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Nonapentafulvalene by Oxidative Coupling of Cyclononatetraenide and Cyclopentadienide.

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of the anion closely resembles that of [Moz05(o-benzenepowder and relatively large deep red crystals had developed. Yield ca.
0.04 g (10%).
d i ~ l a t e ) ~ ]and
~ ~ ~of' ~[MoZO5(3,5-di-tert-1,2-benzenediol[3] V. V. Tkachev, L. 0. Atovmyan, Koord. Khim. 2 (1976) 110.
and possesses two cis-dioxomolybdenum(v1)centers
[4] C. G. Pierpont, R. M. Buchanan, Inorg. Chem. 21 (1982) 652.
bridged by one pz-oxido- and two pz-O-2-sulfidophenolate
151 C. D. Garner, S. Bristow in T. G. Spiro: Metal Ions in Biology ("Molybdeligands. The last-mentioned bridges are asymmetr!c and
num Enzymes"), Chapt. 7, Wiley, New York, in press.
[6] C. G. Pierpont, R. M. Buchanan, Coord. Chem. Rev. 38 (1981) 45.
involve Mo-0 distances of 2.117(2) and 2.482(2) A. The
[7] R. E. Johnson, G. C. Papaefthymiou, R. B. Frankel, R. H. Holm, J. Am.
Mo atom has a very distorted octahedral environment of
Chem. Soc. 105 (1983) 7280.
five 0 and one S donor atoms, with the largest and the
[8] F. A. Cotton, G. Wilkinson: Advanced Inorganic Chemistry, 4th edit., Wismallest bond angles being 02Mo04'= 167.4(1)" and
ley, New York 1980, pp. 820-821, and references therein; K. Sasaki, S.
Ito, Y. Saheki, T. Kinoshita, T. Ydmasaki, J. Harada, Chem. Lett. 1983,
03Mo04'= 67.q l ) O , respectively. The UV/VIS spectrum
37.
of [PPh4]Z[Moz05(SC6H40)z]
contains two bands of a com[9] D. Greenwood, H. A. Stevenson, J. Chem. Soc. 1953, 1514; S. Cabiddu,
parable intensity with A,,,,,= 400 and 350 nm and an abA. Maccioni, M. Secci, V. Solinas, Guzz. Chim. Itul. 99 (1969) 397.
sorption of higher intensity with ;1,,,,,=297 nm.
Complexes containing the (Mo~O~)~@'
core usually exhibit two v(Mo-Otermlnal)bands in the IR spectrum in the region 910-935 cm-' separated by 6 2 0 cm-'[51. We therefore propose that the bands observed at ca. 918 and 924
Nonapentafulvalene by Oxidative Coupling of
cm-' in the IR spectrum of 1 are due to ~(MO-O~,,,,,,,,~)
Cyclononatetraenideand Cyclopentadienide**
stretching vibrations. ( M O ~ O ~ )complexes
~@'
generally absorb at ca. 775 cm-'[5', but although 1 has an absorption at
By Andrk Escher and Markus Neuenschwander*
ca. 765 cm-', its assignment to the v(Mo-03-Mo) vibraAccording to Doering, pentafulvalenesr'] can be pretion is complicated by the presence of 2-sulfidophenolate
pared
by reaction of cyclopentadienides with iodine, folvibrations in this region.
lowed by deprotonation and subsequent oxidation with
2-Mercaptophenol and its singly and doubly deproton0J2];
however, the atmospheric oxidation is often probleated anions are of considerable potential interest as limatic.
We recently reported the oxidative coupling of the
gands, especially as this last form is intermediate between
Huckel
anions 1 with Ag' or Cu" salts[31.After deprotonacatecholates and ortho-benzenedithiolates which form
tion to 3, the almost quantitatively formed dihydrofulvalcomplexes with notable redox properties. However, the
enes 2 are again reacted with Ag' or Cu". This procedure
chemistry of 2-mercaptophenol derivatives is presently
allowed
concentration of the reactive pentafulvalene 4
very limited. The study described herein represents the
(n=2)IZ1to be increased to a level sufficient for NMR
first structural characterization of a complex of the
SC6H4OzGligand. The lengths of the C-0 and C-S bonds
(1.346(3) and 1.763(3) respectively) are taken to indicate
that the ligand is present as a dianion rather than in an oxidized form[61.The singly charged form HOC6H4Se has
been observed in both a monodentate (through S) and chelating (through 0 and S) coordination mode in the same
FeS cluster compound[71.
The in situ synthesis of the 2-sulfidophenolate ligand
(n = 2 , 4 , . . . )
(C H=C H)/
appears to involve the aerial oxygenation of benzenethio1
2
3
4
late and, given the reaction conditions and known precedents[*', is presumed to be a Cu-assisted process. This apspectroscopic studies*31.Recently the same method has
proach could offer a potentially attractive alternative to
been
applied to the synthesis of the 2,5-di-tert-butylcyclothe synthesis['] of 2-mercaptophenol and related systems.
penta[a]pentalenide ionr4'. Here we describe the first synReceived: June 22, 1984;
thesis of nonapentafulvalene 12 (9-(2,4-~yclopentadienylirevised: September 14, 1984 [Z 895 IE]
dene)-l,3,5,7-~yclononatetraene)['~.
German version: Angew. Chem. 96 (1984) 960
When 1 mmol each of Na-cyclopentadienide (Na-CPD)
and cis,cis,cis,trans-Na-cyclononatetraenide (Na-CNT)[']
[I] a) S. R. Acott, C. D. Garner, J. R. Nicholson, W. Clegg, J. Chem. Sac.
are allowed to react with 2.2 mmol of CuCI, in 10 mL of
Dulfon Truns. 1983, 713; b) S. F. Gheller, P. A. Gazzana, A. F. Masters,
tetrahydrofuran
(THF) at -50°C, a mixture of the dihyR. T. C. Brownlee, M. J. O'Connor, A. G. Wedd, J. R. Rodgers, M. R.
drofulvalenes 5 , 6 , and 7[6331is formed in the ratio 5 :4 :1
Snow, Inorg. Chim. Acfu 54 (1981) L131; c) A. Muller, M. Dartmann, C.
(yield 85%, calculated from the NMR and GC). In conRomer, W. Clegg, G. M. Sheldrick, Angew. Chem. 93 (1981) 111; Angew.
Chem. Int. Ed. Engl. 20 (1981) 1060; d) A. Muller, H. Bogge, H. G. Tolle,
trast, if 5 mmol Na-CPD and 1 mmol of Na-CNT are couR. Jostes, U. Schimanski, M. Dartmann, Angew. Chem. 92 (1980) 665; Anpled using 6.6 mmol CuCI2 in THF, in addition to 5 and 6
gew. Chem. Int. Ed. Engl. I9 (1980) 654; A. Miiller, H. Bogge, U. Schi(ratio 1 :4) the product mixture contains only traces of 7.
manski, Inorg. Chim. Actu 69 (1983) 5 ; e) C. D. Garner, J. R. Nicholson,
For the tautomerizations 5 * 5 ' and 6+8, the mixture is
W. Clegg, Actu Ciysfullogr.,Sect. C39 (1983) 552; f ) A. Miiller, U. Schimanski, J. Schimanski, Inorg. Chim. Actu 76 (1983) L245; g) W. Clegg, C.
treated with aluminum oxide (basic I) at - 20°C. The tauD. Garner, J. R. Nicholson, P. R. Raithby, Acfu Crystullogr., Sect. C39
tomeric 9-(cyclopentadieny1)-1,3,5,7-cyclononatetraenes5 '
A,
(1983) 1007; h) J. R. Nicholson, A. C. Flood, C. D. Gamer, W. Clegg, J .
Chem. Sac. Chem. Commun. 1983, 1179.
[2] [PPh4]2[MoOS,(CuC1)3](0.7 g, 0.59 mmol) was dissolved in CH3CN (ca.
40 mL) under an atmosphere of N2. Addition of solid KSPh (0.26 g, 1.8
mmol) and stirring overnight at room temperature led to the precipitation
of KCI, which was separated off by filtration. Et20 (ca. 30 mL) was added to the deep red filtrate to give a small amount of black precipitate.
Separation of this product by filtration and further addition of Et20 led
to the formation of a black tar. The solution was decanted and more EtZO
added with the same result. After standing at room temperature for ca. 3
weeks, with limited exposure to air, the tar was transformed into a black
Angew. Chem. Int. Ed. Engl. 23 (1984) No. I2
[*I Prof. Dr. M. Neuenschwander, DipLChem. A. Escher
Institut fur Organische Chemie der Universitat
Freiestrasse 3, CH-3012 Bern (Switzerland)
[**I Fulvenes, Fulvalenes, Part 41. This work was supported by the Schweizerischer Nationalfonds (Project No. 2.402-0.82) and by Ciba-Geigy AG,
Basel. We thank Dr. T. Jenny, Organisch-chemisches Institut, Universitat Fribourg (Switzerland) for the high-field NMR spectra.-Part 40:
PI.
Q Verlug Chemie GmbH, 0-6940 Weinheim..'l984
0570-0833/84/1212-0973 $ 02.50/0
973
can be separated by chromatography on silica gel (pentane, -20°C) from the slower moving red dihydrofulvalene 817,31
(70% yield relative to CNT). The structure of 5 ' is
proved by the spectroscopic data as well as by the cyclization 5'+9, which is rapid at 20°C.
@
Nao
7
6
5
"
8 - 88
@
L
KQ
+
- KOtBu
25T
K8
+
traces of 7
\ I
/
\
J
5'
10
8
Structure elucidation of 12 is based on the low temperature NMR spectra and on the cyclization 12 -+ 11. In the
'H-NMR spectrum (Fig. l), the ring protons are pairwise
equivalent. The key protons 1-H/8-H appear as a doublet
at 6=6.82. Assignment of the remaining protons of the
nine-membered ring (2-H/7-H: 6.08; 3-H/6-H: 6.13; 4-H/
5-H: 5.96 ppm) follows from decoupling experiments. The
centers of the AA'XX' system of the five-membered ring
protons at 6=6.57 and 6.43 absorb similarly to those of
pentafulvalene 4 (n = 2)13]. In the l3C-NMR spectrum, the
signals of the pairwise equivalent C atoms of the ninemembered ring (C'/C8: 6 = 128.0; C2/C7: 133.0; C3/C6:
129.5; C4/C5: 128.5) appear in the narrow range 6= 128133 typical for nonpolar n o n a f ~ l v e n e s ~
Furthermore,
~~.
the
positions of the five-membered ring C atoms (C9/CI2:
6 = 121.2; C'o/C": 132.2) are very similar to those of pentafulvalene 4 (n = 2) as well as of pentaful~enes~~].
Finally,
the disrotatory cyclization 12-11, which is very rapid relative to that of 10,lO-bis(dimethylamino)nonafulvene~'o]
stabilized by electron-donating groups, is consistent with
the olefinic character of the cyclononatetraene unit of 12.
The structure of 11 has been confirmed by spectroscopic
studies ('H-NMR, 13C-NMR, IR, UV, MS).
Received: August 9, 1984;
revised: September 11, 1984 [Z 961 IE]
German version: Angew. Chem. 96 (1984) 983
For the synthesis of 12, a solution of 5' in THF is deprotonated at -25 "C with potassium tert-butoxide, whereupon the dipotassium salt 10 precipitates. Reaction with
CuC12 at -55°C affords a red suspension which is
worked-up by filtration (silica gel, pentane) and concentrated at - 50°C to yield 12 (ca. 30% relative to 5')-Nonapentafulvalene 12 is a red hydrocarbon which crystallizes
at -5O"C, but is so reactive that it has as yet eluded attempts at recrystallization. According to the NMR spectrum, the half-life of the cyclization 12- 11 is ca. 35 min
in CDCI3 at - 15"C. Therefore, 12 is even more reactive
than nonafulvenets1.
6.57
'I
I
I
6,8
SpiroI23lhexanes by C,
6,L3
I
6,82
6,13
6,6
6,08
6,L
6.2
5,96
6,O
58
Fig. 1. 'H-NMR spectrum of 12 (360 MHz, [Da]acetone, -40°C; 6 values).
Tf&ebreaks in the region 6=5.85, 6.4, 6.5 and 6.65 signify that the original
spectrum contains signals from 9% 11.
974
0 Verlag Chemie GmbH, 0-6940 Weinheim, 1984
+ C2-Coupling**
By Udo H. Brinker* and Michael Boxberger
Cyclobutylidenes 7 are the only small ring carbenes to
undergo exclusively intramolecular reactions12331.
Herein,
we report the first intermolecular additions of 7 (carbenoid) to olefins for the direct synthesis of spiro[2.3]hexanes
8.
Diazocyclobutane Zc4](IR: vcN,=2O30 cm-'), which is
generated from the tosylhydrazone sodium salt 1 in a flash
pyrolysis apparatus['] by sublimation at 140-160°C (ca.
lop4torr), reacts with the styrenes 3a, b to give the 4,5-dihydro-3H-pyrazoles 4a, bL6].The azine 9l4], methylenecyclopropane 10, and cyclobutene 11 are formed at the same
31 I
I
[I] Fulvalenes are cyclic, cross-conjugated molecules in which two fully
conjugated rings with an odd number of carbon atoms are linked via a
central double bond. Penta-, hepta-, and nonafulvalenes consist of two
five-, seven-, and nine-membered rings, respectively; nonapentafulvalene 12 consists of one nine- and one five-membered ring.
[2] W. von E. Doering: Kekult! Symposium, Butterworth, London 1959; E.
Matzner, Ph. D. Thesis, Yale University 1958; R. Brand, H.-P. Krimmer,
H.J. Lindner, V. Sturm, K. Hafner, Tetrahedron Left. 23 (1982) 5131.
131 W. Rutsch, A. Escher, M. Neuenschwander, Chimia 37 (1983) 160.
[4] K. Hafner, G. F. Thiele, Tetrahedron Lett. 25 (1984) 1445.
[5] T. J. Katz, P. J. Garratt, J . Am. Chem. Soc. 86 (1964) 5194; G . Boche, H.
Weber, D. Martens, A. Bieherbach, Chem. Ber. 111 (1978) 2480.
[6] K. Hafner, S. Braun, T. Nakazawa, H. Tappe, Tetrahedron Lett. 1975,
3507.
[7] K. V. Scherer, J . Am. Chem. Soc. 85 (1963) 1550.
[8] M. Neuenschwander, A. Frey, Chimia 29 (1975) 212.
19) G. Boche, F. Heidenhain, B. Staudigl, Chem. Ber. I15 (1982) 3191; R. W.
Millar, M. Neuenschwander, Chimia 33 (1979) 54; G. Sabbioni, A. Otter,
M. Neuenschwander, ibid. 37 (1983) 124.
[lo] K. Hafner, H. Tappe, Angew. Chem. 81 (1969) 564; Angew. Chem. Int.
Ed. Engl. 8 (1969) 593.
[*] Priv.-Doz. Dr. U. H. Brinker, Dipl.-Chem. M. Boxberger
Abteilung fur Chemie der Universitiit
Universitxtsstrasse 150, D-4630 Bochum 1 (FRG)
[**I Carbene Rearrangements, Part 17. This work was supported by the
Fonds der Chemischen 1ndustrie.-Part 16: [I].
057&0833/84/1212-0974 $ 02.50/0
Angew. Chem. Int. Ed. Engl. 23 (1984) No. 12
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