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Oxanickelacyclopentene Derivatives from Nickel(0) Carbon Dioxide and Alkynes.

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How Similar are Tropoquinones and
Benzoquinones? **
By Rolf Gleiter*. Walter Dobler, and
Mirjuna Eckeri- Maks i t
4,6-Cycloheptadiene- I ,2,3-trione 1 [ I 1 and 3,6-cycloheptadiene- 1,2,5-trione 2l2)are structural isomers which have
been designated o-tropoquinone and p-tropoquinone due
to their analogy with o-benzoquinone 3 and p-benzoquinone 4. In order to determine defucto how far the similarity applies, we recorded the He(l) photoelectron (PE) spectra of 1 and 2 and compared those with the PE spectra of
3"' and 4l4] (cf. Fig. I ) .
141 D. W. Turner, C. Baker, A. D. Baker, C. R. Brundle: Molecular Phoroeleclron Spec1roscop.v. Wiley-lnlerscience, London 1970; D. 0. Cowan. R.
Gleiter, J. A. Hashmall. E. Heilbronner. V. Hornung. Anqew. Chenr. 83
(1971) 405: Angun,. C/ieni. In!. Ed. Engl. 1 0 (1971) 401: T. Kobayashi, J .
Eleclron Specrrow. Relar. Plienon. 7 (1975) 341: D. Dougherty. S. P.
McGlynn. J . Ani. Cliem. So<. 99 (1977) 3234: P. Jacques. J. Faure. 0.
Chalvet, H. H. Jaffe. J . P/fF$.Chem. 8.5 (1981) 473.
181 UV-Atlas oryunircher Verhitidi~iiyen.88/23. B8/?7. Verlag Chemie. Weinheim/Bulterworths, London 1966.
Oxanickelacyclopentene Derivatives from Nickel(o),
Carbon Dioxide, and Alkynes
By Georg Burkhart and Heinz Hoberg*
We have extended our investigations of the nickel(o) hetero- 1,2-diene
to carbon dioxide. We have found
that nickel(o) in combination with the strongly basic chelating
ligand
N.N.W.N-tetramethylethylenediamine
(Meden)causes disproportion of CO, to (Mejen)Ni(CO,) 1
and tetracarbonylnickel (cdt = 1,5,9-cyclododecatriene).
5 (cdt)Ni
+
+
8 CO,
Meaen
4 (Me4en)Ni(C03)
RT, 72 h
+
Ni(CO),
I
In the presence of 2-butyne, disproportionation does not
occur and the oxanickelacyclopentene derivative 2 is
formed. [Yield 65%; m.p.= 170°C (decomp.); IR(KBr):
1620 (vCO), 500 c m - ' (vNiO)].
Fig. I . Comparison of the first PE bands o f 1-4.
The PE spectra of the p-quinones 4 and 2 (cf. Fig. I )
contain closely spaced bands which correspond to ionizations from the n orbitals (3b3,, 4b2, for 4, and I l a , , 9b2 for
2) and the 7-c orbitals (2b3., Ib,, for 4, and 3b,, 2a, for 2).
I n contrast, in the o-quinones 3 and 1 the bands corresponding to ionization from n orbitals (13a,, 1 Ib? for 3,
and 9b2, 1 l a , for 1 ) and n orbitals (2a,, 2b, for 3 and 2a2,
3b, for 1) are widely separated from each other. The great
similarity between benzoquinones and tropoquinones with
respect to the position of the cationic states (Fig. 1 ) depends upon the fact that the relative energies and the wave
functions of the n and n orbitals are comparable in both
systems.
A similar conclusion can also be drawn from a comparison of the first excited states: a similar hypsochromic shift
is observed between the 1st bands of the absorption spectraof 3 (16400cm-')'X"Id 4 (21800cm-')[x1andthecorresponding bands of 1 (17800 cm-')['] and 2 (22700
cm - I)l?I.
Received: June 12, 1981 [Z 949 IE]
German version: Angew. Chem. 94 (1982) 62
Angew. Chem. Suppl. 1982. 13
[ I ] M. Hirdma. S. llo. Terrahedron Len. 1975. 1071: M. Hirama. Y. Fukarawa, S. 116. ;hid. 1978. 1299.
121 S . 116, Y. Shoji, H. Takeshita, M. Hirama. K. Tdkahashi, Terrahedron
Leu. 1975. 1075: S . Ito. personal communication.
(31 P. Schang, R. Gleiter. A. Ricker, Bey. Bunsengei. Pl?.r.i. Chem. 8 2 (1978)
629; V. Eck, G. Lauer. A. Schweig. W. Thiel, H. Vermeer. Z . N a r i ~ r f i ~ r ~ c l i .
A 33 (1978) 383.
['I
[**I
76
+
H3CCzCCH3
+
+
CO,
Ue@n
PH3
(Me4en)Ki,
RT 4 8 h
0
2
0
Protonolysis of 2 led to 2-methylcrotonic acid, and reaction of 2 with carbon monoxide gave dimethylmaleic anhydride and tetracarbonylnickel.
r*
H30d
fCH3
H3C\
C=C\
H'
CO,H
+
RT, 5 h
Ni(CO),
Compounds of type 2 are potential intermediates in the
nickel-catalyzed synthesis of 2-pyrone from alkynes and
carbon dioxide["'.
Received: July 30, 1981 [ Z 950 IE]
Angew. Chem. 94 (1982) 75
Angew. Chem. Suppl. 1982. 147
[ I ] H. Hoberg. J. Korff, J . Organomer Chem. IS0 (1978) C20.
[2] H. Hoberg, J. Korff, J . Organomer. Chem. 152 (1978) C39.
131 H. Hoberg. G. Burkhan, C. Kruger, Y.-H. Tsay, J. Organomer. Chem.. i n
press.
141 H. Hoberg, G. Burkhart, Svnrhesrs 1979. 525.
[6] Y. Inoue, Y. Itoh, H . Hashimoto, Chem. Leu. 1978. 633.
Prof. Dr. R. Gleiter, W. Dobler. Dr. M. Eckert-Maksic
lnstitut fur Organische Chemie der Universitit
I m Neuenheimer Feld 270, D-6900 Heidelberg I (Germany)
This work was supported by the Deutsche Forschungsgemeinschaft. the
Fonds der Chemischen lndustrie. and by BASF AG. We thank Prof. ShA
It4 for information on the syntheses of I and 2.
0 Verlag Chemie GmhH. 6940 Weinheim. 1982
(cdt)6i
[*I
Prof. Dr. H. Hoberg, Dr. G. Burkhart
Max-Planck-lnstitut fur Kohlenforsfhung
Postfach 01 1325. D-4330 Mulheim a. d. Ruhr I (Germany)
0S70-0833/82/0101-0076 S 02.50/0
Angew. Chem. Inr. Ed. Etigl. 21 (1982) No. I
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nickell, dioxide, alkynes, oxanickelacyclopentene, carbon, derivatives
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