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Metal Complexes of Diethylthiophosphinic Acid.

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( %)
B p ("C/12 mm) or
m.p. ("C)
(59, from ethanol)
(91-92; from benzenejlight
In contrast to primary aliphatic amines, 1 mole of the more
weakly basic a-naphthylamine uses only 1/2 mole of carbodiimide under the usual conditions and 1,3-di-(a-naphthyl)thiourea is obtained quantitatively.
The formation of the isothiocyanate thus depends on the
relative velocities of competing reactions of the amine,
namely, a) that with carbon disulfide to give the dithiocarbamic acid and b) that with the isothiocyanate formed
to give the thiourea. With strongly basic aliphatic amines,
reaction a) is faster and yields mainly alkyl isothiocyanates;
with aromatic amines reaction b) is faster, yielding only the
thioureas. However, even with aliphatic amines, reaction b)
cannot be entirely suppressed, i.e. some 1,3-dialkylthiomea
RHN-CS-NHR is formed and it is precipitated with the
dicyclohexylthiourea.Therefore, when stoichiometric amounts
are used the residual carbodiimide must be separated from
the alkyl isothiocyanate by fractional distillation or washing
with pentane; it is advantageous to begin with somewhat less
than 1 mole of carbodiimide.
Attempts to prepare isocyanates by an analogous method
gave ureas only.
Received: December 5th, 1966
[Z 395 IE]
German version: Angew. Chem. 79,151 (1967)
A11 these complexes dissolve readily in organic solvents such
as benzene, carbon tetrachloride, chloroform, alcohols, and
acetone. Osmometric determination of the molecular weights
shows that the octahedral In(ur) complex is present only as a
monomer in benzene over a wide range of concentrations
(from ca. 0.005 to ca. 0.1 mole l-l), whereas the tetrahedral
complexes are strongly associated. With rising concentration
the degree of association of the tetrahedral complexes
approaches a limiting value which depends on the solvent
(see Fig. 1) and on the central atom (see Table 1); extra40 t
0 05
clmole l-'I
Fig. 1. Degrees of association calculated from the osmometrically [41
determined apparent number average molecular weights of
C O [ ( C ~ H ~ ) ~ P ( S )at
O I37°C
in CClr,
and CHCl, (mol. wt. of
monomer 333 27).
[*I Dr. J. C . Jochims and Frau A. SeeGger
Max-Planck-Institut fur Medizinische Forschung,
Institut fur Chemie
Jahnstr. 29
69 Heidelberg (Germany)
111 We are very grateful to Prof. R . Kuhn for supporting this
[2] Part 111 of Carbodiimides. - Parts I and 11, J. C. Jochims,
Chem. Ber. 98, 2128 f1965), and Angew. Chem. 77, 454 (1965);
Angew. Chem. internat. Edit. 4, 435 (1965).
131 H . G. Khorunu, Chem. Reviews 53, 145 (1953).
141 H . G . Khorana, Canad. J. Chem. 31, 585 (1953).
Metal CompIexes of Diethylthiophosphinic Acid
By W . Kuchen and H . Hertell*]
Table 1 . Mean degree of association of complexes
M[(C2H&P(S)OJz in benzene at 37 "C.
I corn
I Zn(II)
polation to infinite dilution always leads to the monomer.
Viscometric studies151 of the CO(II)and Zn@) complexes in
benzene disclosed a very steep rise in the reduced viscosity
qSpec/cwith rising concentration. The nature of the chalcogen atom also influences the association. For instance, the
degree of association of the Cd(r1) complexes increases in the
order Cd[(CzHs)zP(Se)Sel~ < Cd[(C2H&P(Se)S12 <
Cd[(C2H&P(S)S]z < Cd[(C2HS)2P(S)0]2 from 1.75 to 2.5
(at c = 0.07 mole/l, osmometrically in benzene at 37 "C).
Metal complexes of diethylthiophosphinic acid show a
greater tendency to associate in solvents free from electron
We assume that association involves formation of chelate
donors than do the corresponding dithiophosphinato combridges as in formula (2), which was previously postulated
plexes 11 21 ;the influence of various factors on the association
or proved for metal complexes of the dialkyldithiophosphinic
thus becomes more evident. To prepare the complexes we
used sodium diethylphosphinate, ( C ~ H S ) ~ P ( S ) O N ~ . ~ H ~ O ,
which was obtained as colorless leaflets (m.p. 58-59 "C) by
neutralization of thiophosphinic acid 131 (C~HS)~P(S)OH,
evaporation, dissolution of the residue in acetone, and precipitation with ligroin.
Complexes of type (1) were precipitated when sodium diethylthiophosphinate was added to aqueous solutions of a
metal salt, and they were recrystallized from 2-propanol.
Complexes with Zn(I1) (m.p. 186-188 "C), Cd(1r) (m.p.
119--122'C), In(m) (m.p. 133 "C), or Pb(rr) (m.p. 99-102°C)
acids 11 21 and for phosphinic acids 161. The influence of
as the central atom formed colorless crystals which, as is
hybridization of the metal ions and the radii of the donor
shown by thermogravimetric analysis, melt with decomposiatoms, in particular, favor our view that bridged structures
of low strain are formed for steric reasons []].That there is n o
A mixture of stoichiometric quantities of (C2H&P(S)OH
tendency towards a higher coordination number on assoand CoCO3 in boiling benzene gives, after several hours, a
ciation could be shown for the CO(II)complex: the intenviscous, deep blue solution of the CO(II)complex, which is
sities and positions o f the absorption maxima in the electronic
obtained as intensely blue crystals (m.p. 186-188 "C) from
= 605 mp, log E = 2.591), measured for benzene
spectra, ,A,(
2-propanol and forms mixed crystals with the Zn(1r) complex.
and carbon tetrachloride solutions of various concentrations,
Angew. Chem. internat. Edit.
/ Vol. 6 (1967) 1 No. 2
indicate in all cases tetrahedral coordination of the metal 171,
which is clearly present also in the crystals since a magnetic
moment of peff = 4.63 B.M. was found181.
The C o complex is monomeric in pyridine, which acts as an
electron donor, the electronic spectrum (Ama, = 515 mp,
log E = 1.496) here indicating octahedral coordination of the
Co[71. In agreement with this, we were able to isolate the
pink bis(diethy1 thiophosphinato)tetrapyridinocobalt(xr),
[(C2H5)2P(S)0]2Co(C5H5N)4(m.p. 63-64 OC; p e =
~ 4.98
B.M. [81; non-electrolyte in pyridine), in which the phosphinato group acts as unidentate ligand.
Received: December Znd, 1966
[Z 396 IE] version: Angew. Chem. 79, 148 (1967)
[*] Prof. Dr. W. Kuchen and Dipl.-Chem. H. Hertel
Institut fur Anorganische Chemie und Elektrochemie der
Rheinisch-Westfalischen Technischen Hochschule Aachen
Templergraben 55
51 Aachen (Germany)
[I] W. Kuchen and J . Metten, Angew. Chem. 72, 584 (1960).
[2] W. Kuchen, J . Metten, and A . Judat, Chem. Ber. 97, 2306
I31 W. Kuchen and H. Meyer, Z . anorg. allg. Chem. 333, 71
[4] M . J. R. Cantow, R . S. Porter, and J. F. Johnson, J. polymer
Sci. 2, 2547 (1964). We used a vapor-pressure osmometer
produced by Knauer, Berlin.
[5] G. V. Schulz and H . J . Cantow in Houben-Weyl, Vol. 3
Part 1. Georg Thieme, Stnttgart 1955, p. 431.
[6] B. P. Block, J . Simkin, and L. Ocone, J. Amer. chem. SOC.84,
1749 (1962); G. E. Coates and D . S . Golightly, J. chem. SOC.
(London) 1962, 2523; C . E. Wilkes and R . A . Jacobson, J. inorg.
Chem. 4 , 99 (1965).
171 F. A . Cotton, D . M . L. Goodgame, and M . Goodgame, J.
Amer. chem. SOC.83, 4690 (1961); C . K . Jorgensen, Acta chem.
scand. 16, 2017 (1962).
[8] B. N . Figgis and R . W. Nyholm, J. chem. SOC.(London) 1954,
be explained by homoallylic rearrangement of the anionic
intermediate (2) to the anion (4) and protonation of the
The olefin (5) can be hydrogenated over platinum in glacial
acetic acid to the hydrocarbon (6) and thence further to
bicyclo-[3.3.1.]- and -[3.2.2]-nonane 111. The structures of the
products (5) and (6) are proved by comparison with the
products of the following syntheses. 3-Cyclohexenylacetic
acid yields its acid chloride ( 7 ) (b.p. 90-92'C/15 mm, 95 %)
and thence a diazo ketone (8) which is decomposed by
copper powder in boiling cyclohexane to yield the ketone
(9) (colorless crystals, m.p. 92-94 'C, yield 52 %). Heating
the tosylhydrazone (10) (m.p. 203-205 "C, 80 %) with
sodium glycolate in ethylene glycol affords a crude product,
85 % of which is compound (5) and the remainder contains
six compounds of unknown structure [31. The compound (5)
can be isolated from this mixture in 6 % yield [ZJ as colorless volatile crystals, m.p. 68-70 'C. Wolff-Kishner reduction
of the ketone ( 9 ) gives the hydrocarbon (6) as colorless
crystals with a pleasant smell (m.p. 128-129'C,
63 % [Zl).
According to the mechanism of the Bamford-Stevens reaction141 the cation (12) should be accessible as a product
from the tosylhydrazone (11) and should become stabilized
by loss of a proton. If this hydrazone (11) (m.p. 202-204 "C,
79 %) is treated in the way described for (lo), then tricyclo[,6-diene(13) is formed. The sublimed
product (m.p. 37-44OC, 57%) contains 97 %[31 of (13)
which, when purified by gas chromatography, forms lightsensitive, colorless crystals (m.p. 46 OC, 43 % C21) with an unpleasant odour 151.
Rearrangements of the Triasterane System 111
By U. Biethan, H. Klusacek, and H . Musso[*1
The cyclopropane rings of triasterane (3) are parallel and
particularly favorably situated for rearrangements induced
by conversion of a methylene bridge into a n anion, radical,
cation, or carbene. For instance, the Wolff-Kishner reduction
of triasteranone ( I ) gives 29 % of triasterane (3), 8.5 % of
bicyclo[3.3.l]nona-2,6- and -2,7-diene, as well as 0.9 % [21 of
(5) 111. The formation of (5) can
The N M R spectrum161 of ( I 3 ) in CCl&DCI3 at room
temperature confirms the constitution assigned and indicates
rapid exchange between the structures of equal energy
content, for it shows only four signals in the intensity
ratio 2:2:4:2, namely: Ha 1.06 ppm (triplet, J = 2.5 Hz),
Hb 2.33 ppm (multiplet), H, 3.97 ppm (triplet, J = 7.5 Hz),
and Hd 5.63 pprn (triplet, J = 7.5 Hz).
Hydrogenation of (13) over platinum in glacial acetic acid
leads, as in the case of (3), t o a mixture of (6) and bicyclo13.3.11- and -[3.2.2]-nonane 131.
Compound (8) was not purified. Results obtained in the
analysis of the other new compounds were consistent with
the constitutions assigned. Compatible IR, NMR, and
mass spectra were also obtained.
Received: December 14th, 1966
[Z 397 IE]
German version: Angew. Chem. 79, 152 (1967)
(7) R = C1
(8) R = CHNz
(9)R = 0
(1O)R = N-NH-Tosyl
[*] Dr. U. Biethan, cand. chem. H. Klusacek, and
Prof. Dr. H. Musso
Institut fur Organische Chemie der Universitat Bochum
Present address: Chemisches Institut der Universitat
Bahnhofstr. 7
355 Marburg (Germany)
[ l ] Part 111 of Asteranes. - Part 11: H . Musso and U. Biethan,
Chem. Ber. 100, 119 (1967).
[2] Yields after preparative gas chromatography: Wilkens
Autoprep, column SE 30, 145 "C, H2.
[3] Analytical gas chromatogram: Perkin-Elmer F 6, column
1G3, 140 "C, Nz.
Angew. Chem. internat. Edit. 1 Voi. 6 (1967)
No. 2
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acid, metali, complexes, diethylthiophosphinic
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