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X-Ray Structure Analysis of Tri--chlorobis[bis(tri-n-butylphosphine)-ruthenium Chloride].

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with a coupling constant of 16 Hz. The signal of the phenyl
protons ortho to the imino nitrogen atom is a multiplet
centered at 7 = 2.4 (relative intensity 2); and that of the
remaining aromatic protons is a multiplet centered at T 2.8
provide an
(relative intensity 8). Analogous substances
indication of the shift of signals of the CH2 protons on the
four-membered ring to lower field owing to the neighboring
nitrogen atom. Further, we also derive structure ( I ) from the
mass spectrum, specifically from the appearance of the ion
M-42 and of a fragment at m ' e 42 (H~C-N-CHZ). The
compound is found to have molecular weight 234. The UV
spectrum (in alcohol) includes a n absorption band at 244 nm
(E = 12200). In the I R spectrum (KBr) the C = N absorption
is at 6.2 pm and, remarkably, three absorption bands occur
between 9.98 p n and 10.16 pm.
It is tempting t o ascribe the formation of ( I ) to addition of
ketene phenyl imine t o phenylazirine. According t o Smolinsk y 111, phenylazirine and ketene phenylimine coexist after
pyrolysis of c/.-azidostyrene. The characteristic ketene imine
absorption[ll at 5 pm in the IR spectrum of our reaction
mixture after photolysis can be explained by presence of a
small amount of ketene phenyl imine. However, no trace of
( I ) is t o be found in the gas chromatogram after pyrolysis of
a-azidostyrene at 350 "C. N o r is any trace of ( I ) t o be found
in the mixture obtained o n addition of azidostyrene t o
boiling phenylazirine (ca. 180 "C). From o u r results, together
with the observation that ( I ) is also formed on photolysis
of phenylazirine, we conclude that it is formed by photochemical and not by thermal activation. This is thus the first
case of intermolecular photocycloaddition t o a carbonnitrogen double bond.
Received: November 23, 1967
[Z 662 LEI
German version: Angew. Chem. 80, 119 (196E')
[*I Dr. F. P. Woerner and Dr. H. Reimlinger
Union Carbide European Research Associates,
95, rue Gatti de Gamond, Bruxelles 18 (Belgium)
Dr. D. R . Arnold
Union Carbide Research Institute
P.O. Box 278, Tarrytown, New York 10592 (U.S.A.)
[l] G. Smolinsky, J. org. Chemistry 27, 3557 (1962).
[2] L. Horner, A. Christmann, and A . Gross, Chem. Ber. 96, 399
(1963); G . R . Harvey and K. W . Ratts, J. org. Chemistry 31, 3907
(1966); A. Hassner and F. W . Fowler, Tetrahedron Letters 1967,
[3] Mercury high-pressure lamp: Philips HPK 125 W.
141 The NMR spectra were measured with a Varian A-60
apparatus for CC14 solutions with tetramethylsilane as internal
[51 S. J . Bruis, J. oig. Chemistry 27, 3532 (1962).
161 W . F. Erman, J. Amer. chem. SOC.89, 3828 (1967); J . A .
Moore, F. J . Marascia, R. W . Medeiros, and R . L. Winehoit, J .
org. Chemistry 31, 34 (1966).
X-Ray Structure Analysis of
Tri- p-chlorobis[bis(tri-n-buty1phosphine)ruthenium Chloride]
2 333
The X-ray analysis confirms the structure ( I ) and the Ru-CI
and Ru-P distances are shown in the figure. The coordination
round the ruthenium atoms is approximately octahedral (the
largest angular distortion is 12.4 ") and the environments of
these atoms are very similar. The Ru....Ru distance is
3.115 A, and is thus much longer than that found in the
metal (2.650 A) [41. The Ru--CI distances fall into two groups:
those trnns to other Ru--C1 bonds are considerably shorter
(2.340-2.376 A) than those (2.444-2.505 A) trans to Ru-P
Received: November 7, 1967
IZ 664 I E I
German version: Angew. Chem. 80, 116 (1968)
[ * ] Dr. G. Chioccola, Dr. J. J. Daly, and Dr. J. K. Nicholson
Monsanto Research S.A.
Binzstr. 39
CH-8045 Zurich (Switzerland)
[I] J . K . Nicholson, Angew. Chem. 79,273 (1967); Angew. Chem.
internat. Edit. 6, 264 (1967).
[2] Determined by Drs. G. and S. OlivP, Zurich.
[3] U.W. Arndf and D. C. Phillips, Acta Crystallogr. 14, 807
141 A . Hellaweit and W. Hiime-Rothery, Philos. Mag. 45, 797
Dimerization of Azaallyl, Diazaallyl, and
Oxaazaallyl Groups by Way of
Copper-containing Intermediateslll
By Th. Kauffmann, G. Beissrrer, E . Koppelmann,
D. Kidilmann, A . Scliott, and H . Schrecken [*I
We are studying systematically the dimerization of organic
compounds by way of organo copper derivatives, a reaction
whose unusually wide applicability[z] is not yet fully recognized [3,41.
We observed dimerization of the 3-azaallyl group contained
in ( I ) when treating the compound 151 with 1 molar equivalent
of CuCl or CuBr2 in tetrahydrofuran/ether (1:l) under
nitrogen at 60 "C. The product (2) was formed in, respectively
72 and 78 % yield with separation of Cu or CuBr [GI.
By G. Chioccola, J . J . Daly, and J . K. Nicholson[*]
The synthesis of Ru~C15[P(n-C4H9)3]4 has been described
recently and the results of chemical investigations suggest 111
the structure ( I ) . The complex has a magnetic moment of
0.75 B.M. per ruthenium atornI21 corresponding to one
unpaired electron in the molecule.
The dark red crystals are monoclinic, space group P21,'c with
a = 13.866, b = 16.003, c = 30.545 A, p = 110.0". There are
four molecules in the unit cell and the observed density gives
a molecular weight of 1170.7 (theoretical 1188.8). The intensities were measured on a linear diffractometer [31 and the
structure was determined by Patterson and Fourier methods.
A least squares refinement of 3776 planes gives a current
R-factor of 0.083. The standard deviations of the Ru-CI and
Ru-P bond lengths are 0.0052 and 0.0054 8, respectively.
Angew. Chem. internat. Edit. 1 Vol. 7 (1968) 1 No. 2
When CuI in dimethoxyethane at 85'C is treated with 1
molar equivalent of the deep red compound (3) (formed by
the action of NaNH2 o n N-benzylidenebenzylamine), the
2-azaallyl group of ( 3 ) dimerizes analogously, yielding
compound (6) (58 % yield) specifically in the meso-form
(m.p. 163 "C; lit. [71, 164 "C).
The 1,2-diazaallyl group in (4) is also coupled by successive
action of 1 molar equivalent of CuCl and oxygen in dimethoxyethane at 60 "C, to give a known [*I product of m.p.
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structure, butylphosphinic, tri, chlorobium, analysis, bis, chloride, ruthenium, ray
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