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An Intermediate and Its Secondary Products in a Nickel-Catalyzed Synthesis of [4]-Radialenes.

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0(13C) = 172 mT
B
1
P
-
with an sp-hybridization rather than with the sp3-hybridization expected for a methyl C atom. Interestingly, it is
reminiscent of the formulation -C=H3 used for a methyl
substituent by Mulliken"' nearly 50 years ago.
The total spin population pc at a C(p) atom in 2 b Q 0
thus amounts to 0.0 I3 0.0 11 = 0.024, while the corresponding value pH for the H(B) atom in 2a00 is pH(ls)=
2.14 mT/50.7 mT=0.042,"21 where 2.14 and 50.7 mT are
the hfc's of 'H(0) in 2a0' (Table 1) and of the ' H nucleus
in atomic hydrogen,[l6I respectively. Should the spin populations, p<.= 0.024 and pH= 0.042, be interpreted in terms
of the "hyperconjugative abilities" of the C-C bonds being markedly smaller than those of the C-H ones, which is
at variance with the previous predictions of MO mode l ~ ? " . Or,
~ ~ d o the radical ions la, b",
2a, be', and
3a, be' represent a special case, so that the conclusions
drawn from the present results are not general? An answer
to these questions demands further investigations.
i
+
+-
H
20s
I
20
I
20s
I
I
I
24
I
I
I
I
Received: October 5, 1984:
revised: March 15, 1985 [Z 1029 :El
German version: Angew. Chem. 97 (1985) 496
I
20 MHz
Fig. I. ESR (top) and "C-ENDOR (bottom) spectra of "C2-ZbQ0 in liquid
solution. Solvent: 1,2-dimethoxyethane; counterion: K G ; T= 193 K. The
triangle in the ESR spectrum indicates the position for the ENDOR experiment. 2 . 0 5 =second-order splitting. Recorded with a Varian E-9 ESR spectrometer and a Bruker ER-252 E N M R system connected to a Bruker ER-200D-SRC-9 spectrometer. 1141
hfc's should be rather small. This conclusion is confirmed
by the ESR and E N D O R spectra of 13C2-2bQB
in a glassy
solution (Fig. 2). The difference A,,('3C)-A1(13C)=3.45
MHz (0.K13 mT), which is derived from the ENDOR
signals, gives an anisotropy parameter B('%) of only
+ 0 . n 3 m T = 0.041
From the experimental
'3C(p)-hfc's (a(13C)=1.72 and B('3C)=0.041 mT)['*I and
the atomic parameters for the C-2s- and C-2p-orbital~['~I
(135 and 3.8 mT, respectively)['51the partial populations
pc(2s)= 1.72 mT/135 mT=0.013 and ~ ~ ( 2 p ) = o . OmT/
4~
3.8 mT=O.Ol 1 are calculated. This result is compatible
CAS Registry numbers:
2b00, 92541-66-7; Zb- '3C00,96412.48.5
[I] R. S. Mulliken, J . Chem. Phw. 7 (1939) 339.
121 L. Radom, Prog. Theor. Org. Chem. 3 (1982) 64.
[3] L. Radom. J. A. Pople, P. v. R. Schleyer, J . Am. Chem. Sac. 94 (1972)
5935.
[4] Y. Apeloig, Z. Rappoport, J . Am. Chem. Soc. I01 (1979) 5095.
(51 D. N. Rao, H. Chandrd, M. C. R. Symons, J . Chem. Soc. Perkin Trans. 2
1984, 1201.
[6] F. Gerson, W. Huber, J. Lopez, J. Am. Chem. SOC.106 (1984) 5808.
171 W. Huber, Helu. Chrm. Acra 67 (1984) 1825.
[S] a) Ch. Elschenbroich, F. Gerson, V. Roekelheide, Helo. Chzm. Acru 58
(1975) 1245; b) F. Gerson, E. Heilbronner. V. Boekelheide, ihid. 47
(1964) 1124.
191 D. H. Whiffen, Mol. Phys. 6 (1963) 223: see also K. Scheffler, H. B. Stegmann: Elektronenspinresonanz, Springer, Be'rlin 1970, p. 173.
[lo] We thank Prof. R. H. Mirchell. Victoria, Canada, for a sample of 3b.
[ I l l The labeled compound "C:-Zb was obtained from the dianion of dicyclopenta[ef;kljheptalene 4 and "CH,Br according to the procedure described for the synthesis of 2b from 4" and Me,SO,. W. Huber, T.
Meul, K. Miillen, Angew. Chem. 93 (1981) 401; Angew. Chem. I n t . Ed.
Engl. 20 ( 198 I ) 39 1.
[ 121 A positive sign is demanded by theory for all hyperfine values reported
in this work, such as a('H), a("C), and B ( " C ) .
[I31 See, e.g., F. Gerson, G. Plattner, A. J. Ashe 111, G. Markl, Mol. Phys. 28
(1974) 601 ; M. C. R. Symons: Chemical and Biochemicaf Apecrs ofEfecIron Spin Resonance Spectroscopy. Wiley, New York 1978, chapter 4.
(141 Review o n ENDOR spectroscopy: H. Kurreck, B. Kirste, W. Lubitz, Angew. Chem. 96(1984) 171: Angew. Chem. Int. Ed. Engl. 23 (1984) 173.We thank Dr. R . Biehl. Bruker Analytische MeBtechnik GmhH, D-7512
Rheinstetten (FRG), for recording the ENDOR spectrum.
[I51 J. R. Morton, K. F. Preston, J . Mugn. Reson. 30 (1978) 577.
1161 R. Beringer, M. A. Heald, Phys. Reu. YS (1954) 1474.
An Intermediate and Its Secondary Products in a
Nickel-Catalyzed Synthesis of 141-Radialenes
R = I3CH3
By Ludwig Stehling and Giinther Wilke*
Dedicated to Professor Schulte-Frohlinde on the occasion
of his 60th birthday
Fig. 2. ESR (top) and " C - L N D O K (bottom) apectra 01 "C2-ZbQQin glassy
solution. Solvent: 2-methyltetrahydrofuran; counterion: K O ; T = 113 K. The
triangle in the ESR spectrum indicates the position for the ENDOR experiment. Taken with a Varian E-9 ESR spectrometer connected to a Varian ENDOR-1700 system.
496
0 VCH Verlagsgesel1.schaflmbH, D-6940 Weinheirn. 1985
1,2,3-Butatrienes can be catalytically cyclodimerized to
[4]-radialene~~'~
o r cyclotrimerized to [6]-radialenes in the
presence of [(Ph3P)2Ni(CO)2].[1.21
In the cyclotrimerization
of butadiene on "naked" nickel it was possible for the first
time to trap an intermediate of a catalytic cyclooligomeri~ a t i o n . [ Subsequently,
~'
numerous other intermediates, in
general metal la cycle^,'^^ have been isolated from related
[*I
Prof. Dr. G. Wilke, L. Stehling
Max-Planck-lnstitut fur Kohlenforschung
Kaiser-Wilhelm-Platz I, D-4330 Miilheim a. d. Ruhr (FRG)
0570-0833/85/0606-0496 $ 02.50/0
Angew. Chem. I n t . Ed. Engl. 24 (1985) No. 6
catalytic reactions. Thus, metallacyclopentanes are formed
on reaction of 2,2'-bipyridyl- 1,5-cyclooctadienenickel(o)2
with 3,3-dimethylcyclopropene'51 or methylcyclopropane;'"l the structure of the former metallacycle was determined X-ray ~rystallographically.~~~
2,5-DimethyI-2,3,4-hexatriene 1 reacts smoothly with 2
in tetrahydrofuran (THF) at 5°C with displacement of 1,5cyclooctadiene (COD) to give the nickelacyclopentane 3,
which can be isolated in crystalline form in over 80% yield.
The structure of 3 was confirmed by 'H- and I3C-NMR
spectra and X-ray structural a n a I y s i ~ . ~ ' ~ * ~
3 is formed by the oxidative addition of two triene molecules to nickel(0) with concomitant CC coupling. In the
presence of maleic anhydride (MA) a reductive elimination takes place, leading to formation of the 141-radialene
4.IU1The Ni-C o-bonds in 3 take part in insertion reactions followed by reductive elimination. Thus, reaction of
3 with C O leads to formation of 2,2'-bipyridyldicarbonylnickel and the cyclopentanone derivative 5 , whose structure is confirmed by IR/Raman, NMR, and mass spectra.'"'] On reaction of methyl acetylenedicarboxylate with
3, insertion and reductive elimination leads to the cyclohexene derivative 6, which has also been unequivocally
characterized." ' I
2
>===<
+
2
1
+co I
[bpy Ni cod]
3
+Me02CC
CCO$de
1
I
+MA
(51 P. Binger, M. J. Doyle, J. McMeeking, C. Kruger, Y.-H. Tsay, J . Orqanomef. Chem. 135 (1977) 405.
[6] P. Binger, Anqew. Chem. 84 (1972) 352; Angew Chern. In/. Ed. Eng/. I I
(1972) 309.
[7] C. Kruger, Y:H. Tsay, unpublished results. Unit cell data: a =9.602(1 j,
b=25.239(3), c=20.127(2jA,fl=97.34(1)", Z=8 w i t h p = 1.18 g cm- ';
9880 reflections, 3834 unobserved (1<20(1)); R=0.039, R, =0.047. Distorted planar coordination to the nickel (interplanar angle N-Ni- N /
C-Ni-C:
33"), Ni-N 1.952(3), NiC 1.926(5)A; N-Ni-N
82.1,
C-Ni-N 84.7'.
[8] 3 : 15.65 g (48.44 mmol) of 2 was dissolved in T H F (350 mL) under argon and treated with a solution of 1 (10.48 g, 96.88 mmol) in T H F (150
mL). After ca. I2 hours' stirring at 5 ° C the solution was evaporated to
40 mL, treated with 200 mL of pentane, cooled to - 7 8 ° C and the resulting precipitate filtered cold on a frit, and dried. Yield: 17.4 g (40.35
mmol), 83.3%. "C-NMR ([D,]THF, TMS. 75.5 MHz): 6 = 151.17, 150.52
( s , C-1, C-2); 108.32 (5, C-3); 121.69 (s, C-4); 26.47 (q, C-5); 23.12, 22.40,
22.08 (4.C-6, C-7, C-8); 152.33 (d, C-9); 127.20, 121.84 (d. C-10, C-12):
135.92 (d, C-l I ) ; 153.74 ( s , C-13); MS: m / z 430 ( M + ,
decomp.).
[9] 4 : 2.1 1 g (4.89 mmol) of 3 was dissolved in THF (40 mLj under argon
and treated with solid maleic anhydride (MA) (0.96 g, 9.78 mmol). Reaction was allowed to proceed for ca. 12 h, the T H F removed by evaporation, and the residue taken up in pentane. After filtration through a frit,
the filtrate was evaporated to dryness. Yield of crude product: 0.9 g
(4.62 mmol) 94"/0. After sublimation in vacuo (60-80°C): 0.75 g (3.47
mmol), 78.8% pure product. 'H-NMR ([DaJtoluene): 6 = 1.83 (I21
(CDCI;): 6 = 1.80); I3C-NMR (CDCI,): 6 = 138.3, 115.5, 23.8 (121:
6= 138.3, 115.5, 23.8); MS: m / z 216 (M+):
UV (n-hexane): L,,,,=269
nm (lg&=4.62), 259 sh (4.16), 280 sh (4.21), 304 sh (3.83) ((21: UV (cyclohexane): /1,,,=272 nm (lg&=4.279), 260 sh (4.176), 283 sh (4.230). 307
sh (3,857)).
[lo] 5 : 2.94 g (6.82 mmol) of 3 was dissolved in THF (80 mL) and treated
with 458.3 mL (20.46 mmol) CO. The T H F was then removed and the residue was taken upon in pentane, filtered through a frit, and the filtrate
evaporated to dryness. The residue was sublimed in a vacuum (80100°C): 1.1 g (4.5 mmol), 66% pure product. "C-NMR (CDCI,, TMS,
75.5 MHz): 6 = 194.05 ( s , C-I); 136.51, 136.05 ( s , C-2, C-3): 125.07 (5, C 4); 140.89 (s, C-5); 25.97, 23.06, 22.72, 20.38 (q, C-6. C-7, C-8, C-9j; MS:
m/z 244 ( M + , 63%); IR (KBr): v = 1696 ( s ) (CO), 1661 (w), 1644 (w).
1619 (5) (C=C) c m - ' : m.p. 1 I I "C.
[ I l l 6 : 1.21 g (2.8 mmol) of 3 was dissolved in toluene under argon and
treated with methyl acetylenedicarhoxylate. After 4 hours' stirring the
mixture was filtered through a frit. The filtrate was evaporated to dryness and the residue was taken up in pentane, filtered through a frit, and
the solvent removed from the filtrate. Yield: 0.6 g (1.67 mmol). 59.8"'o.
"C-NMR (CDCI;, TMS, 75.5 MHz): 6 = 133.42, 133.35, 129.51, 126.18
( s , C-I, C-2, C-6, C-7); 132.38 ( 5 , C-3); 169.87 ( s , C-4); 52.12 (q, C-5):
25.05, 21.47, 20.93, 20.30 (9, C-8, C-9, C-10, C - I t ) ; MS: m / z 358 ( M + ,
29%); IR (KBr): v = 1734 (s), 1721 ( s ) (CO), 1609 (m), 1537 (m) ( C = C )
c m - ' ; m.p. 159°C.
\/
5
4
Nitrogen Monoxide as a Source for 0 x 0 LigandsAcetylene-0x0 Complexes of Tungsten**
6
In the catalytic cyclooligomerization['l of 2,5-dimethyl2,3,4-hexatriene 1 mentioned initially, 4 is formed in only
11% yield along with 38% cyclotrimers.[*]The reaction described here in contrast, affords 4 in yields of more than
90% without necessitating a separation from by-products.
Received: December 28, 1984;
revised: March 28, 1985 [Z 1123 IE]
German version: Anqew. Chem. 97 (1985) 505
CAS Registry numbers:
1, 2431-31-4: 2 , 55425-12-4; 3, 96453-21-3; 4, 88919-66-8: 5, 96446-08-1; 6,
96446-09-2; MA, 108-31-6; CO, 630-08-0; Me0,CC-CCO,Me,
2,2'-bipyridyldicarbonylnickel, 149 17-14-7.
762-42-5:
By Helmut G. Alt* and Heidi I . Hayen
The conventional way to prepare organometallic 0 x 0
complexes involves the thermally or photochemically induced reaction of carbonyl complexes with air or with ox~ g e n . [ ' - In
~ ] special cases, the hydrolysis of alkyl transitionmetal complexes is also suitable.[51
We report here the reaction of the alkenyl ketone complex 1 with nitrogen monoxide in toluene. Nitrogen monoxide is not coordinated to the metal as an intact complex
ligand, but rather provides its oxygen for the Formation of
a terminal 0x0 ligand. Simultaneously, the alkenyl ketone
ligand fragments into a n acetylene and a methyl or acetyl
ligand.
[l] a) L. Hagelee, R. West, J. Calahrese, J. Normant, J . Am. Chem. SOC.101
(1979) 4888; h) B. Hagenhruch, K. Hesse, S. Hunig, K. Klug, Liebiqs
Ann. Chem. 1981, 256.
[2] M. lyoda, S. Tanaka, M. Nose, M. Oda, J . Chem. Soc. Chem. Commun.
1983, 1058.
131 G. Wilke, M. Kroner, B. BogdanoviC, Angew. Chem. 73 (1961) 755.
[4] G. Wilke, Pure Appl. Cheni. 50 (1978) 677.
Angen. Chem. Inr. Ed. Engl. 24 (198s) No. 6
[*I
[**I
Priv.-Doz. Dr. H. G. Alt, H. 1. Hayen
Laboratorium fur Anorganische Chemie der Universitat
Universitatsstrasse 30, D-8580 Bayreuth (FRG)
This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
0 YCH Verla~s,qe~ellschaf~
mhH. 0-6940 Weinheim. 1985
0570-0833/85/0606-0497 $ 02.50/0
497
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