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First Insertion Reaction of Carbon Monoxide into a Rhenium-Carbon -Bond.

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A solution of ( I l i ) (10 g, 19.3 mmol) in 80 ml of anhydrous
toluene, which contains 5 ml ethanol, is heated under reflux
for 12 h. The solvent is removed and the residue digested
with 50 ml pentane. Precipitated Ph3P0 is separated off and
the previously unknown 4,5,6,6a-tetrahydro-2( 1 H)-pentalenone ( 1 3 ) (1.41 g) isolated by bulb-to-bulb distillation.
Received: January 24, 1980 [Z 579 IE]
supplemented: August 8, 1980
German version: Angew. Chem. 92, 856 (1980)
CAS Registry numbers:
( I ) , 21385-80-8; ( 2 ~ )64-19-7;
.
(Zb), 107-92-6. (Zc), 621-82-9; (Zd), 65-85-0 (4a),
75066-52-3; (4b). 75066-534 ( 4 ~ 175066-54-5;
,
pa). 13162-69-1; (5b). 75066-556; (k),75066-56-7; (Sd), 13162-68-0; (6a), 1439-36-7; (6b). 17615-01-9; (6c),
.
(8b). 611-73-4, ( 8 ~ )600-18-0;
.
(Sd),
13527-03-2; (6d), 859-65-4 ( 8 ~ ) 127-17-3;
1821-02-9; @el, 119-67-5; @A. 2051-95-8; (8g). 4316443; (8h). 1438-96-6; (Si),
1460-38-4; (8~).2275-26-5; (Bk), 3296-45-5; @I), 39762-51-1; (8m). 4376-18-5;
( / I / ) . 75066-57-8; ( l l g ) , 75066-58-9; ( l l h ) , 75066-59-0; ( 1 li), 75066-60-3; ( 1 IJ).
75066-61-4; ( I l k ) , 75066-62-5; (110, 75066-63-6; ( f i m ) , 75066-64-7, (1301.
75066-65-8; (/3b),75066-66-9; (14a), 3120-04-5; (14b), 75066-70-5; ( I ~ c ) , 3120.
(158, 3810-26-2; .(ISg), 53253-06-8;
06-7; (14d), 75066-67-0; ( 1 4 ~ )75066-68-1;
(ISh), 39163-29-6; (ISi), 72200-4-0; (lSj), 1196-55-0 (ISk), 1489-28-7; (iSl),
71370-304; (15m). 42393-04-4: (16). 75066-69-2
[I] H. J. Bestmann, G. Schmrd, Angew. Chem. 86,274 (1974); Angew. Chem Int.
Ed. Engl 13, 273 (1974).
[2] Synthesis of the compounds (5) from acyl ylides (6) and phenyl isocyanate
(7) cf. S. Trippelt, D. M . Walker, J . Chem. SOC.1959, 3874.
131 Synthesis of acyl ylides (6). H. J. Bestmann, Angew. Chem. 77, 651 (1965).
Angew. Chern. Int. Ed. Engl. 4, 645 (1965)
[4] R. L. Augustine, J. A . Capufo,Org. Synth. Coll. Vol. 5, 869 (1973).
[ 5 ] P. M . McCurry, R. K. Singh, J. Org. Chem. 39, 2317 (1974); R. N . Lacey, J.
Chem. SOC.1960, 1639.
[6] H. 0.House, W. A . Kleschick. E. J. Zaiko, J. Org. Chem. 43, 3653 (1978).
171 Cf. also: K. Nickisch, W. Klose, E. Nordhoff; i? Bohlmann, Chem. Ber. 113,
3086 (1980).
The colorless, thermally stable metallacycles (3) sublime in
a high vacuum and are soluble in all common organic solvents. They were characterized by complete elemental analysis, IR, MS (Table I), and 'H-NMR spectra [(3a),(36) (C6D6
rel. to TMS): 6=0.89, 1.01 (s, C(cH3)2), 0.92, 1.04(d, J=2.5,
3.1 Hz, P-Re-CH2),
3.19, 3.51 (d, J=17.6, 17.3 Hz,
P-0-CH,)],
as well as by crystal structure analysis of
(3b)1'1.
Table 1. IR and MS data, and melting points of compounds (3)-(6).
u(C0)
[cm '1
(34
(3b)
(4@
f5b)
16bi
2978 rn [a]
1998 s
1975 vs
1945 vs
2082 m [a]
2001 s
1984 vs
1943 vs
21 13 m [b]
2046 m-s
2020 vs
1979 s
2048 vs [c]
1986 vs
1920 vs
21 11 rn [d]
2021 sh
2015 vs
I952 s
1393 rn [c]
1608 s [d]
~ S O d
v(
1161 m [el
1046 m
C=O)
m / e ( M " ) [fi 446
570
634 [gj
840
598
M.p.["C]
117
132
112
= 96
8
[a] In n-hexane. [b] In CCI,. [c] In toluene. [d] In CHC12. [el In KBr.
"'Re. [g] Field desorption.
[fl Rel. to
First Insertion Reaction of Carbon Monoxide into
a Rhenium-Carbon u-Bondr**'
By Ekkehard Lindner and Giinter von A M [ * ]
Dedicated to Professor Helmut Behrens on the occasion
of his 65th birthday
Carbon monoxide has great importance as a reactant in
the hydroformylation of olefins[l1;this reaction is catalyzed
by carbonyl-metal derivatives[21.The lengthening of the Cchain of the metal-bound olefin occurs via labile a-alkyl
complexes, which insert CO into their M-C o-bond. Such
insertions with corresponding carbonyl-rhenium compounds
have not previously been describedf31.We successfully performed this reaction with the six-membered rhenacycles (3)
which we were able to obtain by heterolytic cleavage of the
Re-Re bond in the dianionic, binuclear complexes
with neopentylene bis(trifluoromethanesu1fonate) (2).
Fig. 1. ORTEP representation of (3b) (vibrational ellipsoids with 50% probability).
(OPR2)(OC:,~e NaO
( O P W (OCI43e
(1) +
,C Hz Z
IH~C)ZC,
CHzZ
K*CO,/DME
- 1/2 [(OC)4Re(PR20)l,
- NaZ
i2)
Z = OS02CF3
/a],R = CH3; Ih], R = CsH5
[*]
*
(gPRz):e(CO),
FHZ
Nao
ZH2C-C(CH,)z
1-
NaZ
RZ
P-0
(OC)&'d
228.5(9)
154.6(13)
150.4(11)
147.3( 12)
160.3(6)
239.9(2)
89 8(2)
123.2(6)
1 1 1.3(7)
113.3(7)
121.2(6)
1 16.0(2)
(3)
Preparation and Properties of, and Reactions with Metal-Containing Heterocycles, Pan 6. This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen 1ndustrie.-Part 5: E. Lindner,
Eberle, J. Organomet. Chem 191, 143 (1980).
0 Verlag Chemie, GmbH, 6940 Weinheim. 1980
P2-Re3-C4
Re3-C4-C5
C4-CS-C6
C5-C6-01
C6-01-P2
01-P2-Re3
01-P2
P2-Re3
Prof. Dr. E. Lindner, DiplLChem. G . von Au
Institut fur Anorganische Chemie der Unwersitat
Auf der Morgenstelle 18, D-7400 Tubingen 1 (Germany)
824
Angles
Re3-C4
c4-c5
C5-C6
C6-01
(CH,),
r*]
["I
Bond lengths [pm]
(36) has a distorted chair conformation with a dihedral angle of 115.4' between the C5, C6, 0 1 plane and the approximate plane through 01, P2, Re3, C4, and C5. Thus the tetrahedral angle at C6 is only slightly enlarged. Due to the steric
effect of both methyl groups, the same applies to the angle at
C5, resulting in a considerable expansion of the tetrahedral
angle at C4. This indicates a considerable ring strain, which
leads to greater reactivity.
0570-0833/80/10~0-0824
$ 02.50/0
Angew. Chent. Inl. EZ. Engl. 19 (1980) No. 10
Although in (36) the Re3-C4 distance is clearly greater
than the sum of the single bond radii, and SO2 can easily
cleave the Re-C a-bond with ring expansion to thermally
stable (4b), the insertion of CO will not proceed until 100 "C
and 800 bar. However, if the metal-coordinated carbon monoxide in (3b) is activated with a Lewis acid, such as A1Br3r61,
then the colorless adduct (Sb), obtained in toluene, takes up
CO at 20 "C without pressure. Subsequent hydrolysis with
cleavage of the aluminum group, leads to the colorless, ringexpanded, insertion product (6), which is thermally labile. In
solution, CO is eliminated at 20 "C. In the spectra of (4b) and
(6b), in contrast to (3b), v(C0) is shifted characteristically to
higher frequencies. (4b), (5b), and (66) are soluble only in
more strongly polar organic solvents.
Experimental
(3a, b): A solution of ( l a ) or (Ib) (1.23 mmol) in dimethoxyethane (DME) (50 ml) is added dropwise to (2) (1.10
mmol) and K2C03 (2 mmol) in DME (20 ml) at -10°C
[(3a)Jor 20°C [(3b)],and is heated for 10 h at 60 and 84"C,
respectively. After filtration (D4), (3a) and (3b) are purified
on a chromatographic column (I= 0.3 m, diam. = 25 mm, silica gel, act. 111, eluent: n-hexane). Final purification is by distillation (20 oC/10-2 torr) and recrystallization from n-hexane. Yield: 12-27%.
(46): (3b) (0.38 mmol) in liquid SO, (10 ml) is left to react
for 1 h at -40°C. After removal of SOz, analytically pure
(46) remains in quantitative yield.
(66): (3b) (0.21 mmol) and AIBr, (0.21 mmol) are dissolved in toluene (20 ml) in the absence of air and moisture.
After several minutes, when (56) has formed, CO is bubbled
through the solution for 1 h at room temperature. The solvent is removed and the solution hydrolyzed with aqueous
CHCl,, then filtered (D4). The solvent is removed under vacuum at - 10 "C, and the residue of (6b) is washed with nhexane. Yield: 45%.
Double Cycloaddition Yielding a Tricyclic
Diphosphoranel*'I
By Alfred Schmidpeter, Werner Zeiss, Dietmar Schomburg,
and William S. Sheidrick'''
Dedicated to Professor Roif Huisgen on the occasion of
his 60th birthday
In criss-cross addition to a dienic four-membered chain,
the first [3 + 21-cycloaddition is followed by a second one,
and a five/five-membered bicyclic species results. In the case
of double addition to the three-membered chain of an enephosphane described below, the second addition is likewise a
necessary consequence of the first one. The role of the second ene is assumed by PI" which increases its coordination
number by two and becomes the Pv bridgehead of a four/
five-membered bicyclic species.
(Methy1eneamino)phosphanes"' such as ( I ) represent a
special case of 1,3-dipoles free of formal charges. They react
with electron-deficient olefins and acetylenes via [3 + 21-cycloadditions to form 1,2-azaphospholes and 1,2-azaphospholines, respectivelyr2].Their reaction with carbonyl compounds is more complicated. We found that dimethoxy(diphenylmethy1eneamino)phosphane ( I ) and p-nitrobenzaldehyde (2) afford a 2 :2 and a 1:2 addition product in 40 and
30% yield, respectively, which prove to be the tricyclic diphosphorane (4) and the methyleneaminoethyl phosphate
(6). Both compounds must be regarded as the result of double cycloadditions: a (3+ 21-addition forming the thermodynamically favorable PO bond leads, contrary to kinetic
expectations, regiospecifically to the 1,3,2h5-oxazaphosphol-
MeO,
P-N=C Ph2
M e d
(1)
R-C H-O
Received: March 4, 1980 [ Z 580 I E ]
German version: Angew. Chem. 92, 843 (1980)
(3)
CAS Registry numbers:
( l a ) . 69042-02-0; (1bJ.69042-03-1: (2J. 72610-41-4;(30).75067-39-9; (3bj, 7506740-2: (4b). 75067-36-6, (Sb), 75067-41-3;(66). 75067-42-4;SOz, 7446-09-5;AIBr?.
7727-15-3
i
+
MeOH
[ I ] R. L. Pruelr, Adv. Organomet. Chem. 17, 1 (1979).
[ 2 ] C.-Y. Hsu, M. Orchin, J. Am. Chem. SOC. 97, 3553 (1975).
131 R. B. King. A. D. King. Jr.. M. 2. Iqbal, C. C. Frazier. J. Am. Chem. SOC.100.
1687 (1978).
[4] E Lindner. G. con .4u. H:J. Eberle, Z. Naturforsch. B 33,1296 (1978).
[ S ] (36) crystallizes from n-heptane as triclinic crystals, space group Pi.
a=829.9(4). b=970.0(2), c = 1376.9(3) pm. a=92.85(2), p=97.37(3),
y= 106.48(3)".Z= 2, pCd,'= 1.801 g cm -'. The structure was solved with Patterson- and difference-Fourier syntheses and anisotroprcally refined (except
HI with the program system SHEL-76 until R=0.038. for 3250 independent
reflections (ff = 3-25"). We would like to thank Mrs. M. Gekeler and Mr.
K:P Frank for their help with the structure determination
[6] S. B. Bulls. E. M . Holl, S. H. Siruuss, N . W. Alrock, R. E Srimson, D. F
Shriver. J. Am Chem. SOC.101. 5861 (1979).
Angew. Chem. Int. Ed. Engl. I9 (1980) No. I 0
I*]
Prof. Dr. A. Schmidpeter, Dr. W. Zeiss
Institut fur Anorganische Chernie der Unrversitat
Meiserstrasse 1, D-8000 Munchen 2 (Germany)
Priv.-Doz. Dr. W. S . Sheidrick, Dr. D. Schomburg
Gesellschaft fur Biotechnologische Forschung mbH
Mascheroder Weg I. D-3300 Braunschweig-Stockheim (Germany)
I**] Four- and Five-Membered Phosphorus Heterocycles. Part 46. Thrs work
was supported by the Fonds der Chemischen 1ndustrie.-Part 45. K. C. Dash. H .
Schmidbaur, A. Srhmidpeter, Inorg. Chim. Acta 46, 167 (1980).
0 Verlag Chemre, GmbH, 6940 Weinherm, 1980
0570-0833/80/1010-0825
$ 02.S0/0
825
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