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Ligand Addition and Redox Reactions of Azido-Metal Complexes.

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R H N - C HO
Examples: A mixture of 50 mmole of isocyanide and 5 5
mmole of dimethyl sulfoxide is treated with 5 mmole of
p-toluenesulfonic acid or 1 mmole of triphenylmethyl perchlorate. The temperature is kept at 50 to 80' by periodic
cooling and two or three additions of a little acid; dimethyl
sulfide distils off, and after disappearance of the isocyanide
odor (about 30 min) the residue is fractionated in a waterpump vacuum. Products are tabulated below.
Yield (%)
I Isocyanate (b.p.1
p-CH3- C6 H 4
85 (115-120°C)
92 (62-68 "C/15 mm)
90 (88-91 'Cjl2 mm)
52 (75-78 OCjl5 mm)
- S-CI12X
quantitatively. This pale yellow compound [decomp. at
216OC; vaS(NCO) = 2218, v,(NCO) = 1347 cm-1, suspension
in Nujol] is also obtained directly from K2[Pd(NC0)4] and
triphenylphosphine in ethanoljwater 131. A CO pressure of
200 atm (at 20°C) is necessary for complete conversion of
the platinum(I1) compound [ ( C ~ H ~ ) ~ P I Z P ~ (into
N ~ )the
analogous isocyanate complex [vas(NCO) = 2234 cm-I].
However, no cyanate could be detected after CO had been
passed (at 200 atm and 2OoC) into an aqueous solution of
sodium azide. The reaction N3- + NCO- does occur when
Pd(I1) nitrate is added [1.5 g of NaN3, 0.1 g of Pd(N03)2, in
water], the Pd(1r) being reduced to metallic palladium.
If an excess of carbon disulfide is allowed to act on solid
[(C6H5)3P]2Pd(N3)2 for several days at 20 OC, CS2 is added to
the azide group and the complex(1)is formed.This pale yellow
substance (decomp. at 119-120°C) was also obtained from
Pd(I1) nitrate, Na[CS*N3] ("azidodithiocarbonate") [41, and
The behavior of isocyanides towards alkylating and arylating
agents in dimethyl sulfoxide indicates that only "hard" [5J
electrolytes tend to attack the nitrogen atom.
Received: November 4th, 1966
[Z 382 IE]
German version: Angew. Chem. 79, 145 (1967)
[*] Dr. habil. D. Martin
Dipl.-Chem. A. Weise
Institut fur organische Chemie der Deutschen Akademie der
Wissenschaften zu Berlin
X 1199 Berlin-Adlershof (Germany)
[**I Quantitative isolation of the sulfide is impeded by its
volatility (b.p. 38-40 "C).
[***I We prepared ( I ) with R = cyclohexyl and X = Br from
N-cyclohexylformamide, benzoyl bromide, and dimethyl sulfoxide, and (Z) with R = cyclohexyl and X = SbC16 from N-cyclohexylformonitrilium hexachloroantimonate and DMSO.
[l] H . W . Johnson j r . and P. H . Daughhetee jr., J. org. Chemistry
29, 246 (1964).
[2] I. Hagedorn, U . Eholzer, and H . D . Winkelmann, Angew.
Chem. 76, 583 (1964); Angew. Chem. internat. Edit. 3,647(1964);
I. Hagedorn and U . Eholzer, Chem. Ber. 98, 936 (1965).
[3] D. Martin and A . Weise, Liebigs Ann. Chem., in press.
[4] F. G. Bordwell and B. M . Pitt, J. Amer. chem. SOC.77, 572
(195 5).
[51 R . G. Pearsen, J. Amer. chem. SOC.85, 3533 (1963).
Ligand Addition and Redox Reactions
of Azido-Metal Complexes
By W. Beck and W. P . Fehlhammer
Metal carbonyls, e.g. W(CO)6, react with azide ions, giving
isocyanate complexes [I].
We have found that isocyanates also arise when azido-metal
complexes are treated with free carbon monoxide. Thus when
CO is passed a t 20 "C into a chloroform solution of diazidoM-CO+
M-N3 + C O
P(C6H5)3 in ethanol/water. The characteristic IR absorption
bands of the coordinately bound 1,2,3,4-thiatriazole-5-thiolate ion lie at 1295(m), 1223(s), 1067(s), 1020(m), and 932(m)
cm-1 (KBr disk). The decomposition products arising from
( I ) in chloroform solution at 20 "C give a n intense I R band
at 2095 cm-1 indicating a n isothiocyanate complex.
Reaction of [(C6H5)3P]zPd(N3)2 with trifluoroacetonitrile in
CH2C12 (1 atm, O'C, 1 hr) also leads to formation of a
compound in which a five-membered ring system is bonded
through a nitrogen to the palladium. This reaction is analogous to the 1,3-dipolar cycloadditions of organic azides [51.
The pale yellow tetrazolato complex (2) formed (decomp.
at 258 "C) is sparingly soluble in CH2C12 and its I R spectrum
(KBr disk) shows the bands of the 5-trifluoromethyltetrazolate anion "51: 1507(s) v(C-CF3); 1242(s), 1191(s), 1182(m),
1168(~),1156(~), 1143(s) v(CF3); 746 (s) S(CF3); 1 4 0 1 ( ~ ) ,
1312(w), 1040(s), and 1024fs) (ring vibrations).
A tetrazolato complex, possibly containing a metal-C bond,
is also formed o n treatment of [As(CsH5)4] [Au(N3)4] (21 with
cyclohexyl isocyanide (molar proportions 1 :4.5) in CHzC12
at 20°C for about 1/2 hr. On addition of petroleum ether
shiny, colorless leaflets of tetraphenylarsonium tetra(cyclohexyltetrazolato)aurate(rII) (3) are obtained [m.p.
184OC (decomp.)]. The IH-NMR spectrum (in DCCI,)
+ [M-NCOI-+ Nz
+ M-NCO+Nz
includes three signals (intensity ratio' 5: 1 :10) which can be
bis(triphenylphosphine)palladiurn(Ir), [ ( C ~ H S ) ~ P ] Z P ~ ( N ~ ) ~assigned
[ ~ ] , to the 20 phenyl protons (7 = 2.4), the four tertiary
the isocyanate complex [(C,jH5)3P]zPd(NC0)2 is obtained
H atoms (T = 5.2), and the 40 methylene protons (7 = 8.3) of
Angew. Chem. internat. Edit.
/ Vol. 6 (1967) 1 No. 2
the cyclohexyl ring. The I R spectrum (Nujol suspension)
contains the characteristic bands of I-cyclohexyltetrazole,
except for the v(CH) vibration 171.
The red solution of [As(csH5)4] [Au(N3)4] in tetrahydrofuran
rapidly becomes colorless in daylight, a n intramolecular
redox reaction occurring:
The diazidoaurate(1) complex [decomp. at 127 O C ; vas(N3) =
2039 cm-1, vs(N3) = 1285 cm-1, KBr disk] is precipitated in
crystalline form by petroleum ether. It can also be obtained
directly from Au(I)CI, NaN3, and [ A s ( C ~ H ~ ) ~inI C
Received: November 21st, 1966
[Z 385 IE]
German version: Angew. Chem. 79, 146 (1967)
[*] Doz. Dr. W. Beck
Dip1.-Chem. W. P. Fehlhammer
Anorganisch-Chemisches Laboratorium
der Technischen Hochschule
8 Munchen 2 (Germany)
[l] W . Beck and H . Smedal, Angew. Chem. 78, 267 (1966); Angew. Chem. internat. Edit. 5, 253 (1966).
[2] W. Beck, K . Feldl, and E. Schuierer, Angew. Chem. 77, 458
(1965); 78, 267 (1966); Angew. Chem. internat. Edit. 4, 439
(1965); 5, 249 (1966).
[3] K . Feldl, Dissertation, Technische Hochschule Miinchen,
[4] F. Sommer, Ber. dtsch. chem. Ges. 48, 1833 (1915); E. Lieber,
C . N . PilIai, J . Ramachandran, and R. D . Hites, J. org. Chemistry
22, 1750 (1957).
[ 5 ] Cf. R. Huisgen, Angew. Chem. 75, 604 (1963); L . Birkhofer
and P . Wegner, Chem. Ber. 99, 2512 (1966).
[6] H . B. Jonassen, J. O.Terry, and A . D . Harris, J. inorg.
nuclear Chem. 25, 1239 (1963); J. Amer. Chem. SOC.85, 2927
[7] G . L. Gilbert and C . H. Brubaker jr., Inorg. Chem. 2, 1216
(I) :
Phenethyl chloride,
bromide, iodide
a-Methylphenethyl chloride, bromide, iodide
T y p e (4) :
a-Methylbenzyl bromide
a-Ethylbenzyl bromide
Toluene 74, 80, 67
Ethylbenzene 67
Toluene 89, 85, 73
Toluene 2, ethylbenzene 35
Toluene 1, phenylpropane 41
Toluene 16, 3-phenylpropylhydrazine 47, phenylpropane 6.
Type (5) :
3-Phenylpropyl bromide
For cleavage of compounds of type ( I ) we must consider
not only the route via the olefin (7), but also that via the
hydrazine derivative (8), since hydrazines of this type decompose in the presence of sodium hydrazide according
to (8) + (2) + (3)[41.
In favor of the route via (7) are the facts that P,B-dimethylphenethyl chloride (6), which cannot yield a styrene derivative
by elimination of HHal, gives no trace of isopropylbenzene
on treatment with sodium hydrazide in ether at 35 "C or in
benzene at 60°C, but remains largely unattacked (22 % or
8 % resp. of t-butylbenzene being formed).
Received: November 21st, 1966
[Z 386 IE]
German version: Angew. Chem. 79, 147 (1967)
[*I Prof. Dr. Th. Kauffmann, Dip1.-Ing. W. Burkhardt, and
Cleavage of P-Halogeno-u-phenylalkanesby
Sodium Hydrazide
By Th. Kauffmann, W . Burkhardt, and E. Rauchr*I
On reaction with sodium hydrazide, phenylalkyl halides of
types ( I ) , (4), and (5) [21 formally should be convertible by
elimination of hydrogen halide into olefins that can be
cleaved by the hydrazide [ll.If theelimination of HHal is faster
than competing reactions, then the action of sodium hydrazide should lead to scission between the C atoms that
are a and 8 to the phenyl group and thus to formation of a
hydrocarbon (2) and a hydrazone (3).
We have found that under the conditions of hydrazidolysis
of C = C bonds[ll (in a hydrazine/ether mixture at 35 OC or
in a hydrazine/benzene mixture at 6OoC; excess of sodium
hydrazide) this cleavage does occur to a large extent with
halides of type ( I ) . With (4) or (5) it occurs only to a small
extent, the main reactions being replacement of the halogen
by hydrogen, or a hydrazine group respectively.
la I p
C6H5-C-C I
1) 2NaNH-NH2
2) HzO
Dip1.-Ing. E. Rauch
Organisch-Chemisches Institut der Universitat
Hindenburgplatz 55
44 Munster (Germany)
[l] Cf. Th. Kauffmann, Angew. Chem. 76, 214 (1964); Angew.
Chem. internat. Edit. 3, 349 (1964); Th. Kauffmann, H. Henkler,
E. Rauch, and K. Lotzsch, Chem. Ber. 98, 912 (1965).
[2] When an olefin containing a @,y-doublebond with respect
to a phenyl group is treated with sodium hydrazide, an a,@double bond results which is subsequently cleaved.
[3] Molar ratio; halide: NaNH-NH2:NHz-NHz
= 1:5:5-15.
[4] Th. Kauffmann, K . Lotzsch, and D. WOKChem. Ber. 99, 3148
Stereoselective Synthesis of 1-Butene with Lithium
Sulfate as Elimination Catalyst
By H . Noller, M . Rosa-Brusin, and P. Andrdu[*I
In our studies of the elimination of hydrogen halide on solid
catalysts we have always obtained mixtures of the three linear
trans 2-butene
butenes from n-butyl chloride or bromide&
being formed in large excess 121. Recently, however, using
lithium sulfate and a microcatalytic technique (a pulse
technique) a t temperatures between 320 and 370 O C , we
obtained I-butene exclusively from n-butyl bromide [31; at
390 "C some 10 %, and at 42OoC some 50 %, of 2-butene
was formed.
A nitrogen stream (35 ml/min),saturated at 70 OC with n-butyl
bromide, was passed through a horizontal glass tube (inner
diameter 2 cm) holding ca. 50 g of catalyst, then through a
Angew. Chem. internat. Edit.
Vol. 6 (1967)
1 No. 2
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reaction, azido, metali, redox, additional, complexes, ligand
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