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Metal-Promoted Cyclotrimerization of a 3-Phosphaalkyne Formation of a Molybdenum-Coordinated 1 3 5-Triphosphabenzene.

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ring of 1 (mean values 207.3(7) and 192.5(7) pm), which,
however, can only be referred to for comparison with care
because of the different orientation (apical and equatorial
in 1, apical in 3a). The formation of unsymmetrical Sb0 - S b bridges in 3a can be attributed to the positive partial
charge of the outer antimony atoms. This elicits a stronger
interaction between metal atom and the lone pair of the
bridge oxygen atom and a strengthening of the p-0-Sb
bond.
resembles that of alkynes. Phosphaalkynes thus represent
excellent potential building blocks for the facile construction of a wide variety of phosphorus-containing heterocycles. This capability has been demonstrated recently by the
synthesis of 1,3-diphosphacyclobutadienecomplexes.[" To
the best of our knowledge, 1 , which features two h5-phosphorus atoms, is the sole example of a 1,3,5-triphosphabenzene derivative."' Since the cyclotrimerization of al-
Experimental
3: A subpension of 1 (1.107 g, 1.5 mmol) 12, 41 and 2a (0.496 g, 2 mmol) o r 2b
(0.586 g. 2 mmol) in acetone (15 mL) was prepared at room temperature.
After a short time a clear yellow solution formed, which, after addition of
10 m L of 2.2-dimethoxypropane. was stirred overnight and finally evaporated down under vacuum to about 10 mL. The precipitated microcrystalline,
y e l l o ~powder was filtered off and washed with a small amount of ether.
M p.: 3a 204-206°C (decomp.): 3b 202-206°C (decomp.): yield 3a 30%; 3b
3 Z"'0.
Received: March 30, 1987 [Z 2169 IE]
German version: Angew. Chem. 99 (1987) 948
[ I ) H . Ldndolt, J . Prakt. Chem. 84 (1861) 328; L. Kolditz, M. Gitter, E. Rose],
2. Anorg. Allg. Chem. 316 (1962) 270; G. G. Long, G. 0. Doak, L. D.
Freedmann, J. Am. Chem. SOC.86 (1964) 209.
121 R. Riither, Dissertafion. Unlversitat Dortrnund 1986
[3] J. Bordner, G. 0. Doak, T. S. Everett, J. Am. Chem. Soc. 108 (1986)
4206.
[4] R. Riither. F. Huber, H. Preut, Z. Anorg. Allg. Chem. 539 (1986) 110.
[5] Single crystals suitable for X-ray structure analysis were obtained by recrystallization of 3a from chloroform/petroleum ether. Space group
12/a, 0=2443.6(7), b = 1066.5(5), c=2475(9) pm, [1=99.62(5)', 2=4.
Four-circle diffractometer CAD4 (Enraf-Nonius), MoK,. radiation, graphite monochromator, 28/01 scans, 2 6 8 6 2 3 . 5 " , 3742 observed (1>3u(/))
independent absorption-corrected reflections from 5 104 measured reflections, 412 refined parameters, unit weights, R =0.03, S=2.8, residual
electron density =0.2( 1)x loh e pm-'. Further details of the crystal structure investigation are available on request from the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-75 14 Eggenstein-Leopoldshafen 2 (FRG) on quoting the depository number CSD-52490, the
names of the authors, and the journal citation.
[6] R. Ruther, F. Huber, H. Preut, J . Organornet. Chem. 295 (1985) 21.
[7] a) H. Preut, R. Ruther, F. Huber, A o a Crystollogr. Sect. C42 (1986) 1154;
b) G. Ferguson, F. L. March, 0. R. Ridley, A o a Crystallogr. Sect. 8 3 1
(1975) 1260; G. Ferguson, D. R. Ridley, ibid. 29 (1973) 2221.
IS] Z. A. Starikova, T. M. Shchegoleva, V. K. Trunov, 1. E. Pokrovskaya, Sou.
Phyc Cr.v.itallogr. (Engl. Trans/.) 23 (1978) 547; H. Preut, R. Ruther, F.
Huber. Acra Crystallogr. Sect. C41 (1985) 358.
[Y] a) A. L. Beauchamp, M. J. Bennett, F. A. Cotton, J . Am. Chem. Sor. 91
(1969) 297; K.-W. Shen, W. E. McEwen, S. J. La Placa, W. C. Hamilton,
A. P. Wolf, ibrd. 90 (1968) 1718.
Metal-Promoted Cyclotrimerization of a
k3-Phosphaalkyne: Formation of a
Molybdenum-Coordinated l,3,5-Triphosphabenzenex*
By Andrew R . Barron and Alan H . Cowley*
Despite the fact that phosphaalkynes RC-P are isovalent with nitriles, their reaction chemistry more closely
1'1 Prof. A. H. Cowley, Dr. A. R. Barron
Department of Chemistry, The University of Texas at Austin
Austin, T X 78712 (USA)
[**I
[***I
This work was supported by the National Science Foundation and the
Robert A. Welch Foundation.
Note added by the editorial staff: The following communication reports a related cyclotrimerization giving rise to a valence isomer of a
1,3,5-triphosphabenzene derivative in the coordination sphere of vanadium: R. Milczarek, W. Riisseler, P. Binger, K. Jonas, K. Angermund,
C . Kruger, M. Regitz. Angew. Chem 99 (1987) 957; Angew. Chem. I n r .
Ed. €rig/. 26 (1987) 908.
Angena. Chem lnt Ed. Engl. 26 (1987) Nc). 9
kynes on transition-metal centers is well documented," 'I
we were prompted to investigate the corresponding chemistry of phosphaalkynes and report herein the first example of a coordinated 1,3,5-triphosphabenzene derivative.[*'*'
Treatment of the cycloheptatriene-molybdenum complex 2Is1with tBuC=P'"] afforded the orange, microcrystalline Mo complex 3 . Unfortunately, crystals of 3 were unsuitable for X-ray diffraction study.
fBu
\
f Bu
The composition Cz2H3(,MoOzP4
of 3 was established by
high-resolution mass spectroscopy ( M a , calcd 554.072 1 :
found 554.07 12, relative intensity 23%). The medium-resolution mass spectral fragmentation pattern revealed peaks
at m/z 498 (20%), 497 (19%), and 454 (7%), which correspond to the loss of two CO's, tBu, and tBuC=P, respectively."] The lowest m/z peak of significant intensity (12(!'0)
corresponds to [MO(~BUCP)~]@.
The IR spectrum of 3 exhibits two bands in the carbonyl
region (1950 and 1890 cm-'), which can be assigned to
symmetric and asymmetric C O stretching, respectively.
Use of these data leads to a cornputed['l inter-carbonyl angle of 89+3", thus indicating a cis disposition of the CO
ligands.
The 'H-NMR spectrum of 3 (300 MHz, C,D,, TMS ext.)
consists of two singlets at 6 = 1.46 and 1.30 in a 3 : I intensity ratio. In the "P('H)-NMR spectrum (32.2 MHz, C,D,,
85% H3P04, ext.) two singlets in the same intensity ratio
were detected at 6= + 25.2 and - 228.2. The high-field resonance falls in a region assigned previously to q2-attachment of tBuC=P to Mo.['] The "P chemical shifts for uncoordinated phosphabenzenes fall in the range 6 = 150300.1'.'01Although there is no literature precedent, a "P
chemical shift of 6=25.2 therefore seems plausible for an
q'-coordinated triphosphabenzene.
Experimental Procedure
3 : To a solution of 2 (0.476g, 1.75 mmol) in T H F (60 mL) was added
tBuC-P (1.05 g, 10.5 mmol). After refluxing for 12 h, the solvent was removed (in vacuo) and the residue extracted with cyclopentane (2 x 50 mL);
reduction in volume and cooling (-20°C) gave an orange solid. Yield: 0.57 g
(59Oh). m.p. = 8 3 T (dec.).
0 VCH Ver/uq.igesel/schuf/ m b H . 0 - 6 9 4 0 Wernherm. 1987
Received: May 4, 1987 [Z 2225 IE]
German version: Angew. Chem. 9Y (1987) 956
0570-0833/87/0909-0907 $ 02.50/0
907
[ I ] P Binger, R. Milczarek, R. Mynott, M. Regitz, W. Rosch, Angew. Chem.
98 (1986) 645; Angew. Chem. Int. Ed. Engl. 25 (1986) 644; P. B. Hitchcock, M. J. Maah, J. F. Nixon, J. Chem. SOC.Chem. Commun. 1986.
737.
[2] E. Fluck, G. Becker, 8 . Neumuller, R. Knebl, G. Heckmann, H. Riffel,
Angew. Chem. 98 (1986) 1018; Angew. Chem. Int. Ed. Engl. 25 (1986)
1002.
[3] G. W. Parshall: Homogeneous Catafysrs. Wiley, London 1980, p. 165.
141 The formal cyclotrimerization of PI has also been demonstrated. 0. J.
Scherer, H. Sitzmann, G. Wolmershluser, Angew. Chem. 97 (1985) 358;
Angew. Chem. lnt. Ed. Engl. 24 (1985) 351.
[ 5 ] E. W. Abel, M. A. Bennett, R. Burton, G. Wilkinson, J. Chem. Soc. 1958.
4559.
161 G. Becker, G. Gressner, U.Uhl, 2. Naturforsch. 836 (1981) 16; G. Becker, 2. Anorg. Allg. Chem. 430 (1974) 66.
171 The isotope distribution patterns of all fragment ions were computer
simulated.
[S] F. A. Cotton, G. Wilkinson. Aduanced Inorganic Chemistry. 4th ed., Wiley, London 1980, p. 1074; Anorganische Chemie, 4th ed., Verlag Chemie, Weinheim 1982, p. 1094f.
191 R. Bartsch, P. B. Hitchcock, M. F. Meidine, J. F. Nixon, J. Organomer.
Chem. 266 (1984) C41.
(101 K. Dimroth in A. R. Katritzky, C. W. Rees (Eds.): Comprehensiue Heterocyclic Chemistry, Vol. I . Pergamon, Oxford 1984, p. 506.
gands,".'' reaction of 1 and the Cp,Zr fragment (prepared
in situ) affords a 1,3-diphosphabicyclo[l.l.O]butane-2,4diylzirconium complex.131Free or complexed cyclotrimers
of h3-phosphaacetylenes141were previously unknown.'***1
Herein we report a metal-promoted cyctotrimerization of a
h3-phosphaalkyne.
Reaction of tert-butylphosphaalkyne 1 with the naphthalenevanadium complex 2,15'which is a suitable source
of Cp*V fragments (Cp* = q5-pentamethylcyclopentadienyl), results in liberation of naphthalene in an exothermic
reaction and formation of a new organovanadium complex
as dark brown crystals having the composition
[Cp*V(PCtBu)J 3 (MS, elemental analysis). At room temperature, 3 readily reacts with 1 mol of C O yielding complex 4 (MS, elemental analysis) as dark green crystals.
Metal-Promoted Cyclotrimerization of a
A3-Phosphaalkyne: Formation of
Vanadium-Complexed Valence Isomers of a
1,3,5-Triphospha benzene* *
By Roman Milczarek. Wolfgang Riisseler, Paul Binger, *
Klaus Jonas, Klaus Angermund, Carl Kriiger, and
Manfred Regitz
tert-Butylphosphaacetylene 1 undergoes cyclodimerization on q5-cyclopentadienyl metal complexes: Whereas
reaction of 1 and cyclopentadienylbis(ethene)cobalt results in the formation of a h3-1,3-diphosphacyclobutadienecobalt complex with displacement of the ethene li-
2
+
C9'
4
[*I Priv.-Doz. Dr. P. Binger, Dr. R. Milczarek, Dr. W. Riisseler,
Prof. Dr. K. Jonas, Dr. K. Angermund, Prof. Dr. C. Kriiger
Max-Planck-lnstitut fur Kohlenforschung
Kaiser-Wilhelm-Platz I , D-4330 Miilheim a. d. Ruhr
Prof. Dr. M. Regitz
Fachbereich Chemie der Universitat
Erwin-Schrodinger-Strasse,D-6750 Kaiserslauiern
[**I This work was supported by the Stiftung Volkswagenwerk.
[***I Note added by the editorial staff: A related cyclotrimerization in which
a 1,3,5-triphosphabenzene derivative is formed in the coordination
sphere of molybdenum I S also reported in this issue: A. R. Barron, A.
H. Cowley, Angew. Chem. 99 (1987) 956; Angew. Chem. In! Ed. Engl.
26 (1987) 907.
908
0 VCH Verlagsgesellschafr mbH. 0-6940 Wernheirn. 1987
Fig. 1. Top: Molecular structure of 3. C2SH42P.,V,0=9.664(2), b= 17.935(3).
c = 16.015(1) I\,B= 101.91(l)o, V=2716.0 I\',&.,,,cd= 1.19 g cm-',p(MoK,,)=
5.36 cm-', 2 = 4 , space group P2,/n, 6537 measured reflections ( + h , + k ,
+ I ) (averaged according to point group symmetry 2/m), 6120 unique reflections, 4424 observed ( I > 20(I)), empirical absorption correction (min, 0.861 ;
max, 1.083), 262 refined parameters, R =0.043, R,, =0.050. Selected distances
[A] and angles ["I: V-PI 2.382(1), V-P2 2.437(1), V-P3 2.702(1), V-CI 1.849(3),
V-ClI 1.993(3), PILP3 2.206(1), PLC6 1.845(3), PI-CI 3.047(3), P2-CI
1.850(3), P2-C6 1.904(3), P2-CIl 1.842(3), P3-C6 1.915(3), P3-CI1 1.937(3);
C6-Pl-P3 55.6(1), C6-PI-V 87.3(1), P3-PI-V 72.1(1), C1 I-P2-C6 88.9(1), C I I P2-Cl 98.1(1), CII-P2-V 53.3(1), C6-P2-C1 104.6(1), C6-P2-V 84.4(1), CI-P2V 48.8(1), C I I-P3-C6 85.9(1), CI 1-P3-P1 99.5(1), CI I-P3-V47.4(1), C6-P3-PI
52.6(1), C6-P3-V 77.1(1), PILP3-V 57.0(1), P2-CI-V 82.4(1), P3-C6-P2 91.9(1),
P3-C6-P1 71.8(1), P2-C6-PI 107.2(1), P3-CII-P2 93.2(1), P3-CIl-V 86.9(1),
P2-Cl I-V 78.8(1) [6].-Bottom: Molecular structur? of 4 . C2,H,20P3V,
a=18.525(1),b=15.674(1),~=9.555(1)~, V = 2 7 7 4 . 4 A 3 , ~ E . , l r t l = 1 . 2 3 g c m - 1 ,
p(MoK,.)=5.31 c m - ' , 2 = 4 . Space group Pnma, 4489 measured reflections
( + ) I , + k , + I ) (averaged according to point group symmetry mmm), 4135
unique reflections, 2995 observed reflections ( I > 2 ~ ( 1 ) ) .154 refined parameters, R=0.040, R,,=0.047. Selected distances [A] and angles ["I: V-PI
2.459(1), V-CI 2.17112). PI-CI 1.801(2), PLC6 1.886(1), P2-Cl 1.859(2), P2C6 1.878(3); C6-PI-V 83.3(1), C6-PI-CI 88.0( I), V-PI-CI 58.9(1), C6-P2-CI
86.6(1), CI*-P2-CI 102.6(1), P2-CI-V 85.8(1), P2-CI-PI 94.3(1), V-CI-PI
75.8(1), P2-C6-P1 91.0(1), PI*-C6-P1 105.2(2) 161.
0570-0833/87/0909-0908 3! 02.50/0
Angew Chem Int. Ed. Engl 26 (1987) No. 9
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