
The polycycloalkane C12H16 corresponding to 1 is
but not the 2-analogue C13H18.
The Plz(4)- and P,,(S)-frameworks are essential structural units of Hittorf's phosphorus, in which they are
linked alternatingly via the two-atom bridges as common
zero-bridges to form five-cornered cylindersl4I. In 1 and 2
unaltered, P-rich part structures of the element occur for
the first time as discrete molecules.
Received: July 25, 1983 [Z 486 IE]
German version: Angew. Chem. 95 (1983) 1005
[I] a) M. Baudler, V. Arndt, Z . Nuturforsch., in press; b) M. Baudler, Angew.
Chem. 94 (1982) 520; Angew. Chem. Int. Ed. Engl. 21 (1982) 492; c) M.
Baudler, V. Amdt, Z . Anorg. Aiig. Chem., in press.
[2] Triclinic, Pi, u=879.8(3), b = 1088.5(2), c=1414.1(3) pm, a=93.01(2),
b= 107.61(2), y=92.92(2)", Z = 2 , 4516 reflections, 3549 of which with
142 4u(F), R = 0.026, R, = 0.029 (P and C anisotropic, freely refined H
sites with common isotropic temperature coefficients). For further details
on the crystal structure analysis, see: M. Fehkr, K.-F. Tebbe, Z. Nuturforsch. B. in press.
131 a) M. Baudler, H. Standeke, M. Borgardt, H. Strabel, J. Dobbers, Noturwissenschuften 53 (1966) 106; b) M. Baudler, Pure Appl. Chem. 52 (1980)
755; c) D. McNeil, B. R. Vogt, J. J. Sudol, S. Theodoropulos, E. Hedaya,
J . Am. Chem. SOC.96 (1974) 4613.
[4] H. Thurn, H. Krebs, Angew. Chem. 78 ( 1966) 1101;Angew. Chem. Int. Ed
Engl. 5 (1966) 1047.
Angew. Chem. Int. Ed. Engl. 22 (1983) No. 12
Parallel to Oda's studies we attempted the synthesis of 2
from the olefinic octalene lP1
by the classical sequence of
Diels-Alder reaction with an acetylenic dienophile and
Alder-Rickert cleavage. In combination with transitionmetal complex chemistry this concept now enabled an alternative access to 2.
Reaction of octalene with dienophiles such as maleic anh~dride[~']
or dicyanoacetylene (DCA) afforded sterically
uniform 1 :1 adducts, which-as suggested by the structure
of the corresponding Diels-Alder adducts of cyclooctatetraene-derive from the tricyclic octalene valence isomer
with a central four-membered ring, whereas reaction with
yields an adduct with the
carbon skeleton unchanged [(8 2)-~ycloaddition][~"~.
octalene-dicyanoacetyieneadduct 4 of interest here is obtained on heating a mixture of 1 and dicyanoacetylene
(50% excess) in acetone (40-50°C; 18 h); m.p. 163-164°C
(yield 340/0). Contrary to our expectation the Alder-Rickert
cleavage of 4 presented problems. Under analytical conditions [injection of a solution of 4 in dichloromethane into
the injector of a gas chromatograph at 240"Cl the adduct 4
did in fact thermolyze in the expected way to give 2 and
phthalic dinitrile, but on attempted translation of the reaction to the preparative scale a complex mixture of products
was always formed, from which 2 could be isolated only
with difficulty.
A way out of this impasse was opened by the observation that irradiation of a mixture of 1 and pentacarbonyl-
[*] Prof. Dr. E. Vogel, D. Kawka, Dr. P. Mues
Institut fur Organische Chemie der UniversitZt
Greinstrasse 4, D-5000 Koln 41 (Germany)
0 Verlug Chemie GmbH, 6940 Weinheim. 1983
0570-0833/83/1212-1003 $ 02.50/0
02CI O‘c0
6 (two stereoisomers)
oc/I ‘c 0
oc/ I \co
iron in pentane furnished the 1 :1 complex 5 (together
with 1 :2 complexes), which, like the adduct 4, derives
from the octalene valence isomer with a central four-membered ring; red crystals, m.p. 112-113°C (yield 22%). According to an X-ray structure analysis, the tricarbonyliron
group and the six-membered ring in 5 are located on opposite sides of the eight-membered/four-membered ring system. As anticipated, 5 readily undergoes Diels-Alder reactions at the diene system of the six-membered ring, which
is easily accessible from both sides. The addition of dicyanoacetylene leads to the chromatographically readily separable stereoisomeric adducts 6a and 6b, whose configurations still await assignment; 6a: m.p. 143-144°C (yield
56%), 6b: m.p. 159-161°C (yield 28%). In view of the tendency of tricarbonyl( 1-4-q-9,10-dimethylbicyclo[6.2.0]decapentaene)iron to isomerize to thermodynamically stable
tricarbonyl( 1,8- 10-q-9,lO-dimethylbicyclo[6.2.0]decapentaene)iron at 90”Ci’g1,it would appear that the thermal conversion of 6a/6b into the cyclobutadiene complex 7 (and
phthalic dinitrile) is predestined. When a mixture of solid
6a/6b is heated to 180°C the complex 7 is in fact formed
in a smooth reaction [violet crystals, m.p. 74-75°C (yield
62%)], without any trace of the assumed intermediate 1-4q-bicyclo[6.2.0]decapentaene(tricarbonyl)iron being detectable[51.The oxidative liberation of 2 from 7 with trimethylamine N-oxide dihydrate in acetone (20 h, room temperature) presented no difficulties; with diammonium hexanitratocerate(rv), however, only indefinable products were
obtained. The bicyclo[6.2.0]decapentaene 2, purified by
chromatography on silica gel, precipitates from concentrated pentane solution at -78°C as orange-red crystals
(needles); these were dried in vacuo at the same temperature; m.p. < - 30°C (yield 70%).
The spectra of 211’.2e1,which have now been supplemented by the I3C-NMR spectrum [(75.4 MHz, CD2CI,):
6= 143.90 (C-9,10), 140.80 (C-l,8), 122.86, 122.60 (C3,4,5,6), 109.90 (C-2,7)], do not as yet allow conclusions to
be drawn about the n-electronic structure. In the case of
the ’H-NMR spectrum [(90 MHz; C6D6): 6 ~ 6 . 3 5(s, H2,3,4,5,6,7), 7.47 (s, H-9,10)] it is still unclear why the
chemical shifts of the four-membered and eight-membered
ring protons differ by no less than 1.1 ppm. Consistent with
the theoretical arguments put forward by Aihara[2d1,it is
obvious that application of the ring-current criterium for
aromaticity to annelated ring systems such as 2 is inadmissible. On the basis of the structure analysis of 9,lO-diphenylbicyc10[6.2.O]decapentaene~’~~,
it can be safely assumed
that 2 i s virtually planar and that the non-cyclobutadienoid resonance structure (as in Formula 2) is most plausible. Interestingly, force field calculations predict an almost
0 Verlag Chemie GmbH, 6940 Weinheim. 1983
planar carbon skeleton even for an olefinic 2 parameterized to 1,3-butadiene. It thus appears attractive to determine by measurement of the heat of hydrogenation
whether 2 profits energetically through delocalization of
the peripheral l0n-electron system.
The possibility that 2 can-in analogy to its formation
from 1-be converted by the agency of transition-metal
complexes into the butalene 3 hitherto not isolated in substance[’] [complex intermediates: 7, dicyanoacetylene adduct of 7,and butalene(tricarbonyl)iron] is presently under
Received: July 26, 1983;
revised: September 26, 1983 [Z 487 IE]
German version: Angew. Chem. 95 (1983) 1006
The complete version of this communication appears in:
Angew. Chem. Suppl. 1983, 1371-1378
111 a) P. J. Garratt, R. H. Mitchell, Chem. Commun. 1968, 719; b) G . Schroder, H. Rottele, Angew. Chem. 80 (1968) 665; Angew. Chem. Int. Ed. Engl.
7(1968) 635; c) P. J. Garratt, K. P. C. Vollhardt, R H. Mitchell, J . Chem.
SOC.C 1970, 2137; d) G . Schroder, S. R. Ramadas, P. Nikoloff, Chem.
Ber. I05 (1972) 1072; e) F. A. Kaplan, B. W. Roberts, J. Am. Chem. SOC.
99 (1977) 513,518; f) M. Oda, H. Oikawa, N. Fukazawa, Y. Kitahara, Tetrahedron Lett. 1977, 4409; g) M. Magon, G. Schroder, Liebigs Ann.
Chem. 1978, 1379; h) C. Kabuto, M. Oda, Tetrahedron Lett. 21 (1980)
103; i) M. Oda, H. Oikawa, ibid. 21 (1980) 107; j) B. C. Bems, K. P. C.
Vollhardt, Tetrahedron 38 (1982) 291 1.
[21 a) R. Breslow, Ace. Chem. Res. 6 (1973) 393; b) A. Rosowsky, H. Fleischer, S. T. Young, R. Partch, W. H. Saunders, Jr., V. Boekelheide, Tetrahedron I 1 (1960) 121; c) M. RandiC, J. Am. Chem. SOC.99 (1977) 444;d) J.
Aihara, ibid. 103 (1981) 5704; e) A. Tajiri, M. Hatano, M. Oda, Chem.
Phys. Lett. 78 (1981) 112; f) T. C. W. Mak, W.-K. Li, J. Mol. Stmcr. 89
(1982) 281; g) N. L. Allinger, Y. H. Yuh, Pure Appl. Chem. 55 (1983)
131 a) E. Vogel, H.-V. Runzheimer, F. Hogrefe, B. Baasner, J. Lex, Angew.
Chem. 89 (1977) 909; Angew. Chem. Int. Ed. Engl. 16 (1977) 871; b) J. F.
M. Oth, K. Miillen, H.-V. Runzheimer, P. Mues, E. Vogel, ibid. 89 (1977)
910 and 16 (1977) 872; c) P. Mues, Dissertation, Universitat Koln 1980.
[ S ] For an interpretation of the thermal 1-4-q-bicyclo[6.2.0]decapentaene(tricarbony1)iron-1,8- 1O-q-bicyclo[6.2.0]decapentaene(tricarbonyl)iron
isomerization in terms of a “partially allowed” haptotropic rearrangement see: T. A. Albright, P. Hofmann, R. Hoffmann, C. P. Lillya, P. A.
Dobosh, J. Am. Chem. SOC.105 (1983) 3396.
191 On the detection of butalene as short-lived intermediate see: R. Breslow,
J. Napierski, T. C. Clarke, J. Am. Chem. SOC.97(1975) 6275.
The First Organodithioxophosphorane**
By Rolf Appel*, Falk Knoch, and Holger Kunze
Dedicated to Professor Ernst Otto Fischer on the occasion
of his 65th birthday
Until now, the last member of the triply coordinated
planar phosphoranes 1 [ 1 1 , 2IZ1,and 3 was missing; its existence had previously only been speculated aboutI31.
We have now been able to synthesize the first compound
of this type. Dithioxo(tri-tert-butylpheny1)phosphorane 6
was obtained by reaction of bis(trimethylsilyl)(tri-tert-buty1phenyl)phosphane
with disulfur dichloride 5 .
This result is surprising in that phenylbis(trimethy1si1yl)phosphane reacts with S2C1, and phenyldichlorophos[*I Prof. Dr. R. Appel, F. Knoch, H. Kunze
Anorganisch-chemisches Institut der Universitat
Gerhard-Domagk-Strasse 1, D-5300Bonn 1 (Germany)
[**I Low-Coordinated Phosphorus Compounds. Part 24.-Part 23: R. Appel,
W. Paulen, Angew Chem. 95 (1983) 807; Angew. Chem. Int. Ed. Engl. 22
(1983) 785.
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Angew. Chem. Int. Ed. Engl. 22 (1983) No. 12
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octaleneчbicyclo, metali, decapentaen, transitional, complexes, conversion, mediated
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