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Nitrogen Monoxide as a Source for Oxo LigandsЧAcetylene-Oxo Complexes of Tungsten.

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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[7] C. Kruger, Y:H. Tsay, unpublished results.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
The mechanism of this instantaneous reaction is still unclear. Nitrogen monoxide, which is readily reduced, could
react via a transient hyponitrito complex to form dinitrogen m~noxide,~'.'~
thus acting as a source of oxygen.[*]
However, no N 2 0 is detected in the reaction gas. Complex
1 does not react with NOz to form 2a and 3a. With air,
only a small amount of 3a is formed after 30 min.
e+
l
+ NO
toluene
-
78OC
I
1
Experimental Procedure
0 7 W p
c ===c,
H'
H
2a (25%)
3a (47%)
In order to prepare acetylene-oxo complexes of type 2,
the reaction of the acetylene-alkyl-carbonyl complexes
4a-c with NO (as a source of oxygen) can also be used.
For L = C5H5 and C5H4Me, the acetylene-nitrosyl complexes 5I9l are formed in 38 and 61% yield, respectively. No
0x0 complexes result from the reaction of the chromium
and molybdenum analogues of 1 with NO under the same
reaction conditions. The reaction of 6a with NO did not
afford a tractable product; complex 6b reacts with NO to
give the dinitrosyl complex 7 .
[(C,R,)(CO),h( HC=CH-C(b)MeJ]
6 ; a, R = H , M = M o ; b, R = M e , M = C r
[(C,Me,)Cr(NO)z(NOz)l
7
[Re(0)(C2MeZ)I]
9
[W(0)(CzH2)(S~CNR2)21
8, R = Me, Et
[(C,H,)W(NO),(HC=CHCOMe)]
10
In the IR spectra (cf. ["I) of the acetylene-oxo complexes
2a-c and 3a, a relatively intense band is observed at 940
cm-', which is characteristic of the W=O vibration.['-5'
The v(CC) absorption of the C2H2 ligand appears as a
strong band in the region 1580-1630 cm-'. Similar values
have been reported for the alkyne-oxo complexes 8l4]and
9.["l Especially noticeable in the 'H-NMR spectra'ln1is the
large downfield shift of the signals of the methyl ligands.
This is due to the positive charge induced on the central
metal atom by the 0x0 ligand. A similar effect is observed
for the chemical shifts of the C2H2hydrogen atoms in the
'H-NMR spectrum and for those of the C2H2 carbon
atoms in the "C-NMR spectrum.
The alkyne ligand in the 0x0 complex 8, R=Me,[41has a
relatively low barrier for rotation around the metal-alkyne
498
bond (AG' =66.4 kJ/mol); the C2H2 signals of the complexes 2a-c and 3a do not change upon heating of the
samples to 130°C (in [D,]toluene under pressure). This indicates that the complexes 2a-c and 3a exhibit high
tungstacyclopropene character and that tungsten is present
in its highest formal oxidation state +6.
Selective nitrosylation of 1 is achieved when nitrosylchloride is used as a nitrosylation reagent: in this case,
equal proportions of the stable alkenyldinitrosyl complex
and the known compound 11 are formed.
0 V C H Verlagsgesellcchafr mbH, 0-6940 Weinheim, 1985
All operations were carried out under inert atmosphere with dry solvents.
Reaction of 1 with N O : 1 (0.24 g, 0.64 mmol) [I21 was dissolved in 20 mL of
toluene. The solution was cooled to -78°C and allowed to react with excess
NO gas. The solution immediately changed from dark red to orange. Subsequent column chromatography (silica gel/pentane) afforded the yellow 0x0
complex 2a (eluted with ether) and the orange acetyl compound 3a (eluted
with tetrahydrofuran). Both solutions were evaporated to dryness under high
vacuum. 2 a : m.p. =77-80°C (under argon), m / z 306 (relative to '84W),yield
0.05 g (25'?/0). 3a, oil at room temperature, m / z 334 (relative to ""W), yield
0.10 g (47%).
Received: January 10, 1985;
supplemented: April 3, 1985 [Z 1129, 1156 1 4
German version: Angew. Chem. 97 (1985) 506
CAS Registry numbers:
1, 63325-53-1; Za, 96395-41-4; 2b, 96395-42-5; Zc, 96395-43-6; 3a, 96395.447: 4a, 62798-73-6; 4b, 96395-45-8; 4c, 96395-46-9; 5 , (I =q'-C5Hq), 87862-575 ; 6, ( l = ~ ) ' - c ~ H , M e )96395-47-0;
,
6a, 64466-36-0; 6b, 96395-48-1: 7, 9639549-2; 10, 96395-50-5: 11, 12091-65-5; nitrogen monoxide, 10102.43-9; nitrosyl chloride 2696-92-6.
[ I ] a) W. A. Herrmann, R. Serrano, H. Bock, Angew. Chem. 96 (1984) 364;
Angew. Chem. I n / . E d . Engl. 23 (1984) 383; b ) W. A. Herrmann, R. Serrano, U. Kiisthardt, M. L. Ziegler, E. Guggolz, T. Zahn, Angew. Chem.
96 (1984) 498: A n g e w . Chem. Inr. E d . Engl. 23 (1984) 515; c) W. A. Herrmann, R. Serrano, A. SchBfer, U. Kusthardt, M. L. Ziegler, E. Guggolz,
J . Organomet. Chem. 272 (1984) 55.
[2] A. H. Klahn-Oliva, D. Sutton, Organnmerallics 3 (1984) 1313.
13) N. G . Bokiy, Y. V. Gatilov, Y . T. Struchkov, N. A. Ustynyuk, J . Organomet. Chem. 54 (1973) 213.
J . L. Templeton, B. C . Ward, C. J.-J. Chen, J. W. McDonald, W. E. Newton, Inorg. Chem. 20 (1981) 1248.
1. Feinstein-Jaffe, D. Gibson, S. J. Lippard, R. R. Schrock, A. Spool, J .
Am. Chem. SOC.106 (1984) 6305.
J . A. McCleverty, Chem. Rev. 79 (1979) 53.
A. R. Middleton, G. Wilkinson, J . Chem. Soc. Dalton Trans. 1981.
1898.
F . Bottomley, I. J. B. Lin, P. S. White, J . A m . Chem. Sac. IU3 (1981 j
703.
H. G. Alt, H. 1. Hayen, Angew. Chem. 95 (1983) 1030: Angew. Chem. Inf.
E d . Engl. 22 (1983) 1008: Angew. Chem. Suppl. 1983, 1364.
2 a : I R : v(CC)= 1585 (THF), v(W=0)=940 c m - ' (KBr). 'H-NMR
([Da]acetone, -2O"C, 2.04 internal standard): 6=6.07 (s, C,H,),
S(A)=10.35 (d, q: q : 4J(HH)=1.3 Hz), S(B)=8.90 (d) (AB system,
J(A,B)=0.5 Hz; 'J(WH)=9.7 and 7.0 Hz; C2HZ), 1.71 (d, "J(HH)=1.3
Hz; CH3). "C('H)-NMR ([DJacetone, -2O"C, 29.75, internal standard): 6(CsH5)= 105.3. 6(CrH2)= 152.6, 148.4. S(CH,)=2.3: 'J(WC)=
89.7 Hz.-3a:
IR: v(C=0)=1630, v(CC)= 1630 (THF), v(W=O)=
950 c m - ' (Nujol). 'H-NMR ([D,]acetone, -2O"C, 2.04, internal standard): 6=6.10 (s, CsHs), &A)= 10.38, S(Bj=8.80 (d) (AB system,
J(AB)=0.5 Hz; 'J(WH)=6.8 and 6.6 Hz; C2H2);2.75 ( 5 , CH3). "C('H}NMR ((D6]acetone, -20"C, 29.75 internal standard): G(C<H,f= 105.9,
6(C=O)=261.4, &(C2H2)=144.0, 139.3: 'J(WC)=23.9 and 58.1 Hr,
S(CH7) = 52. I.
J. M. Mayer, T. H. Tulip, J . Am. Chem. Soc. 106 (1984) 3878.
a) H. G. Alt, Angew. Chem. 88 (1976) 800; Angew. Chem. I n t . E d . Engl.
15 (1976) 759; b) H. G. Alt. Chem. Ber. II0 (1977) 2862.
I R : v(NO)= 1780, 1625, v(C=O)= 1605 c m - ' (THF). ' H - N M R ([DJacetone, -2O"C, 2.04 internal standard): S=6.23 (s, 5 H, C,H,), 6(A)=7.80
(d, I H),S(B)=5.12 (d, I H)(AB system,J(AB)=6.1 Hz),S= 1.90(s, 3 H ,
Me). "C-NMR ([D,]acetone, -20°C, 29.25 internal standard): S = 105.7
(C,H,), 175.5 (CO), 148.4, 92.5 (-CH=CH-), 27.7 (Me). MS: m / z 414
(relative to '"'w), decomp. 171°C.
0570-0833/85/0606-0498 $! 02.50/0
Angew. Chem. Int. Ed. Engl. 24 (19851 No. 6
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