Reactions of nitrosoarenes containing electron-withdrawing substituents with coordinated CO. Synthesis and structure of complexes Pd2(OAc) 2(p-ClC6H4N[p-ClC6H 3NO])2 and Pd2(OAc)2(o-ClC 6H4N[o-ClC6H3NO])2

Article abstract of DOI:10.1023/B:RUCB.0000037849.06365.7f

The reaction of tetranuclear Pd₄(μ-COOCH₃) ₄(μ-CO)₄ cluster (1a) with p- and o- chloronitrosobenzenes was found to give dinuclear nitrosoamide complexes, Pd₂(OAc)₂(p-ClC₆H₄N[p-ClC ₆H₃NO])₂ (4) and Pd₂(OAc) ₂(o-ClC₆H₄N[o-ClC₆H ₃NO])₂ (5), respectively. The formation of complexes 4 and 5 is accompanied by evolution of CO₂, resulting from oxidation of CO coordinated in cluster 1. Complexes 4 and 5 were characterized by elemental analysis and IR and ¹H NMR spectroscopy; their structures were studied by EXAFS. The reactions of dinuclear complex 4 with molecular hydrogen and CO were studied. The major products of reduction of 4 with hydrogen include metallic palladium, acetic acid, cyclohexanone, and molecular nitrogen. Treatment of complex 4 with CO under mild conditions (1 atm, 20°C) affords p-chlorophenyl isocyanate.

Full text of DOI:10.1023/B:RUCB.0000037849.06365.7f

Russian Chemical Bulletin, International Edition, Vol. 53, No. 4, pp. 819—824, April, 2004
819
Reactions of nitrosoarenes containing
electronꢀwithdrawing substituents with coordinated CO.
Synthesis and structure of complexes Pd2(OAc)2(pꢀClC6H4N[pꢀClC6H3NO])2
and Pd2(OAc)2(оꢀClC6H4N[оꢀClC6H3NO])2
S. T. Orlova,a T. A. Stromnova,aꢀ D. N. Kazyul´kin,a L. I. Boganova,a D. I. Kochubey,b and B. N. Novgorodovb
aN. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
31 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 954 1279. Eꢀmail: strom@igic.RAS.ru
bG. K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences,
5 prosp. Akad. Lavrent´eva, 630090 Novosibirsk, Russian Federation.
Fax: +7 (383 2) 34 3056. Eꢀmail: kochubey@catalysis.nsk.su
The reaction of tetranuclear Pd4(µꢀCOOCH3)4(µꢀCO)4 cluster (1a) with pꢀ and
oꢀchloronitrosobenzenes was found to give dinuclear nitrosoamide complexes, Pd2(OAc)2(pꢀ
ClC6H4N[pꢀClC6H3NO])2 (4) and Pd2(OAc)2(оꢀClC6H4N[оꢀClC6H3NO])2 (5), respectively.
The formation of complexes 4 and 5 is accompanied by evolution of CO2, resulting from
oxidation of CO coordinated in cluster 1. Complexes 4 and 5 were characterized by elemental
1
analysis and IR and H NMR spectroscopy; their structures were studied by EXAFS. The
reactions of dinuclear complex 4 with molecular hydrogen and CO were studied. The major
products of reduction of 4 with hydrogen include metallic palladium, acetic acid, cyclohexꢀ
anone, and molecular nitrogen. Treatment of complex 4 with CO under mild conditions
(1 atm, 20 °C) affords pꢀchlorophenyl isocyanate.
Key words: palladium, carbonyl complexes, clusters, nitrosoarenes, arylnitrenes, chloroꢀ
nitrosobenzene.
Palladium complexes containing nitrosoarene ligands
are few and far in between.1—8 Some of these have been
prepared in our study dealing with the reactions of PdI
carbonyl carboxylate clusters Pd4(µꢀCOOR)4(µꢀCO)4
(R = Me (1a), CF3 (1b), But (1c), and Ph (1d)) with
nitrosobenzene9,10 and oꢀnitrosotoluene.10,11 In this work,
we studied the reactions of cluster 1a with pꢀ and
oꢀchloronitrosobenzenes.
Results and Discussion
Early, we found9—11 that the reactions of clusters 1
with nitrosobenzene and оꢀnitrosotoluene proceed
through deoxygenation of the nitrosoarene molecule by
the coordinated CO group to give CO2 and an arylnitrene
species, [oꢀR´C6H4N:] (R´ = H and Me, respectively).
In the case of nitrosobenzene, the phenylnitrene speꢀ
cies formed react with a second nitrosobenzene molecule,
yielding finally dinuclear complex Pd2(µꢀCOOR)2(η2ꢀ
PhNC6H4NO)2 (2a—c), where the η2ꢀcoordinated ligand
can be considered as both a nitrosoarene derivative and
an amide ligand containing a nitroso group.
R = Me (a), CF3 (b), But (c), Ph (d)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 783—788, April, 2004.
1066ꢀ5285/04/5304ꢀ0819 © 2004 Plenum Publishing Corporation

820
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
Orlova et al.
The reaction of 1 with оꢀnitrosotoluene furnishes the
C,H,Nꢀelemental analysis data for the brown substance
isolated by fractional crystallization are in good agreeꢀ
ment with the molecular formula C14H10Cl2N2O3Pd. The
1H NMR spectrum contains a broadened singlet at δH 2.1,
corresponding to protons of the AcO groups and a poorly
resolved multiplet with a maximum at δH 7.0, correspondꢀ
ing to protons of the Ph groups. The integral intensities of
the signals for the AcOꢀ and Phꢀgroup protons are related
as ∼3 : 7. In the IR spectrum of the complex, the bridging
AcO groups are responsible for the bands with νas(COO) =
1560 cm–1 and νs(COO) = 1450 cm–1 (∆ν(COO) =
110 cm–1). The data of C,H,Nꢀanalysis and IR and
1H NMR spectroscopy indicate that this complex also
contains nitrosoamide ligands, its composition being deꢀ
scribed as Pd2(OAc)2(оꢀClC6H4N[оꢀClC6H3NO])2 (5).
The structures of complexes 4 and 5 were studied by
EXAFS. In the simulation, the EXAFS spectra of comꢀ
plexes 4 and 5 were compared with the spectra of comꢀ
plex 2, whose structure has been established by Xꢀray
diffraction. In all cases, good agreement to within the
accuracy of the method was attained. In the calculation,
O and N were taken as the ligands nearest to Pd and all
bond lengths for each ligand were taken to be equal. The
spectra of the complexes show a set of distances correꢀ
sponding to the Pd—O and Pd—N bonds in the range of
1.9—2.2 Å. This does not provide a reliable description of
the coordination environment and, in particular, gives
rise to underestimated effective coordination numbers.
The EXAFS data for complexes 2a, 4, and 5 and the
Xꢀray diffraction data for 2a are listed in Table 1. Comꢀ
parative analysis of the data demonstrates that all comꢀ
plexes are in fact dimers with relatively short distances
between the metal atoms linked by the bridging AcO
groups. The underestimation of the Pd...Pd distance
(2.74 Å) in the EXAFS spectrum of complex 2a with
respect to the distance derived from the Xꢀray diffraction
data (2.84 Å) can be attributed to the large Debye factor
caused by the pronounced nonrigidity of the complex
nitroso complexes Pd2(µꢀCOOR)2(η2ꢀCH2C6H4NO)2
(3a—d) in which each Pd atom bears an оꢀnitrosotoluene
molecule metallated at the Me group.
We assumed that the introduction of electronꢀwithꢀ
drawing substituents into the nitrosoarene molecule can
change the reaction pathway and the composition of prodꢀ
ucts. Therefore, we studied the reactions of cluster 1a
with оꢀ and pꢀchloronitrosobenzenes in which the subꢀ
stituents have similar electronꢀwithdrawing properties but
somewhat different steric factors.
Reactions of cluster 1a with pꢀ and оꢀchloronitrosoꢀ
benzenes. The reaction of cluster 1a with pꢀchloronitrosoꢀ
benzene at 50 °C is completed over 10—15 h (reaction
with nitrosobenzene requires 4—5 h at the same temperaꢀ
ture). Some of the coordinated carbonyl groups are oxiꢀ
dized to CO2, the amount of the gas evolved being at most
half the amount calculated from the stoichiometry (based
on cluster 1). By fractional crystallization, a greenishꢀ
brown powder was isolated from the reaction mixture.
The elemental analysis of this product was in good agreeꢀ
ment with the composition C14H10Cl2N2O3Pd. This gross
composition corresponds to a compound containing one
acetate group per Pd atom and one nitrosoamide ligand
pꢀClC6H4N[pꢀClC6H3NO] (similar to the ligand, which
arises upon the interaction of cluster 1 with nitrosoꢀ
benzene). The 1H NMR spectrum exhibits a signal for the
acetateꢀgroup protons as a broadened singlet with a maxiꢀ
mum at δH 2.1 and signals for the Phꢀgroup protons as a
broad multiplet with a maximum at δH 7.2. The ratio of
the integral intensities of the proton signals of these ligands
equals ∼3 : 7, which confirms the presence of one acetate
group (3 H) and one nitrosoamide group (7 H). Accordꢀ
ing to IR spectroscopy data, the resulting complex conꢀ
tains bridging acetate groups (νas(COO) = 1552 cm–1
,
νs(COO) = 1420 cm–1, ∆ν(COO) = 127 cm–1) and, hence,
the complex is at least a dimer. The composition of the
complex can be described as Pd2(OAc)2(pꢀClC6H4N[pꢀ
ClC6H3NO])2 (4), i.e., pꢀchloronitrosobenzene reacts
with palladium carbonyl acetate in the same way as
nitrosobenzene. The yield of complex 4 was ∼50% based
on cluster 1, while the rest of Pd was found as Pd black
(the yield of Pd black was also ∼50%).
Table 1. Comparative analysis of the EXAFS data for complexes
2a, 4, and 5 and Xꢀray diffraction data for complex 2a
Comꢀ Bond
plex
EXAFS (Xꢀray diffraction) data
Thus, the electronꢀwithdrawing effect of the substituꢀ
ent in the paraꢀposition of nitroso compound has an inꢀ
fluence on the reaction rate but does not prevent the
interaction of the resulting chlorophenylnitrene species
with the pꢀchloronitrosobenzene molecule.
The reaction of carbonyl acetate cluster 1a with
оꢀchloronitrosobenzene proceeds similarly to the reacꢀ
tion described above. The enhancement of the steric hinꢀ
drance in the molecule of substituted nitrosoarene inꢀ
creases the reaction duration at 50 °C to 15—20 h. The
amount of carbon dioxide evolved also does not exceed
half the stoichiometric amount based on cluster 1. The
Bond length/Å
CN*
Debye factor
2a
4
Pd—N
Pd—O
Pd—Pd
Pd—N
Pd—O
Pd—Pd
Pd—N
Pd—O
Pd—Pd
2.05 (2.02, 1.98) 1.1 (2)
0.008
0.001
0.025
0.006
0.004
0.017
0.001
0.001
0.027
1.99 (2.06)
2.74 (2.84)
2.11
1.1 (2)
0.7 (1)
1.2
2.00
1.3
2.78
0.6
5
2.12
0.8
2.01
1.4
2.77
0.9
* The number of bonds of this type.

Chloronitrosoarene palladium complexes
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
821
molecule and by the great amplitude of thermal vibrations
of the metal atom. Apparently, the same situation holds
for complexes 4 and 5. Each metal atom is chelated by a
nitrogenꢀcontaining arylnitrosoarene ligand, which is
linked to the Pd atom through the N atoms of the amide
and nitroso groups.
Thus, the reactions of carbonyl carboxylate clusters 1
with оꢀ and pꢀchloronitrosobenzenes appear to proceed
similarly to the reaction with nitrosobenzene. The first
stage is elimination of the O atom from the chloronitrosoꢀ
benzene molecule coordinated by the CO group giving
rise to a chlorophenylnitrene species (Scheme 1).
nitrene with оꢀchloronitrosobenzene. The insertion of
оꢀchlorophenylnitrene species into the solvent (toluene)
molecule affords 2ꢀchlorophenyltolylamines. оꢀChloroꢀ
aniline may result from the reduction of оꢀchlorophenylꢀ
nitrene. Finally, оꢀchlorophenyl isocyanate is produced
in the reaction of оꢀchlorophenylnitrene with the coordiꢀ
nated carbonyl group.
Thus, the reaction of carbonyl carboxylate clusters 1
with оꢀ and pꢀchloronitrosobenzenes proceeds similarly
to the reaction with unsubstituted nitrosobenzene and
gives finally dinuclear complexes with the chelating
arylnitrosoarene ligand. The presence of electronꢀwithꢀ
drawing atoms in the nitrosoarene molecule results only
in a substantial retardation of the reaction, without influꢀ
encing the composition or the structure of Pdꢀcontaining
products.
Chemical properties of the complexes obtained. The
chemical behavior of the synthesized compounds was studꢀ
ied in relation to complex 4. The major products formed
in the reaction of 4 with hydrogen include palladium
metal, acetic acid, cyclohexanone, and molecular nitroꢀ
gen (identified by GC); the two lastꢀmentioned substances
could be formed only from the chelating amide ligand.
Judging by the final products, complex 4 reacts with H2
similarly to complexes 2 and 3.12 The first step affords
aromatic amine (Scheme 3).
Scheme 1
∼Pd[CO]∼ + Cl—C6H4—NO
CO2 + ∼Pd[Cl—C6H4—N:]∼
The subsequent transformations of the chlorophenylꢀ
nitrene species include, as those of the phenylnitrene speꢀ
cies, insertion into the C—H bond of the benzene ring of
the second chloronitrosobenzene molecule yielding the
nitrosoamide ligand ClC6H4N[ClC6H3NO]. Apparently,
in the reaction of cluster 1a with оꢀchloronitrosobenzene,
which has no C—H bond in position 2, the chloronitrene
species is inserted in position 6 of the Ph ring (Scheme 2).
Scheme 2
Scheme 3
Pd2(OAc)2(pꢀClC6H4N[pꢀClC6H3NO])2 + H2
4
Pd0 + AcOH + pꢀClC6H4NH2 + ...
Although we were unable to detect the intermediate
products of transformation of the aromatic amine into
cyclohexanone, we may consider that the process is simiꢀ
lar to the transformation of complexes 2 and 3. The reꢀ
duction of aromatic amine yields an unstable unsaturꢀ
ated cyclic amine, which can rearrange into imine
(imino—enamine tautomerism). On treatment with water
Scheme 4
Apart from the organopalladium products, the reacꢀ
tion of cluster 1 with оꢀchloronitrosobenzene yields a
broad set of Nꢀcontaining organic products, which were
detected by GC/MS analysis. The analysis confirms the
intermediate formation of the chlorophenylnitrene speꢀ
cies during the reaction. Bis(2ꢀchlorophenyl)diazene
arises apparently upon dimerization of two chlorophenylꢀ
nitrene species. N,N´ꢀBis(2ꢀchlorophenyl)diazene
Nꢀoxide is the product of reaction of оꢀchlorophenylꢀ
i. H2O or AcOH.

822
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
Orlova et al.
with xenon (complete absorption) and an Ar—He mixture (1 : 1)
(monitoring chamber) up to a pressure of 1 atm. The energy
resolution was ∼4 eV. Samples of the complexes were prepared
by mixing the powder with Apieson and squashing the paste
between two flat surfaces. The absorption jump in the palladium
Kꢀedge was 0.8—1.0.
The oscillating part of the absorption spectrum was cut out
by a standard procedure14 using the VIPER program package.15
The preꢀedge part of the absorption spectrum was interpolated
to the EXAFS region by Victoreen polynomials. The smooth
part of the absorption coefficient was simulated by three interꢀ
polating cubic splines. The inflection point at the edge of the
absorption jump was taken as the initial point E0 (k = 0). The
spectrum was simulated by the k2χ(k) function in the range of
wave numbers of 3.5—15.0 Å–1. The simulation was carried out
using the EXCURV92 program.16
or carboxylic acid, the imine is converted into cyclic keꢀ
tone and ammonia (Scheme 4).
Apparently, this hydrolysis (or acidolysis) is facilitated
by a decrease in the basicity of the imine due to its coordiꢀ
nation to the PdII atom and by binding of the ammonia
evolved into the palladium amino complex. Molecular
nitrogen is formed, most likely, in the innerꢀsphere oxiꢀ
dation of the Pdꢀcoordinated ammonia (or amines).
Treatment of complex 4 with CO under mild condiꢀ
tions (1 atm, 20 °C, ∼20 h) gives rise to pꢀchlorophenyl
isocyanate (Scheme 5).
Scheme 5
Organic solvents were purified by standard procedures.17
Nitrosoaromatic compounds, pꢀ and oꢀClC6H4NO, were preꢀ
pared by the general procedure18,19 by reduction of pꢀ and
оꢀchloronitrobenzene with zinc dust to pꢀ and оꢀchlorophenylꢀ
hydroxylamine followed by oxidation of phenylhydroxylamine
with sodium dichromate in aqueous H2SO4 to the correspondꢀ
ing chloronitroso compound. The resulting chloronitrosoarenes
were isolated from the reaction mixture by azeotropic distillaꢀ
tion with steam under atmospheric pressure. The purity of comꢀ
pounds was checked by TLC on Silufol and on the basis of the
melting point. Due to the possibility of oxidation of the nitroso
group in nitrosoaromаtic compounds with air oxygen, chloroꢀ
nitrosoarenes were stored for short periods in a Schlenk vessel
under argon in refrigerators and all reactions with these comꢀ
pounds were carried out under argon.
Pd2(OAc)2(pꢀClC6H4N[pꢀClC6H3NO])2 + CO
4
Pd0 + AcOH + pꢀClC6H4NCO
The results of this study indicate that the presence of
electronꢀwithdrawing substituents in the arylnitrosoarene
ligand of complexes 4 and 5 does not affect much the
behavior of these complexes in reducing media, and the
compounds resulting from reductive decomposition are
similar to those obtained upon the reduction of comꢀ
plex 2.12,13
Experimental
Palladium carbonyl acetate Pd4(µꢀCOOMe)4(µꢀCO)4 (1a)
was prepared by procedures reported previously.20—22
Elemental microanalysis of the reaction products for carbon,
nitrogen, and hydrogen was carried out using a C,H,Nꢀanalyzer
(Carlo Erba, Italy). The IR spectra of complexes in the region of
400—4000 cm–1 were measured on a Specord Mꢀ80 spectromꢀ
eter (as a suspension in mineral oil). The H NMR spectra of
complexes in CD2Cl2 solutions were recorded on a Varianꢀ200
instrument (200 МHz).
Syntheses of complexes 4 and 5 were carried out at 50 °C in a
twoꢀnecked jacketed flask equipped with a magnetic stirrer, conꢀ
nected to a thermostat and to a gas burette for measuring the
volume of the evolved gas and to a system for evacuation and
filling with an inert gas (argon). The flask was charged with
cluster 1 (1 mmol, 4 mgꢀat Pd). Then toluene (16 mL) was
added, the system was evacuated and filled with argon, and the
reaction mixture was stirred. A solution of chloronitroso comꢀ
pound (4 mmol) in 24 mL of toluene was added in an argon flow
to the resulting suspension, the system was again purged with
argon, and the mixture was stirred and heated to 50 °C. The
reaction was monitored by volumetry based on CO2 evolution.
After completion of the reaction (10—20 h), the solution was
filtered to remove the Pd black, toluene was completely evapoꢀ
rated at a reduced pressure, and the complex thus obtained was
dissolved in CH2Cl2. The complex was isolated in two steps:
precipitation with pentane from a partially concentrated soluꢀ
tion in CH2Cl2, and, after repeated drying of the filtrate, dissoꢀ
lution of the residue in CH2Cl2, and concentration, precipitaꢀ
tion with heptane (in the presence of a small amount of Et2O in
CH2Cl2). After collection on a filter, the product was dried in
vacuo and stored under argon.
1
The reaction products were analyzed by GC for CO, CO2,
O2, H2, Ar, N2, and NOx on an LKhMꢀ80 instrument (molecuꢀ
lar sieves and Polysorb). The liquid phase was analyzed by GLC
on a 3700 chromatograph (OVꢀ101 column for the analysis of
cyclic hydrocarbons, cyclic ketones, and highꢀboiling aromatic
amines; a REOPLEX column for the analysis of volatile polar
organic products) and by CC/MS on an Automass instrument
(Delsi Nermag, France) (columns with the silicon SEꢀ30 phases
for the analysis of cyclic hydrocarbons, cyclic ketones, and highꢀ
boiling aromatic amines, and with PEGꢀ20М for the analysis of
volatile polar organic products).
The palladium Kꢀedge EXAFS absorption spectra were reꢀ
corded on an EXAFS station of a VEPPꢀ3 storage ring (Siberian
Center of Synchrotron Radiation, Novosibirsk) with an electron
beam energy of 2 GeV and an average current during measureꢀ
ment of 60 mA. A double singleꢀblock Si(111) monochromator
crystal was used for monochromatization. No harmonic supꢀ
pression was applied, because only the third harmonics (72 keV),
whose intensity is negligibly low, is reflected from the monoꢀ
chromator crystal. The spectra were recorded at ~20 °C in the
transmission mode using for detection ionization chambers filled
Bis(acetato)bis[2ꢀ(5ꢀchloroꢀ2ꢀnitrosophenyl)ꢀ(4ꢀchloropheꢀ
nyl)amine]dipalladium, Pd2(OAc)2(pꢀClC6H4N[pꢀClC6H3NO])2
(4). The reaction of cluster 1a with pꢀchloronitrosobenzene was
over within 10—15 h. A finely crystalline greenishꢀbrown preꢀ
cipitate was isolated from the reaction mixture. Found (%):
C, 38.73; N, 5.71. C28H20Cl4N4O6Pd2. Calculated (%): C, 38.94;

Chloronitrosoarene palladium complexes
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
823
N, 6.49. IR, ν/cm–1: 1632; 1552; 1420; 1088. 1H NMR, δ: 2.10,
7.20 (both br.m). The ratio of the integral intensities of the
signals of AcOꢀ and Phꢀgroup protons was ∼3 : 7. The yield of
compound 4 was 45—50% (based on Pd), decomp. point (in
argon) 185 °C.
Bis(acetato)bis[2ꢀ(3ꢀchloroꢀ2ꢀnitrosophenyl)ꢀ(2ꢀchloropheꢀ
nyl)amide]dipalladium, Pd2(OAc)2(оꢀClC6H4N[оꢀClC6H3NO])2
(5). The reaction of cluster 1a with оꢀchloronitrosobenzene was
over within 15—20 h. A finely crystalline greenishꢀbrown preꢀ
cipitate was isolated from the reaction mixture. Found (%):
C, 37.24; N, 5.57. C28H20Cl4N4O6Pd2. Calculated (%): C, 38.94;
N, 6.49. IR, ν/cm–1: 1700; 1560; 1450; 1240. 1H NMR, δ: 2.10,
7.00 (both br.m). The ratio of the integral intensities of the
signals of AcOꢀ and Phꢀgroup protons was ∼3 : 7. The yield of
compound 5 was 50—60% (based on Pd).
[M – CH2CO]+ (13), 55 [M – Me – 2 CH2]+ (79), 42 [M –
CH2CO – CH2]+ (100), 41 [M – Me – 3 CH2]+ (50), 39 [M –
Me – 2 CH2 – O]+ (50).
In the carbonylation of complex 4, AcOH and pꢀchloroꢀ
phenyl isocyanate were the major products.
AcOH, MS (EI, 70 eV), m/z (Irel (%)): 60 [M]+ (46), 45
[M – Me]+ (88), 44 [M – O]+ (8), 43 [M – OH]+ (100), 42
[M – OH – H]+ (17).
pꢀClC6H4NCO, MS (EI, 70 eV), m/z (Irel (%)): 155—153
[M]+ (33—100), 127—125 [M – CO]+ (8—29), 98 [M – CO –
NCH]+ (2), 90 [M – CO – Cl]+ (17), 85 [M – CO – CH2CN]+
(4), 63 [M – CO – Cl – NCH]+ (33), 50 [M – CO –
CH2CN – Cl]+ (17).
The authors are grateful to A. E. Gekhman for
assistance in GLC/MS analysis of the reaction soluꢀ
GC/MS analysis of the reaction mixture revealed a mixture
of organic products.
1
tions and to S. G. Sakharov for recording the H NMR
Bis(2ꢀchlorophenyl)diazene. MS (EI, 70 eV), m/z (Irel (%)):
252—250 [M]+ (18—29), 152 [M – C5H3Cl]+ (11), 141—139
[M – C6H4Cl]+ (18—54), 113—111 [M – C6H4Cl – N2]+
(32—100), 85 [M – C6H4Cl – N2 – C2H2]+ (7), 75
[M – C6H4Cl – N2 – HCl]+ (71), 50 [M – C6H4Cl – N2 –
C2H2 – Cl]+ (18).
spectra.
This study was financially supported by the Ministry
of Education of the Russian Federation (Project Е02ꢀ5.0ꢀ
185) and the Russian Foundation for Basic Research
(Project No. 04ꢀ03ꢀ32436).
N,N´ꢀBis(2ꢀchlorophenyl)diazene Nꢀoxide. MS (EI, 70 eV),
m/z (Irel (%)): 268—266 [M]+ (1—4), 252—250 [M – O]+ (4—7),
233—231 [M – Cl]+ (32—93), 168 [M – C5H3Cl]+ (28), 152
[M – C5H3Cl – O]+ (4), 141—139 [M – C6H4Cl – O]+ (4—11),
127—125 [M – C5H3Cl – O – NCH]+ (7—18), 113—111 [M –
C6H4Cl – O – N2]+ (36—100), 101—99 [M – C5H3Cl – O –
CH – NCH – NC]+ (4—14), 90 [M – C5H3Cl – O – NCH –
Cl]+ (36), 75 [M – C5H3Cl – O – CH – N2 – HCl]+ (82).
2ꢀChlorophenyltolylamines. 2ꢀChlorophenylꢀоꢀtolylamine,
MS (EI, 70 eV), m/z (Irel (%)): 219—217 [M]+ (32—93), 182
[M – Cl]+ (100), 180 [M – H2Cl]+ (93), 167 [M – Cl – Me]+
(68), 106 [M – Cl – C6H4]+ (7), 90 [M – Cl – Me – C6H4 – H]+
(18). 2ꢀChlorophenylꢀpꢀtolylamine, MS (EI, 70 eV),
m/z (Irel (%)): 219—217 [M]+ (25—75), 182 [M – Cl]+ (79),
180 [M – H2Cl]+ (29), 167 [M – Cl – Me]+ (100), 90 [M –
Cl – Me – C6H4 – H]+ (11).
оꢀChloroaniline. MS (EI, 70 eV), m/z (Irel (%)): 129—127
[M]+ (35—100), 92 [M – Cl]+ (21), 91 [M – HCl]+ (7), 65
[M – Cl – NCH]+ (35), 39 [M – Cl – NCH – C2H2]+ (11).
оꢀChlorophenyl isocyanate MS (EI, 70 eV), m/z (Irel (%)):
155—153 [M]+ (33—100), 127—125 [M – CO]+ (15—43), 98
[M – CO – NCH]+ (6), 90 [M – CO – Cl]+ (47), 63 [M –
CO – Cl – NCH]+ (25), 49 [M – CO – Cl – NCH – CH2]+ (4).
Reduction of nitrosoarene complex 4 with hydrogen or carbon
monoxide was carried out at 20 °C and a gas pressure of 1 atm in
a twoꢀnecked flask equipped with a stirrer and a sampler for
gases and liquids. The flask was charged with the complex
(0.25 mmol), 2 mL of a solvent (benzene or toluene) was added,
and the system was evacuated. Then H2 or CO was fed and the
mixture was stirred. The gaseous and liquid reaction products
were analyzed by GLC and GC/MS in the course of experiꢀ
ments, which lasted for several weeks for the reaction with H2
and for 2—3 days for the reaction with CO.
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