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Nonaphenyltristiboxane-1 5-diyl Disulfonates.

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171 M. H. Chisholm, Po!i,hedron 2 (1983) 681.
[8] Mok,,, 6'<28<45". Of the 2917 reflections collected, 2884 were
unique, and the 2543 with F>2.33rr(f) were used in the full least
squares refinement. Final
residuals are R(f)=0.028
and
R,,(F)=O.O32.-Further details of the crystal structure investigations are
available o n request from the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-7514 Eggenstein-Leopoldshafen2 (FRG), on
quoting the depository number CSD-52610, the names of the authors,
and the journal citation.
19) a) T. J. Ziegler, J. Am. Chem. Snc. 106 (1984) 5901 : ibrd. 1#7( 1985) 4453;
b) E. M. Kober, D. L. Lichtenberger, ibid. 107 (1985) 7199: c) W. C.
Trogler, J. Chem. Educ. 57 (1980) 424.
[lo] a) F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 4th Ed.,
Wiley, New York 1980; b) N. N. Greenwood, A. Earnshaw: Chemi.ytry of
the Elements. Pergamon Press, Oxford 1984: c) H. Block, H. Muller,
Inorg. Chem. 23 (1984) 4365.
[ I 11 F. A. Cotton, R. A. Walton: Mulfiple Bonds Between Metal Afoms. Wiley-Interscience, New York 1982.
trimethylantimony compounds analogous to 3 cannot be
synthesized, and the reaction of CF,SO,H with 1 leads
only to the distiboxane.
The X-ray structure analysis of 3ai5]reveals a chain of
three 0-coupled SbPh, units; two monodentate bonded
2,4-dinitrobenzenesulfonicacid residues function as terminal groups of this chain (Fig. 1). The trigonal-bypyrimidal
Nonaphenyltristiboxane-1,5-diyl Disulfonates**
By Robert Ruther, Friedo Huber,* and Hans Preut
The long known distiboxanes (XR,Sb),OL'I may be regarded as products of the partial hydrolysis of triorganoantimony(v) compounds R,SbX, (X = e.g. CI). A hydrolysis proceeding beyond the stage of the distiboxanes and
accompanied by condensation reactions takes place only
under relatively drastic conditions. In such a case polymeric (R,SbO), is formed. Intermediates of this reaction
are not known. We have now succeeded in synthesizing
and characterizing for the first time the tristiboxanes
XPh3Sb-O-SbPh3-O-SbPh3X
(X=2,4-(NOz)ZC,H,SO,,
2,4,6-(NOz),C,H,so,).
Dimeric triphenylantimony oxide li2.31
reacts with the
free sulfonic acids 2 (molar ratio 3 :4) in the presence of
2,2-dimethoxypropane as water-trapping reagent to give
the compounds 3 [Eqn. (a)].
2 XPh3Sb-O-SbPhz-O-SbPhzX
+ 2H20
3a, b
a , X=2,4-(N02)2C,H3S0,;
1
Fig. I . Crystal structure of 3a viewed along the Cz axis, which runs through
the atoms Sb2, C61, and C64 (ORTEP 11, without H atoms); C61 and C64
are hidden by Sb2, C63 is hidden by C62. Selected bond lengths [pm] and
angles ["I: Sbl-Ol l92.1(4), Sb2-01 203.5(5), S b l - 0 1 I 250.9(5), S1-01 I
145.8(5), S I - 0 1 2 143.0(7), SI-013 144.9(7); Sbl-01-Sb2 140.8(3), 0 I-Sbl011 174.4(2), 01-Sb2-01' 176.8(2).
arrangement of the three equatorial phenyl groups is virtually undistorted, while the phenyl groups of the outer antimony atoms are tilted from the equatorial plane in the
direction of the respective sulfonate group (mean value of
the 011-Sb-C angle ( C = C I I , C21, C31): 82.3"), and the
01-Sbl-011 angle of 174.4(2)' also deviates more from
linearity than the 01-Sb2-01' angle. The large Sbl-011
distance of 250.9(5) pm (cf. Table l), the distortion also
found in other comparable compounds, and the IR data
(Table 2) point to a relatively high degree of ionic character for the Sb-OS02 bonds.
b, X=2,4,6-(NO2),C6H2SO3
Table I.Typical S b - 0 distances in stibonylsulfonates.
3a and 3b form yellow, air-sensitive crystals which are
moderately soluble in alcohol and dimethyl sulfoxide,
sparingly soluble in chloroform, and very sparingly soluble
in water and hexane. The 'H-NMR spectra of 3a and 3b
exhibit several multiplets, indicating concomitant presence
of various phenylantimony species in solution. Comparable observations on hexaphenyl-lh5,3h5-distiboxane-1,3diyl disulfonates in CHC13 or acetone implicate establishment of rearrangement equilibria.l*l In analogous reactiogs
of 1 with less acidic sulfonic acids ( X = M e S 0 3 , PhS03,
4-CH3C6H4S03,HOCH,CH,SO,) mixtures of the corresponding distiboxanes and excess oxide are formed.
As previously r e p ~ r t e d , ' the
~ ] preparation and structure
of the organoantimonyl(v) sulfonates are strongly influenced by the nucleophilicity of the respective sulfonate
ion, while the size of the organic moiety of the sulfonate
group plays only a subordinate role. Moreover, the electronic properties and the size of the organo-substituents on
the antimony atom are of considerable importance."' Thus
[*] Prof. Dr. F. Huber, Dr. R. Riither, Dr. H. Preut
Fachbereich Chemie der Universitat
Otto-Hahn-Strasse 6, D-4600 Dortmund 50 (FRG)
[**I This work was supported by the Fonds der Chemischen Industrie.
906
0 V C H Verlagsgesell.~chajimbH. 0-6940 Weinherm. 1987
Compound
4 S b - O ) Ipml
Ref.
Ph,Sb(OX,Hs)2
Ph,Sb0,SC,H5. H 2 0
( PhlSb0.,SC,H5)20
212.8(2) and 210.6(3)
250.6(4)
224.7(5) and 228.0(5)
[41
I61
[7al
Table 2. IR data of the compounds 3 ( N u J o ~G; i n cm-I).
3a
3b
1275
1290
1192/1 185
1212
1020
1030
750
750
Sb-0-Sb bridges can be linear'81or bent.['I In 3a the angle is 140.8(3)" and thus essentially corresponds to the values observed in bent di~tiboxanes.['~
Remarkable is the unsymmetric disposition of the Sb-0-Sb bridges. The Sb2-0 1
distance (203.5(5) pm) corresponds to the normal S b - 0 distance for a covalent bond in organoantimony(v) compounds.['] The substantially shorter Sbl-Ol bond (192.1(4)
pm) is comparable to the p-0-Sb bonds in the previously
known distib~xanes.['.~]Substantially different p-0-Sb
bonds are also found in the Sb-0-Sb-0 four-membered
0570-0833/87/0909-0906 $ 02.50/0
Angew Chem. In!. Ed. Engl. 26 (1987) No. 9
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
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