Imido/nitrene ligands in the complexes of platinum metals

Article abstract of DOI:10.1016/S0022-328X(97)00441-5

A synthetic search for palladium and platinum complexes with nitrene ligands via reaction of tetranuclear cluster Pd₄(μ²-CO)₄(μ²-OAc) ₄ with nitrosobenzene and reactions of mononuclear complexes [MX₄]^2- (M=Pt, Pd; X=Cl, NO₂) with o-phenylenediamine and its N-phenyl derivative have been carried out. The complexes obtained, [Pd(OAc)o-(PhN)(NO)C₆H₄]₂, Pd[o-(NPh)(N)C₆H₄]₂, Pt[o-(NPh)(N)C₆H₄]₂, Pt₂[o-(NPh)(N)C₆H₄]₄[O ₃SCF₃]₂, and Pt₂[o-(NPh)(N)C₆H₄]₄Br₂, have been structurally characterized by single crystal X-ray diffraction studies. The oxidation of complex Pt[o-(NPh)(N)C₆H₄]₂ by excess AgO₃SCF₃ afforded a heterotricyclic quinoxaline derivative, whose structure has been determined by X-ray analysis. The data obtained suggest that labile nitrene species coordinated to Pd and Pt complexes are possible intermediates in the reactions under study.

Full text of DOI:10.1016/S0022-328X(97)00441-5

Ž
.
Journal of Organometallic Chemistry 551 1998 171–194
1
Imidornitrene ligands in the complexes of platinum metals
I.L. Eremenko a,), S.E. Nefedov , A.A. Sidorov , M.O. Ponina , P.V. Danilov ,
a
a
a
a
a
a
a
a
a
T.A. Stromnova , I.P. Stolarov , S.B. Katser , S.T. Orlova , M.N. Vargaftik ,
b,3
I.I. Moiseev a,2, Yu.A. Ustynyuk
a
N.S. KurnakoÕ Institute of General and Inorganic Chemistry, Russian Academy of Sciences 31, Leninski Prospect, GSP-1, Moscow 117907,
Russian Federation
b
Department of Chemistry, M.V. LomonosoÕ Moscow State UniÕersity, Vorobery Gory, Moscow 119899, Russian Federation
´
Received 19 May 1997; received in revised form 10 July 1997
Abstract
2
2
Ž
. Ž
4
A synthetic search for palladium and platinum complexes with nitrene ligands via reaction of tetranuclear cluster Pd4 m -CO m -
2
y
.
w
x
Ž
.
OAc with nitrosobenzene and reactions of mononuclear complexes MX4
MsPt, Pd; XsCl, NO2 with o-phenylenediamine and
4
w
Ž
.
Ž
.Ž .Ž .
.
x
w
Ž
x
,
its N-phenyl derivative have been carried out. The complexes obtained, Pd OAc o- PhN NO C6H4 2, Pd o- NPh N C6H4 2
.Ž . .Ž . x w .Ž .
w
Ž
x
w
Ž
x
w
Ž
x
Pt o- NPh N C6H4 2, Pt2 o- NPh N C6H4 4 O3SCF3 2, and Pt2 o- NPh N C6H4 4Br2, have been structurally characterized by
w
Ž
.Ž .
x
single crystal X-ray diffraction studies. The oxidation of complex Pt o- NPh N C6H4 2 by excess AgO3SCF3 afforded a heterotricyclic
quinoxaline derivative, whose structure has been determined by X-ray analysis. The data obtained suggest that labile nitrene species
coordinated to Pd and Pt complexes are possible intermediates in the reactions under study. q 1998 Elsevier Science S.A.
Keywords: Ligands; Nitrene; Clusters
1. Introduction
Complexes of the platinum group metals, particularly palladium, are known as promising catalysts for the
w
x
industrially desirable syntheses of aryl isocyanates and carbamates based on nitroarenes 1,2 :
ArNO2 q3C0sArNCOq2CO2
1
Ž .
ArNO q3C0qROHsArNHCO O ORq2C0
2
Ž .
Ž
.
2
2
Ž
.
Ž
.
Due to the presence of an oxidant nitroarene and a reductant CO in the reaction system, both low- and
high-valent metal compounds could be formed as key reaction intermediates from a starting metal complex or disperse
metal, regardless of its initial valence state. Despite numerous works having been published on this topic, the valence
)
Corresponding author. Tel.: q7-095-952-12-03; fax: q7-095-954-12-79; e-mail: iimois@ionchran.msk.ru.
1 Dedicated to Professor Peter Maitlis in recognition of his outstanding contribution to homogeneous catalysis and organometallic chemistry.
2 Also corresponding author.
3 Fax: q7-095-939-0126.
0022-328Xr98r$19.00 q 1998 Elsevier Science S.A. All rights reserved.

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172
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
state, nuclearity, and particularly the nature of ligands in the metal compounds responsible for the catalysis of
Ž . Ž .
reactions 1 and 2 are still poorly understood.
w x
w
x
Previously 3 , the low-valent palladium-561 giant clusters 4,5 have been found to be effective catalyst precursors
Ž .
for both the synthesis of phenylisocyanate from nitrobenzene via reaction 1 and its conjugate reaction, the
carbonylation of nitrobenzene coupled with the oxidation of CO to diphenyl carbonate by nitrobenzene
PhNO q3COq2PhOHsPhNCOq PhO COqCO qH O
3
Ž .
Ž
.
2
2
2
2
Ž .
The conjugation of two redox processes within reaction 3 has been suggested as a concerted electron-transfer
w x
process, where the metal core of Pd-561 cluster or a similar compound serves as an electron transfer mediator 3 .
Although the detailed mechanism of these reactions is still unclear, the loss of two O atoms from the nitrobenzene
Ž .
Ž .
molecule during its transformation to phenylisocyanate via reactions 1 or 3 can be suggested as a successive
elimination of the O atoms to form, at some of the reaction stage, an intermediate nitrene moiety attached to a
palladium cluster: PhNsPd-. Similar nitrene intermediates were also suggested for the hydrogen-transfer reduction
w x
of nitrobenzene by formic acid in the presence of the giant Pd cluster 6 .
w
x
Stable nitrene complexes are fairly common for the IV–VI metal groups 7,8 and, to a less extent, for the early
VIII group metals and Ru and Os 8–15 . Meanwhile, nitrene derivatives remain rarities in the chemistry of the late
VIII group metals. To the best of our knowledge, such compounds are still unknown among complexes of Pd and Pt
w
x
w
x
7,8 . In this work, we attempted to gain insight into nitrene chemistry of palladium and platinum.
2. Results and discussion
2.1. General approach
w
x
Based on the literature data 7–15 , the following approaches seem to be the candidates for the syntheses of
Ž .
Ž
platinum metal–nitrene complexes: 1 reaction with azo and diazo compounds e.g., ArNsNAr, Me3SiNsNSiMe3,
Ž . . Ž .
Ž
. Ž .
ArC H N2 ; 2 oxidation of amines e.g., ArNH2 , Me3SiNHR ; 3 reduction of nitroarenes.
In this work, some poly- and mononuclear Pd complexes and mononuclear Pt complexes were examined in
reactions with amines, azo and azoxybenzene, phenylhydroxylamine, nitro compounds, and nitrosobenzene as possible
2
2
Ž
. Ž
. Ž .
w x
ways to synthesise the nitrene complexes. The tetranuclear palladium cluster Pd4 m –CO
m –OAc I 16 could
4
4
Fig. 1. Molecular structure of complex II.

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I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
173
Table 1
The main geometric parameters for structure II
˚
( )
Bond lengths A
Ž .
Pd 1 –N 2
Ž .
Ž .
2.840 1
1.97 1
Ž . Ž .
Pd 1 –N 1
Ž .
1.970 9
Pd 1 –Pd 1
Ž . Ž .
Ž .
Ž . Ž .
Pd 1 –O 2
Ž .
2.072 8
Ž . Ž .
Ž .
Ž . Ž .
N 1 –C 1
Ž .
1.31 2
Pd 1 –O 3
2.068 8
Ž . Ž .
Ž .
Ž . Ž .
N 2 –O 1
O 2 –C 13
Ž .
1.24 1
N 1 –C 7
1.43 1
Ž . Ž .
Ž .
Ž .
Ž
.
Ž .
1.25 2
N 2 –C 2
Ž .
1.37 1
Ž
.
Ž .
Ž
.
Ž
.
Ž .
1.50 2
O 3 –C 13
1.24 2
C 13 –C 14
Ž
.
Ž
.
Ž .
C 11 –C 15
1.71 2
( )
Bond angles 8 :
X
X
Ž . Ž . Ž .
Ž .
77.5 2
Ž . Ž . Ž .
Ž .
95.8 3
Pd 1 Pd 1 N 1
103.5 3
Pd 1 Pd 1 N 2
X
X
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
81.3 2
Pd 1 Pd 1 O 2
Pd 1 Pd 1 O 3
Ž . Ž . Ž .
Ž .
81.8 4
Ž . Ž . Ž .
Ž .
178.8 4
N 1 Pd 1 N 2
N 1 Pd 1 O 2
Ž . Ž . Ž .
Ž .
92.5 4
Ž . Ž . Ž .
Ž .
97.5 4
N 1 Pd 1 O 3
N 2 Pd 1 O 2
Ž . Ž . Ž .
Ž .
172.8 4
Ž . Ž . Ž .
Ž .
88.3 3
N 2 Pd 1 O 3
Ž . Ž . Ž .
O 2 Pd 1 O 3
Ž .
113.7 8
Ž . Ž . Ž .
Ž .
123.5 7
Pd 1 N 1 C 1
Pd 1 N 1 C 7
Ž . Ž . Ž .
Ž .
122.3 9
Ž . Ž . Ž .
Ž .
125.3 7
C 1 N 1 C 7
Pd 1 N 2 O 1
Ž . Ž . Ž .
Pd 1 O 2 C 13
Ž . Ž . Ž .
O 2 C 13 O 3
Ž .
113.0 7
Ž . Ž . Ž .
Ž .
121.3 9
Pd 1 N 2 C 2
Ž . Ž . Ž
O 1 N 2 C 2
.
Ž .
123.0 8
Ž . Ž . Ž
.
Ž .
119.1 8
Pd 1 O 3 C 13
Ž .
127 1
Ž
.
Ž
act as both an oxidant in reactions with phenylhydroxylamine and azobenzene and a reductant for azoxy, nitro and
.
Ž
.
Ž
.
nitroso compounds owing to the intermediate oxidation state q1 of its palladium atoms. Mononuclear Pt, Pd q2
Ž
.
Ž
.
complexes K2 PtX4 XsCl, NO2 and K2 Pd NO2 were used as both the metal atom source and oxidants in
4
experiments with 1,2-phenylenediamine and its N-phenyl derivative.
Table 2
Main geometric parameters for complex IV
˚
( )
Bond lengths A
Ž . Ž .
Pt 1 –N 2A
Ž .
1.954 4
1.989 6
Ž . Ž .
Pt 1 –N 2
N 1 –C 1
Ž .
1.331 9
Ž .
Ž
.
Ž .
1.954 4
Pt 1 –N 1
1.989 6
Pt 1 –N 1A
Ž . Ž .
N 2 –C 2
Ž .
Ž
.
Ž .
Ž . Ž .
Ž .
Ž .
1.368 7
Ž . Ž .
Ž .
Ž . Ž .
Ž .
Ž . Ž .
C 1 –C 6
Ž . Ž .
C 4 –C 5
Ž .
1.391 8
N 2 –C 7
1.410 7
C 1 –C 2
1.443 8
Ž . Ž .
Ž
.
.
Ž . Ž .
Ž .
Ž .
1.407 9
C 2 –C 3
1.387 10
C 3 –C 4
1.403 8
Ž . Ž .
Ž
Ž . Ž .
C 9 –C 10
Ž
.
.
Ž .
Ž
.
Ž
.
.
C 5 –C 6
1.369 11
C 7 –C 8
1.410 10
C 7 –C 12
1.389 12
Ž . Ž .
Ž .
Ž .
Ž
.
Ž
Ž
.
Ž
.
Ž
1.416 12
C 8 –C 9
1.380 9
1.398 14
C 10 –C 11
Ž
.
Ž
.
.
Ž .
Ž . Ž .
Ž .
Ž . Ž .
Ž .
C 11 –C 12
1.375 8
Pt 2 –N 3
1.949 5
Pt 2 –N 4
Ž . Ž .
N 3 –C 13
1.971 6
Ž .
Ž
Ž
Ž .
Ž .
N 4 –C 19
Ž
.
Ž .
Ž .
Pt 2 –N 3A
1.949 5
Ž .
Pt 2 –N 4A
1.971 6
Ž .
1.331 9
Ž .
.
Ž .
Ž
.
Ž
.
Ž
.
.
.
.
Ž .
N 4 –C 18
1.366 7
1.433 7
C 13 –C 14
1.434 8
Ž .
1.401 9
Ž
.
.
Ž
Ž
.
.
.
.
Ž .
Ž
.
Ž
.
.
.
.
Ž
.
.
Ž
.
Ž
C 13 –C 18
1.437 8
C 14 –C 15
1.348 10
C 15 –C 16
Ž
Ž .
Ž
.
Ž
Ž
Ž
.
Ž
Ž
.
.
C 16 –C 17
1.380 8
C 17 –C 18
1.424 10
C 19 –C 20
1.388 10
Ž
.
Ž
Ž
.
.
Ž
.
.
Ž
Ž .
Ž
.
Ž
Ž
1.378 11
C 19 –C 24
1.381 10
C 20 –C 21
1.364 9
Ž .
1.401 9
C 21 –C 22
Ž
.
Ž
Ž
Ž
Ž
C 22 –C 23
1.391 11
C 23 –C 24
( )
Bond angles 8
Ž . Ž . Ž .
Ž .
79.7 2
100.3 2
Ž . Ž .
N 1 –Pt 1 –N 2A
Ž
.
.
Ž .
180.0 1
N 1 –Pt 1 –N 2
N 1 –Pt 1 –N 1A
Ž . Ž .
N 2 –Pt 1 –N 2A
Ž
.
.
Ž .
Ž . Ž .
Ž
Ž .
100.3 2
N 2 –Pt 1 –N 1A
Ž . Ž .
Ž
Ž .
Ž
.
Ž .
Ž
.
Ž .
79.7 2
180.0 1
N 1A –Pt 1 –N 2A
Ž . Ž . Ž .
Ž . Ž . Ž .
Ž .
Ž .
115.6 4
Pt 1 –N 1 –C 1
117.4 4
Pt 1 –N 2 –C 2
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
120.8 6
Pt 1 –N 2 –C 7
123.6 4
C 2 –N 2 –C 7
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
126.7 6
N 1 –C 1 –C 2
114.5 5
N 1 –C 1 –C 6
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
112.8 6
C 2 –C 1 –C 6
118.7 6
N 2 –C 2 –C 1
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
120.5 7
N 2 –C 2 –C 3
126.3 5
N 2 –C 7 –C 8
Ž . Ž .
Ž
Ž
Ž
.
Ž .
Ž . Ž . Ž .
Ž .
N 2 –C 7 –C 12
120.6 6
N 3 –Pt 2 –N 4
80.0 2
Ž . Ž .
.
.
Ž .
Ž . Ž .
Ž
.
.
.
Ž .
N 3 –Pt 2 –N 3A
180.0 1
N 4 –Pt 2 –N 3A
100.0 2
Ž . Ž .
Ž .
Ž . Ž .
Ž
Ž .
N 3 –Pt 2 –N 4A
100.0 2
N 4 –Pt 2 –N 4A
180.0 1
Ž
.
Ž .
Ž
.
Ž .
Ž . Ž .
Ž
Ž .
117.4 4
N 3A –Pt 2 –N 4A
Ž . Ž .
80.0 2
Pt 2 –N 3 –C 13
Ž
.
Ž .
Ž . Ž .
Ž
.
Ž .
124.7 4
Pt 2 –N 4 –C 18
115.2 4
Pt 2 –N 4 –C 19
Ž
.
Ž .
Ž
.
.
.
.
Ž .
Ž .
Ž
.
Ž
.
.
.
Ž .
127.4 6
C 18 –N 4 –C 19
120.1 6
N 3 –C 13 –C 14
Ž .
Ž
.
Ž
Ž .
Ž .
Ž
.
Ž
Ž
Ž .
113.6 6
N 3 –C 13 –C 18
113.7 5
N 4 –C 18 –C 13
Ž .
Ž
.
Ž
Ž .
126.9 5
Ž .
Ž
.
Ž .
119.9 6
N 4 –C 18 –C 17
N 4 –C 19 –C 20
Ž .
Ž
.
Ž
Ž .
119.0 6
N 4 –C 19 –C 24

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I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
Fig. 2. Two independent molecules of complex IV.
2.2. Reactions of palladium cluster I
2.2.1. Azobenzene
Our experiments showed that cluster I does not react with azobenzene in a benzene solution neither at room
w
x
temperature nor in boiling benzene 17 . In the last case, only thermal decomposition of cluster I was observed
w
x
according to the following reactions 18,19 :
Pd4 m2 yCO m2 yOAc ™PdqCO q MeCO .
Ž
.
Ž
.4Ž
.
2
2
4
Pd4 m2 yCO m2 yOAc qC H ™Pdq MeCO 2 qC H COOH,
Ž
.
Ž
.4Ž
.
6
6
6
5
4
no products from the reaction with azobenzene were found.
Fig. 3. Molecular structure of initial ligand N-phenyl-o-phenylenediamine.

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I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
175
2.2.2. Azoxybenzene
Reaction of cluster I with azoxybenzene proceeds slowly at 808C in toluene. Only CO was observed in the gas
phase, whereas neither CO2 nor any product of the azoxybenzene conversion were found. Under more severe
Ž
.
conditions 1208C , azoxybenzene oxidized coordinated CO to CO2 , itself being reduced to azobenzene:
Pd4 m2 yCO m2 yOAc qPhN O sNPh™PdqPhNsNPhqCO
Ž
.
Ž
.4Ž
.
2
4
2.2.3. Phenylhydroxylamine
Cluster I readily reacts with phenylhydroxylamine: in benzene and toluene solutions, 50% conversion of I is
achieved in 1 h at room temperature to form Pd metal and CO2 and traces of CO in the gas phase; the liquid products
are aniline, azobenzene, and azoxybenzene. No metal complexes but unreacted cluster I were found.
2.2.4. Nitro compounds
Reaction of carbonyl metal clusters with nitroarenes and nitroalkanes is a well-known route to nitrene complexes
w
x
10 . Our experiments showed that cluster I does not react with PhNO2 and MeNO2 at 208C. Neither reduction of the
w
x
nitro compounds nor other products but the formation of those resulting from the normal thermolysis of I 18 were
found even at temperatures up to 808C.
2.2.5. Nitrosobenzene
In contrast to nitro compounds, nitrosoarenes were found to actively react with cluster I in a toluene or benzene
solution at 608C evolving CO2.
In the synthetic practice of cluster chemistry, aliphatic tertiary amine oxides are commonly used for removing CO
ligands from the coordination sphere of transition metals. The tertiary amines formed coordinate only weakly to
low-valent transition metals, and the free coordination vacancy just formed is used for growing the cluster metal
w
x
skeleton, ligand substitution, etc. 20 . By analogy, in the case of nitrosobenzene, the PhNO molecule could be
expected to donate its O atoms to the coordinated CO ligand of I to produce a nitrene ligand:
)PdyCOqPhNO™)PdsNPhqCO2 .
4
Ž .
Ž .
The supposed nitrene species which could form in reaction 4 is expected to either dimerize to the corresponding
azo compound or become attached to the Pd atom forming a nitrene complex.
We found that the product of the reaction between cluster I and nitrosobenzene is an air-stable brown solid, readily
Ž
.
soluble in low-polar organic solvents, with empirical formula PdC14 H12O3N2 complex II : according to IR spectra,
1
Ž
complex II does not contain coordinated carbonyl groups. H NMR spectrum displayed acetate group singlet at
.
Ž
.
ds1.9 ppm and phenyl moiety characteristic multiplet at ds6.8–8.0 ppm in the composition of complex II.
These facts could have been considered as an indication to the oxidation of the coordinated CO ligands by
Ž
.
nitrosobenzene without reducing Pd q1 , and the reaction could be tentatively described by the following equation:
Pd4 CO OAc 4 q4PhNO
Ž
.4 Ž
.
™4CO q4 Pd OAc PhN
.
5
Ž .
Ž
. Ž
.
2
However, the elemental analysis data of complex II corresponds to a compound containing one acetato group and
Ž
.Ž
.Ž
.
one nitrosobenzene molecule, along with a nitrene moiety, PhN, per one Pd atom, ‘‘Pd OAc PhN PhNO ’’.
Table 3
Main geometric parameters for the molecule of N-phenyl-o-phenylenediamine
˚
( )
Bond lengths A
Ž . Ž .
N 1 –C 1
Ž .
1.384 5
1.419 3
Ž .
N 2 –C 7
Ž
.
Ž
.
Ž .
Ž
.
.
Ž
.
.
N 1 –H 1N
Ž . Ž .
0.960 52
Ž .
N 1 –H 2N
0.776 46
Ž
0.852 39
Ž . Ž .
Ž .
Ž .
Ž
N 2 –C 2
1.387 3
N 2 –H 3N
Ž . Ž .
Ž .
Ž . Ž .
Ž .
Ž . Ž .
Ž .
1.382 4
Ž .
1.365 4
Ž .
1.368 4
Ž .
1.383 4
C 1 –C 2
1.397 4
C 1 –C 6
1.395 4
C 2 –C 3
Ž . Ž .
Ž .
Ž . Ž .
Ž .
Ž . Ž .
C 5 –C 6
C 3 –C 4
1.381 4
C 4 –C 5
1.374 4
Ž . Ž .
C 9 –C 10
Ž .
Ž .
Ž
.
Ž .
Ž . Ž .
C 8 –C 9
C 7 –C 8
1.395 4
C 7 –C 12
1.390 4
Ž .
Ž .
Ž
.
Ž .
Ž
.
Ž
.
Ž
.
Ž .
1.374 5
C 10 –C 11
1.374 4
C 11 –C 12
( )
Bond angles 8
Ž . Ž . Ž .
Ž .
124.0 2
121.1 3
Ž . Ž . Ž .
C 2 –C 1 –C 6
Ž . Ž . Ž .
N 2 –C 2 –C 3
Ž .
120.9 3
C 2 –N 2 –C 7
N 1 –C 1 –C 2
Ž . Ž . Ž .
Ž . Ž . Ž .
Ž .
Ž .
117.9 2
N 1 –C 1 –C 6
Ž . Ž . Ž .
Ž .
Ž .
120.4 2
N 2 –C 2 –C 1
119.9 2
Ž . Ž .
Ž
.
Ž .
121.8 2
N 2 –C 7 –C 12

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I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
Fig. 4. Molecular structure of complex V.
w
x
The single-crystal X-ray structural study of complex II 21 confirmed the complete elimination of the coordinated
Ž
.
CO groups from the initial cluster I and the presence of acetato groups in II Fig. 1, Table 1 . However, neither
coordinated nitrene nor nitrosobenzene were found in this molecule. Instead, the complex contains a chelating amido
ligand, phenyl-o-nitrosophenylamide:
The formation of this ligand can be rationalized as the result of insertion of the intermediate nitrene ligand to the
C–H bond of the nitrosobenzene molecule
The reaction can be speculated as proceeding via the following scheme
which includes concerted elimination of CO2 and formation of coordinated nitrene species followed by coordination
of another nitrosobenzene molecule; the nitrene ligand then inserts into the C–H bond of the phenyl ring of

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I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
177
nitrosobenzene molecule producing an amino complex. Phenyl-o-nitrosophenylamine, which could be anticipated as
the product of the reaction between the nitrene moiety and nitrosobenzene, undergoes deprotonation to form a
coordinated amide.
Ž
.
According to the X-ray data Fig. 1, Table 1 , complex II contains two single-charged anionic ligands, OAc- and
phenyl-o-nitrosophenylamide, per each palladium atom. It should be emphasized that no protons attached to the O or
1
N atoms of phenyl-o-nitrosophenylamide were detected by H NMR and X-ray studies. Hence, the metal atoms
Ž
.
should be treated as being in the formal oxidation state q2 , although the distance between the two palladium atoms
˚
Ž
.
Ž
.
2.840 A suggests some metal–metal interaction, which is not typical of Pd q2 compounds.
Ž
.
Ž
.
Therefore, palladium q1 is oxidized to palladium q2 , carbon monoxide is oxidized to carbon dioxide, and the
redox transformations of nitrosobenzene lead successively to the elusive nitrene and observable amido ligands.
In addition to complex II, azoxybenzene was found in the reaction products in 10–15% yield based on the CO2
formed. The formation of azoxybenzene can be considered as a result of the reaction between the intermediate nitrene
species and nitrosobenzene:
PdsNPh qPhNO™PhN O NPhq Pd .
Ž
.
Among the reaction products, small amounts of azobenzene and aniline were also observed. Azobenzene can be
Table 4
Main geometric parameters for the molecule of V
˚
( )
Bond lengths A
Ž . Ž .
Pd 1 –N 1
Ž .
1.970 3
1.995 3
Ž . Ž .
Pd 1 –N 2
Ž .
1.996 3
1.335 5
Ž . Ž .
Pd 1 –N 3
Ž .
1.969 3
Ž . Ž .
Ž .
Ž . Ž .
Ž .
Ž . Ž .
Ž .
1.352 4
Pd 1 –N 4
N 1 –C 1
N 2 –C 6
Ž . Ž .
N 4 –C 19
Ž .
Ž .
C 1 –C 2
Ž
.
Ž .
Ž .
C 1 –C 6
Ž
.
Ž .
1.357 4
N 2 –C 7
1.426 3
N 3 –C 13
Ž . Ž .
1.345 5
N 4 –C 18
Ž .
Ž
.
Ž .
Ž .
Ž . Ž .
Ž .
1.439 4
1.422 3
1.413 5
Ž . Ž .
Ž .
Ž . Ž .
Ž .
Ž .
Ž
.
Ž .
Pd 2 –N 5
1.965 2
Pd 2 –N 6
2.005 3
Pd 2 –N 5A
1.965 2
Ž .
1.359 3
Ž .
N 6 –C 31
Ž
.
.
Ž .
Ž .
Ž
.
Ž .
Ž . Ž .
Pd 2 –N 6A
2.005 3
N 5 –C 25
1.336 4
N 6 –C 30
Ž .
Ž
.
Ž .
Ž
.
Ž
.
.
Ž .
Ž
.
Ž
Ž
.
.
Ž .
1.420 4
Ž .
C 25 –C 26
Ž . Ž .
1.411 4
Ž .
C 25 –C 30
Ž .
1.432 5
Ž . Ž .
Ž .
Pd 3 –N 7
1.993 3
Pd 3 –N 8
Ž .
1.975 3
Pd 3 –N 7A
Ž .
1.993 3
Ž .
Ž
Ž .
Ž
.
Ž .
Ž
.
Ž .
Pd 3 –N 8A
1.975 3
N 7 –C 42
1.352 4
N 7 –C 43
1.422 5
Ž .
Ž
.
Ž .
Ž
.
Ž
Ž .
Ž . Ž .
Ž .
1.439 5
N 8 –C 37
1.345 4
C 37 –C 38
1.418 4
C 37 –C 42
( )
Bond angles 8
Ž .
Ž . Ž .
Ž .
100.0 1
Ž .
Ž . Ž .
Ž .
179.6 1
N 1 –Pd 1 –N 2
Ž . Ž . Ž .
80.3 1
N 1 –Pd 1 –N 3
Ž .
Ž .
Ž . Ž .
Ž .
99.3 1
N 2 –Pd 1 –N 3
N 1 –Pd 1 –N 4
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
80.4 1
N 2 –Pd 1 –N 4
179.1 1
N 3 –Pd 1 –N 4
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
114.4 2
Pd 1 –N 1 –C 1
116.1 2
Pd 1 –N 2 –C 6
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
119.3 3
Pd 1 –N 2 –C 7
Ž . Ž .
126.3 2
C 6 –N 2 –C 7
Ž . Ž .
Ž
Ž
.
.
Ž .
Ž
Ž
.
Ž .
114.9 2
Pd 1 –N 3 –C 13
115.8 2
Pd 1 –N 4 –C 18
Ž . Ž .
Ž .
Ž
.
Ž .
.
Ž .
120.7 3
Pd 1 –N 4 –C 19
123.9 2
C 18 –N 4 –C 19
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
N 1 –C 1 –C 6
Ž .
114.4 3
N 1 –C 1 –C 2
126.2 3
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
N 2 –C 6 –C 5
Ž .
126.3 2
N 2 –C 6 –C 1
114.7 3
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
120.5 3
C 1 –C 6 –C 5
Ž . Ž .
119.0 3
N 2 –C 7 –C 8
Ž
.
Ž .
Ž .
Ž
.
Ž
.
.
.
Ž .
126.2 2
N 2 –C 7 –C 12
119.7 2
N 3 –C 13 –C 14
Ž .
Ž
.
Ž
.
.
.
.
.
Ž .
Ž .
Ž
.
Ž
Ž .
114.1 3
N 3 –C 13 –C 18
114.8 3
N 4 –C 18 –C 13
Ž .
Ž
.
Ž
Ž .
Ž .
Ž
.
Ž
Ž .
119.8 3
N 4 –C 18 –C 17
127.6 2
N 4 –C 19 –C 20
Ž .
Ž
.
Ž
Ž .
Ž . Ž . Ž .
Ž .
79.9 1
N 4 –C 19 –C 24
121.2 2
N 5 –Pd 2 –N 6
Ž . Ž .
Ž
Ž .
Ž . Ž .
Ž
.
.
.
.
.
.
Ž .
100.1 1
N 5 –Pd 2 –N 5A
180.0 1
N 6 –Pd 2 –N 5A
Ž . Ž . Ž
N 6 –Pd 2 –N 6A
Ž . Ž .
Ž
Ž .
Ž .
180.0 1
N 5 –Pd 2 –N 6A
100.1 1
Ž
.
Ž .
Ž
.
Ž .
Ž . Ž .
Ž
Ž .
116.6 2
N 5A –Pd 2 –N 6A
Ž . Ž .
79.9 1
Pd 2 –N 5 –C 25
Ž
.
Ž .
Ž . Ž .
Ž
Ž .
Pd 2 –N 6 –C 30
114.5 2
Pd 2 –N 6 –C 31
125.3 2
Ž .
126.6 3
Ž
.
Ž .
Ž
.
.
.
.
Ž .
Ž .
Ž
.
Ž
C 30 –N 6 –C 31
120.1 3
N 5 –C 25 –C 26
Ž .
Ž
.
Ž
Ž .
Ž .
Ž
.
Ž
Ž .
114.3 3
N 5 –C 25 –C 30
114.7 2
N 6 –C 30 –C 25
Ž .
Ž
.
Ž
Ž .
Ž
.
Ž
.
Ž
.
Ž .
118.5 2
N 6 –C 30 –C 29
127.0 3
C 25 –C 30 –C 29
Ž .
Ž
.
Ž
Ž .
Ž .
Ž
.
Ž
.
.
.
Ž .
121.5 3
N 6 –C 31 –C 32
119.7 3
N 6 –C 31 –C 36
Ž . Ž . Ž .
Ž .
Ž . Ž .
Ž
Ž .
180.0 1
N 7 –Pd 3 –N 8
80.5 1
N 7 –Pd 3 –N 7A
Ž . Ž .
Ž
Ž
.
.
.
.
.
.
.
Ž .
Ž . Ž .
Ž
Ž .
99.5 1
N 8 –Pd 3 –N 7A
Ž . Ž .
99.5 1
N 7 –Pd 3 –N 8A
Ž .
Ž
.
Ž .
Ž
.
Ž .
80.5 1
N 8 –Pd 3 –N 8A
180.0 1
N 7A –Pd 3 –N 8A
Ž . Ž .
Ž . Ž .
C 42 –N 7 –C 43
Ž
Ž .
Ž
.
.
.
.
.
Ž .
Pd 3 –N 7 –C 42
Ž
114.8 2
Pd 3 –N 7 –C 43
124.7 2
Ž .
115.2 3
.
Ž .
Ž
Ž .
Ž . Ž .
Ž
120.4 3
Pd 3 –N 8 –C 37
Ž .
Ž
.
Ž
Ž .
Ž .
Ž
.
Ž
Ž .
115.2 3
N 8 –C 37 –C 38
125.5 4
N 8 –C 37 –C 42
Ž .
Ž
.
.
Ž
Ž .
Ž .
Ž
.
Ž
Ž .
127.8 3
N 7 –C 42 –C 37
114.1 3
N 7 –C 42 –C 41
Ž .
Ž
Ž
Ž .
120.4 3
Ž .
Ž
.
Ž
Ž .
121.2 3
N 7 –C 43 –C 44
N 7 –C 43 –C 48

(
)
178
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
considered as the product of coupling of the nitrene ligands, and aniline forms through the reduction of the nitrene
ligands.
Ž
The formation of the amide ligand and above-mentioned organic compounds viz., azobenzene, azoxybenzene, and
.
w
x
aniline gives evidence for the participation of a nitrene species sNPh as a reaction intermediate:
The pathway leading to complex II seems to include the intermediate product of insertion of the nitrogen atom into
the aromatic ring, phenylnitrosoazepine:
which is typical of the reactions of free nitrene species.
w
x
According to data 22 , the azepine derivatives are fairly unstable to convert into the corresponding amine.
(
)
(
)
2.3. Reactions of mononuclear Pt q2 and Pd q2 complexes
2.3.1. Reaction of PtCl4 2-with o-phenylenediamine
[
]
1,2-phenylenediamine is known to be readily oxidized into a quinomide species by alkaline solutions of K2 PtCl4
w
Ž
.Ž .
x2
Ž
.
w x
in air, forming the bis-chelate mononuclear complex Pt NH N C6 H4 III as the reaction product 23 :
Due to the fairly complicated character of this reaction and low solubility of the phenylenediamine-derived
complexes, in this work the N-phenyl substituted analogue of phenylenediamine was used as a ligand source.
Ž .
Ž .
Scheme 1. The nitrene a rimido b resonance in description of the ligand structure.

(
)
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
179
2y
2y
[
]
[
]
2.3.2. Reaction of PdX4
and PtX4
with N-phenyl-o-phenylenediamine
Ž
.
4
The reaction of K2 Pt NO2 with N-phenyl-o-phenylenediamine in a MeCN–H2O solution was found to form the
diamagnetic mononuclear complex Pt NPh N C6 H4 IV . The same complex was obtained via the reaction of
K2 PtCl4 with N-phenyl-o-phenylenediamine in the presence of LiOH.
wŽ
.Ž .
x2
Ž
.
Ž
.
Ž
.
According to the X-ray data Fig. 2, Table 2 , the molecule IV contains the Pt q2 atom in a square-planar
˚
Ž
Ž . .
Ž .
.
Ž
Ž .
environment of four nitrogen atoms. The Pt–N bond lengths 1.954 4 –1.989 6 A and angle N–Pt–N 79.7 2 –80.08
˚
w x.
Ž
Ž .
Ž .
in two independent molecules are averaged and very close to the values observed in III 1.95 2 –1.99 2 A 23 .
˚
.
Ž
Ž .
Ž .
Ž .
However, the NsC bonds of the quinoide ligands in IV 1.331 9 –1.368 7 A are somewhat longer than in III
˚
˚
.
Ž
Ž .
.
Ž
Ž .
1.31 3 A but noticeably shorter than N–Ph C–N 1.410 7 –1.433 7 A . It should be noted that the significance of
˚
Ž
.
Ž
the Pt–N bonds in III and IV from normal values for the Pt q2 complexes with diamine ligands 2.03–2.07 A
w
x.
Ž
24,25 , and the redistribution of electron density in the N2C2 fragment of the ligand the C–C distance in IV is equal
˚
.
Ž .
Ž .
to 1.443 8 –1.437 8 A point to a high delocalization of electrons within the PtN2C2 system, including the
participation of lone pairs of formally nonequivalent nitrogen atoms.
Since the structural data for the N-phenyl-o-phenylenediamine molecule were not found in the literature, its
Ž
.
structure was determined in this work by a single-crystal X-ray study. The data obtained Fig. 3, Table 3 allow one to
immediately compare the geometries of the initial ligand and those in complexes III and IV. The changes in the ligand
Ž
.
geometry cf. Figs. 2 and 3 attest that the ligand is deprotonated to form o-quinoimide anion upon its reaction with
Ž
.
the Pt q2 complexes:
Ž
.
4
The palladium complex K2 Pd NO2 reacts with N-phenyl-o-phenylenediamine in a similar manner as with the
Ž
.
w
Ž
.Ž .
x2 Ž .
V was obtained.
platinum q2 complexes. In the presence of LiOH, diamagnetic complex Pd NPh N C6 H4
Complex V is more sensitive to protonation and decomposes during column chromatography on silica gel. It was
Table 5
Main geometric parameters for binuclear complex VII
˚
( )
Bond lengths A
Ž . Ž .
Ž .
1.964 5
Ž . Ž .
Pt 1 –N 4
Ž .
2.024 4
Ž . Ž .
N 1 –C 1
Ž .
2.019 5
Pt 1 –Pt 1
3.260 1
Pt 1 –N 1
Ž . Ž .
1.962 4
Pt 1 –N 2
Ž . Ž .
Ž . Ž .
Ž .
Ž .
Ž .
1.323 8
Pt 1 –N 3
Ž . Ž .
N 4 –C 12
Ž .
Ž .
N 4 –C 19
Ž
.
.
Ž .
Ž . Ž .
Ž .
1.321 8
N 2 –C 6
1.322 7
N 2 –C 13
1.453 6
N 3 –C 7
Ž .
Ž
.
Ž .
Ž .
Ž
Ž .
Ž . Ž .
Ž .
1.434 8
1.326 8
1.456 6
C 1 –C 2
Ž . Ž .
Ž .
Ž . Ž .
Ž
.
.
Ž . Ž .
Ž .
1.455 8
C 1 –C 6
1.459 7
C 2 –C 3
1.344 1 0
Ž .
C 3 –C 4
Ž . Ž .
Ž .
Ž . Ž .
Ž . Ž .
C 9 –C 10
Ž .
1.419 9
C 4 –C 5
1.334 9
C 5 –C 6
1.413 9
C 7 –C 8
Ž .
Ž
.
Ž .
1.464 7
Ž . Ž .
C 8 –C 9
Ž
Ž .
Ž
.
Ž .
1.439 8
C 7 –C 12
1.367 1 0
Ž
.
Ž
.
.
.
.
.
Ž
.
.
.
Ž
.
Ž
.
.
.
.
.
Ž .
Ž
.
Ž
.
.
.
.
Ž
.
.
.
.
C 10 –C 11
1.315 10
C 11 –C 12
1.429 9
C 13 –C 14
1.368 10
Ž
.
Ž
Ž
Ž
.
Ž
Ž .
Ž
.
Ž
Ž
1.365 12
C 13 –C 18
1.362 11
C 14 –C 15
1.368 7
Ž .
C 15 –C 16
Ž
.
Ž
Ž
Ž
.
Ž
Ž
.
.
Ž
Ž
Ž
1.381 11
C 16 –C 17
1.348 12
C 17 –C 18
1.399 8
C 19 –C 20
Ž
.
Ž
Ž .
Ž
.
Ž
Ž .
Ž
Ž
C 19 –C 24
1.372 9
C 21 –C 22
1.388 8
C 21 –C 22
1.357 11
Ž
.
Ž
Ž
.
Ž
.
Ž
Ž .
Ž . Ž .
Ž .
C 22 –C 23
1.356 12
C 23 –C 24
1.395 7
Ž .
S 1 –O 1
1.344 8
Ž . Ž .
Ž .
Ž . Ž .
Ž .
Ž
Ž
.
.
Ž
.
.
S 1 –O 2
1.418 9
S 1 –O 3
1.366 5
S 1 –C 25
Ž .
1.736 10
Ž .
Ž
.
Ž .
Ž .
Ž
.
Ž
.
Ž
1.315 15
F 1 –C 25
1.223 8
F 2 –C 25
1.291 13
F 3 –C 25
( )
Bond angles 8
Ž . Ž . Ž .
Ž .
171.9 2
Ž . Ž . Ž .
N 1 –Pt 1 –N 4
Ž .
172.7 2
N 1 –Pt 1 –N 2
79.1 2
N 1 –Pt 1 –N 3
Ž . Ž . Ž .
94.5 2
Ž .
Ž . Ž . Ž .
Ž .
N 2 –Pt 1 –N 3
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
N 2 –Pt 1 –N 4
107.0 2
N 3 –Pt 1 –N 4
79.1 2
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
C 6 –N 2 –C 13
Ž .
115.6 3
Pt 1 –N 1 –C 1
117.2 3
Pt 1 –N 2 –C 6
Ž . Ž .
Pt 1 –N 3 –C 7
Ž
.
Ž .
Ž . Ž .
Ž
.
Ž .
116.2 5
Pt 1 –N 2 C 13
128.0 4
Ž . Ž . Ž .
Ž .
Ž . Ž .
C 12 –N 4 –C 19
Ž . Ž . Ž .
N 1 –C 1 –C 6
Ž
.
Ž .
115.5 3
117.4 3
Pt 1 –N 4 –C 12
Ž . Ž .
Ž
.
Ž .
Ž
.
Ž .
Ž
.
Ž .
116.4 4
Pt 1 –N 4 –C 19
128.1 4
Ž . Ž . Ž .
N 1 –C 1 –C 2
Ž .
126.5 5
Ž .
114.3 5

(
)
180
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
Fig. 5. Dinuclear dication of VII.
separated by extraction with hydrocarbons from the reaction mixture. The X-ray study showed that the geometrical
Ž
.
parameters of complex V are very close to those of the platinum analog IV Fig. 4, Table 4 .
Analogously to the Pt atom in IV, the palladium atom in V has a square-planar environment of two N-donor
˚
˚
Ž
Ž .
Ž .
Ž .
Ž .
Ž
.
Ž .
ligands in the o-quinoide form Pd–N 1.965 3 –2.005 3 A, NsC 1.335 5 –1.357 4 A, N–C Ph 1.412 5 –1.426
˚
Ž .
Ž .
.
A, angle N–Pd–N 79.9 1 –80.5 1 8 in three independent molecules . In both complexes IV and V, the Ph substituents
formally oriented trans and, hence, point toward the metal center due to steric hindrance.
Ž
.
Examination of the ligand geometry in both complexes and that of the free diamine cf. Figs. 2–4 points
unequivocally to the fact that quinoimide structure b is much more pronounced than nitrene structure a among the two
Ž
.
main resonance structures of the ligand Scheme 1 .
Hence, the expected labile nitrene species is stabilized in this case due to the formation of chelate ortho-quinoimi-
ide structure of the ligand.
2.4. Oxidation of bis-quinonimine Pt complexes by Agq
Complex III is known to be readily oxidised by Agq ion under the action of 1 equivalent of AgO3SCF3 per Pt
Ž
. w x
atom in the presence of a small amount of acetone 2–5 ml per 1 mmol of reagents 26 . The reaction results in the

(
)
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
181
Fig. 6. Molecular structure of complex VIII.
Ž
. Ž
.
elimination of one electron from the metal orbital to form a dinuclear Pt q3 VI complex with fairly long Pt–Pt
˚
Ž
.
w x
bond 3.031 A between two metal-bis-chelate moieties 26 :
Ž
.
When the N-phenyl derivative complex IV was used as a starting compound in the reaction with AgO3SCF3, an
Ž
.
Ä
w
Ž
.Ž .
x
4
w
x
Ž
.
analogous diamagnetic Pt q3 cationic complex Pt2 NPh N C6 H4 O3SCF3 VII was obtained. According to
2
˚
Ž
.
4Ž
Ž .
.
the X-ray data Fig. 5, Table 5 , dication VII has a longer Pt–Pt bond 3.260 1 A as compared to that in complex
VI.
This effect is apparently caused by nonvalent intramolecular interaction between the bis-chelate fragments of the
Ž
.
neighbouring Pt q3 atoms having an eclipsed conformation. Moreover, the Ph-substituents of the ligands coordi-
nated to each Pt atom are positioned in a cis-configuration, in contrast to complex IV which contains nonbonding
˚
Ž
.
M–M distance Pt . . . Pt 4.8 A . Such steric constrains lead to slight protruding of the Pt atoms out of the PtN4 plane
˚
Ž
.
approx. 0.26 A and the sliding of the mononuclear bis-chelate fragments at the opposite sides to result in the
Ž
Ž . .
nonorthogonal angle between the PtN4 plane and the Pt–Pt bond angle PtN4rPt–Pt 113.2 2 8 . The Pt–N bonds in
˚
˚
Ž
Ž . .
Ž .
Ž
.
Ž .
Ž
VII vary in length due to the same reason Pt–N 1.962 4 and 1.964 5 A; Pt–N Ph 2.024 4 A, angle N–Pt–N Ph
˚
˚
Ž . .
Ž .
Ž
Ž .
Ž .
Ž .
79.1 2 8 ; however, the ligands remain a quinoide structure C5N 1,321 8 A and 1.326 8 A, C–C 1.459 7 and
1.464 7 A in the PtN2C2 cycle .
˚
.
CuBr2 also reacts with complex IV. The reaction proceeds only in the presence of a small amount of water. The
reaction of IV with anhydrous CuBr2 in an acetone solution containing 3–5% of H2O afforded the diamagnetic

(
)
182
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
Table 6
Main geometric parameters for complex VIII
˚
( )
Bond lengths A
Ž .
Pt 1 –N 2
Ž .
Ž .
2.414 2
1.980 15
Ž .
N 1 –C 1
Ž .
Ž .
2.412 3
1.249 24
Ž . Ž .
N 1 –H 1N
Ž
.
.
.
.
.
.
Pt 1 –Br 1
Ž . Ž .
Pt 1 –Br 2
Ž . Ž .
Pt 1 –N 1
1.901 14
Ž
0.674 35
Ž
.
.
.
.
.
.
Ž
.
.
.
.
.
Ž .
Ž
.
Ž . Ž .
Ž
Ž . Ž .
Ž
Ž . Ž .
Ž
1.540 28
N 2 –C 6
1.290 23
N 2 –C 7
1.505 21
C 1 –C 2
Ž . Ž .
Ž
Ž . Ž .
Ž
Ž . Ž .
Ž
1.359 29
C 1 –C 6
1.405 24
C 2 –C 3
1.251 28
C 3 –C 4
Ž . Ž .
Ž
Ž . Ž .
Ž
Ž . Ž .
C 9 –C 10
Ž
1.383 16
C 4 –C 5
Ž .
1.211 28
C 5 –C 6
1.510 26
C 7 –C 8
Ž
.
Ž
Ž . Ž .
Ž
Ž .
Ž
.
Ž
1.377 18
C 7 –C 8A
1.383 16
C 8 –C 9
1.357 21
Ž
.
Ž
.
Ž
C 10 –C 9A
1.377 18
( )
Bond angles 8
Ž . Ž .
Ž .
Ž .
175.5 4
Ž . Ž . Ž .
Br 1 –Pt 1 –N 1
Br 1 –Pt 1 –N 2
Ž .
93.1 4
Br 1 –Pt 1 –Br 2
91.3 1
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
170.5 4
Br 2 –Pt 1 –N 1
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
77.4 6
Br 2 –Pt 1 –N 2
98.2 4
N 1 –Pt 1 –N 2
Ž . Ž . Ž .
Ž
.
.
.
.
.
Ž . Ž .
Pt 1 –N 2 –C 6
Ž
.
Ž
.
.
.
.
.
Pt 1 –N 1 –C 1
119.1 13
Pt 1 –N 1 –H 1N
Ž . Ž . Ž .
124.9 29
Ž . Ž .
Pt 1 –N 2 –C 7
Ž
.
Ž
Ž
116.1 11
C 1 –N 1 –H 1N
Ž . Ž . Ž .
116.0 31
Ž
Ž . Ž . Ž .
Ž
118.9 15
125.0 12
C 6 –N 2 –C 7
Ž . Ž . Ž .
Ž
Ž . Ž . Ž .
Ž
115.2 17
N 1 –C 1 –C 2
128.3 17
N 1 –C 1 –C 6
Ž . Ž . Ž .
Ž
Ž . Ž . Ž .
Ž
N 2 –C 6 –C 1
112.3 16
N 2 –C 6 –C 5
129.7 15
Ž .
118.9 8
Ž . Ž . Ž .
Ž .
Ž . Ž . .
Ž
N 2 –C 7 –C 8
118.9 8
N 2 –C 7 –C 8A
Ž
.
w
Ž
.Ž
.
x
Ž
.
mononuclear Pt q2 complex Pt NPh NH C6 H4 Br2 VIII , which contains the protonated quinoimide ligand.
Ž
.
Ž
According to the X-ray data Fig. 6, Table 6 , the Pt atom in the molecule of VIII is bound with two bromine Pt–Br
˚
Ž
.
Ž .
.
ŽŽ
Ž
Ž
Ž
.
2.412 3 and 2.414 2 A; angle Br–Pt–Br 91.38 and two N atoms of the amido and imido groups Pt–N Ph 1.980 15
˚
˚
˚
˚
˚
.
.
Ž .
Ž
.
.
.
Ž
.
Ž .
Ž
.
Ž
A and Pt–N H 1.901 14 A of the ligand Ph N5C 1.290 23 A, H N5C 1.249 24 A, C–C 1.405 24 A,
˚
˚
.
Ž
.
Ž
.
Ž .
N–C Ph 1.505 21 A, N–H 0.67 4 A which is also in the quinoimide form. The formation of such a ligand, which
is unstable as a free molecule, in the reaction with CuBr2 points to a tendency of the N atom in IV to be attacked by
Fig. 7. Molecular structure of compound IX.

(
)
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
183
the proton of the water molecule activated by the copper atom. In contrast to this, the action of water on complex IV
Ž
.
in the absence of copper q2 does not affect the platinum complex.
An unusual activation of the N atom of the quinoimide ligand was observed on removal of one electron from
complex IV. Further oxidation of IV by Agq initiated unexpected transformation of the organic ligands. The reaction
Ž
.
of IV with a large excess of AgO3SCF3 5–6 equivalents in acetone proceeded through the formation of complex VII
TLC monitoring and eventually produced the heterotricyclic compound of a quinoxaline series IX
Ž
.
Ž
.
which is built up of two ligand molecules and the CMe2 fragment of the acetone molecule. When using VII as the
Ž
.
initial reagent in this reaction, a smaller amount of the oxidant 3–4 equivalents of AgO3SCF3 is required. The X-ray
Ž
.
investigation of IX Fig. 7, Table 7 showed that the nitrogen atoms of one ligand are connected with two 4- and
Table 7
Main geometric parameters for compound IX
˚
( )
Bond lengths A
Ž . Ž .
N 2 –C 13
Ž .
1.506 6
Ž .
N 2 –C 16
Ž
.
.
.
Ž .
1.424 4
Ž . Ž .
N 3 –C 3
Ž .
1.362 6
N 1 –C 1
1.303 6
N 1 –C 13
1.453 5
N 2 –C 6
Ž . Ž .
Ž .
Ž
.
Ž .
Ž .
Ž
Ž .
Ž .
1.385 5
Ž . Ž .
Ž .
Ž .
Ž
Ž .
Ž . Ž .
Ž .
1.312 6
Ž .
1.456 5
Ž .
1.430 6
Ž .
1.398 6
Ž .
1.368 6
Ž .
1.521 5
Ž .
1.393 6
Ž .
1.376 6
Ž .
1.390 6
Ž .
1.391 6
N 3 –C 7
1.395 6
Ž .
N 3 –C 22
1.447 4
Ž .
N 4 –C 4
Ž . Ž .
Ž . Ž .
Ž . Ž .
N 4 –C 8
1.387 5
C 1 –C 2
1.434 6
C 1 –C 6
Ž . Ž .
Ž .
Ž . Ž .
Ž .
Ž . Ž .
C 2 –C 3
1.364 7
C 3 –C 4
1.471 5
C 4 –C 5
Ž . Ž .
Ž .
Ž . Ž .
Ž .
Ž . Ž .
C 5 –C 6
1.341 7
C 7 –C 8
1.410 5
C 7 –C 12
Ž . Ž .
Ž .
Ž .
Ž
.
Ž .
Ž
.
Ž
.
.
.
.
.
.
C 8 –C 9
1.399 7
Ž .
C 9 –C 10
1.372 7
Ž .
C 10 –C 11
Ž
.
Ž
.
.
.
.
.
Ž
.
Ž
.
.
.
.
.
Ž
.
Ž
C 11 –C 12
1.357 8
C 13 –C 14
1.526 9
C 13 –C 15
Ž
.
Ž
Ž .
Ž
.
Ž
Ž .
Ž
.
Ž
C 16 –C 17
1.368 7
C 16 –C 21
1.383 7
C 17 –C 18
Ž
.
Ž
Ž .
Ž
.
Ž
Ž .
Ž
.
Ž
C 18 –C 19
1.355 9
C 19 –C 20
1.349 9
C 20 –C 21
Ž
.
Ž
Ž .
Ž
.
Ž
Ž .
Ž
.
Ž
C 22 –C 23
1.387 6
C 22 –C 27
1.344 5
C 23 –C 24
Ž
.
Ž
Ž .
Ž
.
Ž
Ž .
Ž . Ž
C 24 –C 25
1.369 6
C 25 –C 26
1.381 8
C 26 –C 27
( )
Bond angles 8
Ž . Ž .
C 6 –N 2 –C 16
Ž
.
.
Ž .
123.7 4
Ž . Ž .
C 13 –N 2 –C 16
Ž
.
Ž .
109.2 3
C 1 –N 1 –C 13
108.4 3
C 6 –N 2 –C 13
Ž . Ž .
Ž
Ž .
Ž
.
Ž .
Ž
.
Ž .
125.2 4
Ž . Ž . Ž .
Ž .
Ž . Ž .
Ž
.
Ž .
118.4 4
C 3 –N 3 –C 7
121.7 3
C 3 –N 3 –C 22
Ž . Ž .
Ž
.
Ž .
Ž . Ž . Ž .
Ž .
118.7 3
C 7 –N 3 –C 22
119.7 3
C 4 –N 4 –C 8
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
113.3 4
N 1 –C 1 –C 2
127.6 3
N 1 –C 1 –C 6
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
118.4 3
C 2 –C 1 –C 6
119.1 4
C 1 –C 2 –C 3
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
115.8 4
N 3 –C 3 –C 2
122.1 3
N 3 –C 3 –C 4
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
123.6 4
C 2 –C 3 –C 4
122.1 4
N 4 –C 4 –C 3
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
118.3 4
N 4 –C 4 –C 5
118.1 3
C 3 –C 4 –C 5
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
105.0 4
C 4 –C 5 –C 6
119.4 3
N 2 –C 6 –C 1
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
118.3 4
N 2 –C 6 –C 5
132.4 3
N 3 –C 7 –C 8
Ž . Ž .
Ž
.
Ž .
Ž . Ž .
Ž
.
.
Ž .
118.3 4
N 3 –C 7 –C 12
123.4 3
C 8 –C 7 –C 12
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
Ž .
119.3 3
N 4 –C 8 –C 7
121.9 4
N 4 –C 8 –C 9
Ž . Ž . Ž .
Ž .
Ž . Ž .
Ž
Ž .
121.5 4
C 7 –C 8 –C 9
118.9 4
C 8 –C 9 –C 10
Ž .
Ž
.
Ž
.
.
Ž .
Ž
.
Ž
.
Ž
.
Ž .
122.3 5
C 9 –C 10 –C 11
118.5 5
C 10 –C 11 –C 12
Ž .
Ž
.
Ž
Ž .
Ž . Ž .
Ž
.
Ž .
103.9 4
C 7 –C 12 –C 11
120.5 4
N 1 –C 13 –N 2
Ž .
Ž
Ž
.
.
Ž
Ž
.
Ž .
Ž .
Ž
.
Ž
.
.
.
Ž .
112.0 3
N 1 –C 13 –C 14
108.4 4
N 2 –C 13 –C 14
Ž .
.
Ž .
Ž .
Ž
.
.
Ž
Ž .
110.8 4
N 1 –C 13 –C 15
109.9 3
N 2 –C 13 –C 15
Ž
.
Ž
.
Ž
.
Ž .
Ž .
Ž
Ž
Ž .
C 14 –C 13 –C 15
111.6 5
N 2 –C 16 –C 17
119.9 4
Ž .
118.9 3
Ž .
Ž
.
Ž
.
Ž .
Ž
.
Ž
.
Ž
.
.
.
N 2 –C 16 –C 21
121.1 4
C 17 –C 16 –C 21
Ž
.
Ž
.
Ž
.
.
.
Ž .
Ž
.
Ž
.
Ž
Ž .
119.9 5
C 16 –C 17 –C 18
120.0 5
C 17 –C 18 –C 19
Ž
.
Ž
.
Ž
Ž .
Ž
.
Ž
.
Ž
Ž .
120.2 5
C 18 –C 19 –C 20
120.7 4
C 19 –C 20 –C 21
Ž
.
Ž
.
Ž
Ž .
Ž .
Ž
.
Ž
.
Ž .
117.3 3
C 16 –C 21 –C 20
120.3 5
N 3 –C 22 –C 23
Ž .
Ž
.
Ž
.
Ž .
Ž
.
Ž
.
Ž
.
.
.
Ž .
121.5 4
N 3 –C 22 –C 27
121.2 4
C 23 –C 22 –C 27
Ž
.
Ž
.
Ž
.
.
.
Ž .
Ž . Ž . Ž
Ž .
120.1 5
C 22 –C 23 –C 24
118.4 3
C 23 –C 24 –C 25
Ž
.
Ž
.
Ž
Ž .
Ž . Ž . Ž
C 25 –C 26 –C 27
Ž .
118.7 4
C 24 –C 25 –C 26
120.8 5
Ž
.
Ž
.
Ž
Ž .
C 22 –C 27 –C 26
120.4 4

(
)
184
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
Table 8
Data collection and processing parameters for investigated compounds
Compound
II
V
N-phenyl-o-
phenylenediamine
Formula
Mol. wt.
C16 H24 N4O4 Pd2CH2Cl2
810.2
C24 H18 N4 Pd
468.9
C12 H12 N2
184.3
Color and habit
Space group
Brown prism
C2rc
Ž .
6.801 4
Black-blue prism
P-1
Ž .
12.267 4
White prism
P21 rn
Ž .
10.818 4
˚
Ž .
a A
˚
Ž .
b A
Ž .
29.68 2
Ž .
12.321 3
Ž .
5.864 2
˚
Ž .
Ž .
Ž .
14.793 4
Ž .
c A
15.078 9
90
15.721 4
90
Ž .
Ž .
82.90 2
a 8
Ž .
Ž .
92.36 5
Ž .
76.96 2
Ž .
66.69 2
Ž .
96.09 2
b 8
g
Ž .
8
90
90
3
˚
Ž
.
Ž .
3041 3
Ž .
Ž .
991.6 5
V A
1998.9 9
Z
4
4a
4
y1
Ž
.
rcalcd g cm
Abs. coefficient cm
1.770
14.1
1.558
9.46
1.234
0.74
y1
Ž
.
Scan type
u –2u
u –2u
u –2u
Scan speed
Scan width 8
Variable, 2.02–14.65
1.80
4–60
2499
2119
Variable, 2.02–14.65
1.60
Variable, 2.02–14.65
1.80
Ž .
Ž .
2u range 8
2–52
7899
x6084
2–56
1898
1030
Unique data
Reflections observed
Weighting scheme
GOF
2
Unit weights
0.96
wy1 ss 2 F q0.0003F
wy1 ss 2 F q0.0205F
2
Ž
.
Ž .
1.80
0.49
R
0.054
0.032
0.058
Rw
0.053
0.042
0.073
Residual extrema in
0.79–0.90
0.61–0.86
0.56–0.04
y3
˚
Ž
.
final diff. Map e A
Compound
Formula
Mol. wt.
IV
VII
VIII
w
x w x
C24 H18 N4 Pt
557.5
C48 H36 N8 Pt2 2 CF3O3S 2C6 H6 C12 H16 Br2 N2 Pt
1569.4
543.2
Color and habit
Space group
Black-blue prism
P-1
Brown prism
P-1
Black prism
P21 rm
Ž .
Ž .
Ž .
Ž .
10.496 2
a A
9.668 2
11.755 2
Ž .
Ž .
Ž .
12.035 2
Ž .
6.775 2
b A
10.342 3
Ž .
Ž .
Ž .
12.267 2
Ž .
c A
11.808 2
11.291 2
90
Ž .
Ž .
Ž .
94.97 3
a 8
73.83 2
Ž .
Ž .
Ž .
107.12 3
Ž .
91.64 3
b 8
g
75.81 2
Ž .
Ž .
Ž .
112.99 3
8
62.60 2
90
802.6 4
3
Ž
.
Ž .
Ž .
Ž .
V A
997.2 3
1486.1 9
1
Z
2b
2
y1
Ž
.
rcalcd g cm
1.857
70.5
1.754
48.5
2.248
137.0
y1
Ž
.
Abs. coeff. cm
Scan type
u –2u
k –2u
k –2u
Scan speed
Scan width 8
Ž .
2u range 8
Unique data
Reflections observed
Weighting scheme
GOF
Variable, 2.02–14.65
1.60
Variable, 2.00–29.30
1.20
Variable, 2.00–29.30
1.20
Ž .
3–58
4884
3056
4–54
5822
4603
3–55
1662
1285
wy1 ss 2 F q0.2054F
wy1 ss 2 F q0.0005F
wy1 ss 2 F q0.0061F
2
2
2
Ž
.
Ž
.
Ž .
0.20
1.16
1.04
R
0.067
0.036
0.063
Rw
0.087
0.055
0.087
Residual extrema in
3.25– 3.63
1.19– 0.67
1.12– 1.15
y3
˚
Ž
.
final diff. Map e A
Compound
Formula
Mol. Wt
IX
C27 H24 N4
324
Color and habit
Space group
Orange prism
R-3

(
)
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
185
Ž
.
Table 8 continued
Compound
IX
˚
Ž .
a A
Ž .
32.118 5
˚
Ž .
b A
Ž .
32.118 5
˚
Ž .
Ž .
11.919 5
c A
Ž .
a 8
Ž .
b 8
g
Ž .
8
3
˚
Ž
.
Ž .
10650 5
V A
Z
12
1.130
0.7
y1
Ž
.
rcalcd g cm
Abs. coeff. cm
y1
Ž
.
Scan type
k –2u
Scan speed
Scan width 8
Variable, 2.00–29.30
1.20
Ž .
Ž .
2u range 8
4–55
4090
2024
Unique data
Reflections observed
Weighting scheme
GOF
wy1 ss 2 F q0.0053F
2
Ž
.
1.08
R
0.062
Rw
0.087
Residual extrema in
0.46– 0.25
y3
˚
Ž
.
final diff. Map e A
a
Ž
.
Three independent molecules in unit cell one in common and two in special positions .
b Two independent molecules in special positions of unit cell.
˚
˚
.
Ž
Ž .
Ž
.
Ž .
5-positioned carbon atoms of the phenylene ring of the second ligand N5C 1.312 6 A, Ph N–C 1.385 5 A . In
addition, the N-atoms of the second ligand are attached to the carbon atom of the CMe2 group derived from acetone
˚
˚
.
Ž
Ž .
Ž
.
Ž .
N–C, 1.506 6 A, Ph N–C 1.453 5 A . In the absence of the oxidant, IV or VII does not react with acetone.
Ž
.
At the first glance, the ligand resonance structure b see Scheme 1 is readily suited to undergoing the Diels-Alder
reaction. However, the formation of triheterocyclic compound IX cannot be rationalized within a scheme involving a
Table 9
4
2
Ž
.
Ž
.
Atomic coordinates =10 and equivalent isotropic displacement parameters =10 for II
Atom
Ž .
a
Ž .
U eq
X
Y
Z
Ž .
Ž .
Ž .
4.02 2
Pd 1
Ž .
2910 1
1212
Ž .
851 3
2451 1
1383 6
3034 6
3844 5
1526 7
2445 7
2659 7
2023 9
Ž .
Ž .
Ž .
4.0 3
N 1
226 1
260 1
273 1
227 2
247 1
249 1
231 2
Ž .
Ž .
Ž .
Ž .
Ž .
4.0 3
N 2
623 3
Ž .
555 3
Ž .
Ž .
Ž .
Ž .
5.7 3
O 1
Ž .
Ž .
Ž .
Ž .
Ž .
4.0 4
C 1
Ž .
415 4
Ž .
272 3
Ž .
Ž .
Ž .
3.6 4
C 2
Ž .
Ž .
Ž .
Ž .
Ž .
4.3 4
C 3
y189 4
Ž .
Ž .
Ž .
Ž .
Ž .
5.3 4
C 4
y512 4
Ž .
Ž .
Ž .
Ž .
Ž .
C 5
Ž .
204 2
Ž .
y376 4
1125 8
Ž .
5.1 4
Ž .
5.0 4
Ž .
C 6
203 2
66 4
873 7
Ž .
Ž .
Ž .
Ž .
Ž .
4.1 3
C 7
204 2
1039 4
1297 4
1489 5
1428 5
508 7
Ž .
Ž .
Ž .
Ž .
Ž .
5.2 4
C 8
Ž .
C 10
44 2
293 8
Ž .
Ž .
Ž .
Ž .
7.1 6
C 9
Ž
23 2
y54 1
.
.
.
Ž .
Ž .
Ž .
Ž .
6.9 5
165 3
324 2
349 2
354 1
339 1
492 2
492 2
167 1
0
y1141 9
Ž
Ž .
Ž .
Ž .
y933 8
Ž .
6.6 5
C 11
1175 5
Ž
Ž .
Ž .
980 5
Ž .
Ž .
6.2 5
C 12
y105 8
Ž .
Ž .
Ž .
Ž .
Ž .
O 2
1587 3
1786 3
1818 4
2152 5
3586 6
1712 5
1305 8
5.4 3
Ž .
5.2 3
Ž .
Ž .
Ž .
Ž .
O 3
Ž
.
.
Ž .
Ž .
Ž .
Ž .
5.1 4
C 13
Ž
Ž .
Ž .
Ž .
Ž .
6.8 5
C 14
Ž .
559 9
Ž .
Ž .
Ž .
Ž .
16.7 3
Cl 1
2788 3
Ž .
3067 5
Ž
.
Ž .
9 1
C 15
2455 8
1r4
a
Ž
.
U eq is defined as one third of the trace of the orthogonalized U tensor.
i j

(
)
186
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
Diels-Alder mechanism. More probably, a reactive species with a nitrene N atom and an N-centered free radical
Ž
.
amido group is formed as the result of oxidation of the Pt q3 complex:
Hence, the formation of IX can be speculated as involving an insertion of the nitrene species into the C–H bond of
the neighbouring ligand molecule simultaneously with a radical attack of the ArNPPh species to an aromatic ring of
the same ligand.
Table 10
4
2
3
˚
Ž
.
Ž
.
Ž .
Atomic coordinates =10 and equivalent isotropic displacement coefficients A =10 U eq for IV
Atom
Ž .
X
Y
Z
U
Žeq.
Ž .
24 1
Pt 1
Ž .
0
0
Ž .
Ž .
604 5
0
Ž .
Ž .
Ž .
25 1
N 1
1171 6
y1849 5
1035 5
1577 5
2198 6
2532 6
3718 6
4593 6
4255 7
3089 6
Ž .
Ž .
Ž .
Ž .
26 1
N 2
y846 6
Ž .
Ž .
901 7
Ž .
y1859 6
Ž .
Ž .
25 1
C 1
Ž .
Ž .
Ž .
Ž .
Ž .
29 1
C 2
Ž .
y257 8
y474 7
Ž .
y698 8
Ž .
y338 6
Ž .
Ž .
30 1
C 3
Ž .
Ž .
Ž .
Ž .
Ž .
33 1
C 4
14 8
y1567 7
Ž .
Ž .
Ž .
y2904 8
Ž .
Ž .
40 1
C 5
1159 8
Ž .
Ž .
Ž .
Ž .
Ž .
32 1
C 6
1572 8
y3059 7
Ž .
Ž .
Ž .
2047 6
Ž .
Ž .
C 7
y1954 7
1729 5
1381 7
25 1
Ž .
Ž .
Ž .
Ž .
Ž .
C 8
Ž .
C 10
y3458 8
2647 7
38 1
Ž .
Ž .
Ž .
Ž .
C 9
Ž
y4540 8
4034 7
1592 7
Ž .
42 1
Ž .
.
.
.
Ž .
y4180 9
Ž .
4886 7
2108 7
53 1
Ž
Ž .
Ž .
Ž .
4288 7
Ž .
Ž .
0
Ž .
C 11
y2653 8
2425 7
2249 6
41 1
Ž
Ž .
Ž .
C 12
y1596 8
2886 7
33 1
Ž .
Ž .
Pt 2
y5000
0
29 1
Ž .
Ž .
Ž .
Ž .
2078 6
Ž .
N 3
Ž .
y6501 7
y255 6
41 1
Ž .
Ž .
Ž .
Ž .
N 4
y5637 7
310 6
1657 5
32 1
Ž
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
y7225 8
Ž .
Ž .
Ž .
C 13
2689 7
704 6
31 1
Ž
Ž .
Ž .
Ž .
Ž .
C 14
y8337 7
4195 7
736 6
30 1
Ž .
Ž
Ž .
y8942 8
Ž .
Ž .
C 15
4639 7
1790 6
2866 7
2889 6
1801 6
2673 5
3513 6
4483 7
4618 7
37 1
Ž
Ž .
Ž .
Ž .
Ž .
C 16
y8486 8
3678 7
38 1
Ž
Ž .
y7367 8
Ž .
Ž .
Ž .
C 17
2235 7
33 1
Ž
Ž .
Ž .
Ž .
Ž .
C 18
y6734 7
1701 6
25 1
Ž .
Ž
Ž .
y5050 8
Ž .
Ž .
C 19
y806 7
28 1
Ž
Ž .
Ž .
Ž .
Ž .
C 20
y6051 8
y1329 7
36 1
Ž
Ž .
y5486 8
Ž .
y2382 7
Ž .
Ž .
44 1
C 21
Ž
Ž .
Ž .
Ž .
Ž .
46 1
C 22
y3923 9
y2955 7
Ž
Ž .
y2889 8
Ž .
y2495 7
Ž .
Ž .
47 1
C 23
3754 7
Ž .
2767 6
Ž
Ž .
y3470 8
Ž .
y1396 7
Ž .
35 1
C 24
Ž
.
Ž
.
Ž
.
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
77 1
H 3A
y1532 14
565 14
3950 14
5358 14
4947 14
2846 14
Ž
.
.
.
.
.
Ž
.
.
.
Ž
.
.
.
Ž
Ž .
80 1
H 4A
y293 14
y1597 14
Ž
Ž
Ž
Ž
Ž .
81 1
H 5A
1620 14
2369 14
y3731 14
Ž
Ž
Ž
Ž
Ž .
79 1
H 6A
y3885 14
Ž
Ž
.
.
.
.
Ž
.
.
.
.
.
.
.
.
.
.
Ž
Ž .
H 8A
y3700 14
2087 14
988 14
79 1
Ž
Ž
Ž
Ž
Ž .
H 9A
y5595 14
4374 14
5830 14
4877 14
2503 14
4839 14
5646 14
4048 14
1638 14
1324 14
2193 14
2740 14
2523 14
79 1
Ž
.
.
.
.
.
.
.
.
.
.
.
.
Ž
Ž
Ž
Ž .
H 10A
y4916 14
80 1
Ž
Ž
Ž
Ž
Ž .
79 1
H 11A
y2392 14
Ž
Ž
.
Ž
Ž
Ž .
79 1
H 12A
y548 14
Ž
Ž
.
.
.
.
Ž
Ž
Ž .
78 1
H 14A
y8593 14
y86 14
Ž
Ž
Ž
Ž
1813 14
Ž .
79 1
H 15A
y9780 14
Ž
Ž
Ž
Ž
Ž .
78 1
H 16A
y8929 14
3567 14
3682 14
3417 14
5140 14
5380 14
3776 14
2221 14
Ž
Ž
Ž
Ž
Ž .
H 17A
y6985 14
77 1
Ž
Ž
.
Ž
Ž
Ž .
H 20A
7184 14
y936 14
77 1
Ž
Ž
.
.
.
.
Ž
.
.
.
.
Ž
Ž .
H 21A
y6201 14
y2724 14
79 1
Ž
Ž
Ž
Ž
Ž .
79 1
H 22A
y3542 14
y3665 14
Ž
Ž
Ž
Ž
Ž
Ž .
79 1
H 23A
y1776 14
y2919 14
Ž
Ž
Ž
Ž .
79 1
H 24A
y2749 14
y1075 14
Equivalent isotropic U defined as one-third of the trace of the orthogonalized U tensor.
i j

(
)
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
187
3. Experimental
3.1. General comments
All gases, organic solvents, and reagents were reagent grade. All operations on separation, crystallization and
isolation of the final compounds were carried out under dry, oxygen-free argon using standard Schlenk techniques.
Tetrahydrofuran was additionally purified by distillation from sodiumrbenzophenone ketyl in argon atmosphere.
Hydrocarbon solvents were dried by refluxing over sodium metal and distilled under argon. Acetonitrile and
Ž
dichlorometane were purified by double distillation under argon. Thin-layer chromatography Merck, 5=7.5 cm,
.
Kieselgel 60 F254 was used whenever possible to monitor the progress of the reactions under study. Column
Ž
.
chromatography was applied to separate the reaction mixtures Kieselgel 60, Merck, 60–230 mesh ASTM . IR spectra
were recorded on a Specord M80 instrument in KBr pellets or in nujol mulls. All NMR measurements were performed
on a Bruker 300 instrument in solutions of CDCl3 predried over molecular sieves.
2
2
Ž
. Ž
. Ž .
w x
Palladium cluster Pd4 m -CO m -OAc I was prepared by the method published in Ref. 16 .
4
4
[
(
) (
)(
)
] ( )
II
3.1.1. Synthesis of Pd OAc o- NPh NO C6 H4
2
Ž
.
Ž
.
200 mg of cluster I 0.25 mmol, 1 mg-atom Pd , 5 ml of toluene, and a solution of 107 mg 1 mmol of
nitrosobenzene in 5 ml of toluene were placed into a water-jacketed two-neck reaction vessel connected with a gas
burette under argon. The system was evacuated, purged with argon, and stirred at 608C until complete cessation of the
Ž
.
CO2 evolution 3 to 4 h, volumetrical monitoring . The reaction mixture was filtered, and the filtrate was concentrated
to ca. 1r4 of the initial volume. Complex II was precipitated by hexane, filtered off, and dried in vacuo; yield: 180
Ž
.
Ž
.
Ž .
mg 0.16 mmol, 32% based on Pd . For Pd2C29 H26O6 N4Cl2 calcd. % : C, 42.96; H, 3.21; N, 6.91. Found % : C,
42.5; H, 3.5; N, 5.3. Crystals suitable for X-ray diffraction analysis were obtained from a CH2Cl2-pentane mixture.
[ (
)( )
] ( )
IV
3.1.2. Synthesis of Pt o- NPh N C6 H4
2
Ž
.
Ž
.
.
Ž
.
To a solution of 200 mg 0.44 mmol of K2 Pt NO2 in 70 ml of the MeCNrH2O 1:1 mixture was added
4
Ž
N-phenyl-o-phenylenediamine 162 mg, 0.88 mmol at 508C. The reaction mixture was stirred at 50–808C until the
Ž
.
formation of dark blue solution. After storing the solution for one day at room temperature, TLC benzene indicated
Table 11
4
2
3
˚
Ž
.
Ž
.
Ž
.
Ž .
Atomic coordinates =10 and equivalent isotropic displacement coefficients A =10 U eq for N-phenyl-o-phenylenediamine L
Atom
X
Y
Z
U
Žeq.
Ž .
N 2
Ž .
1612 3
384 2
Ž .
1056 8
2550 4
Ž .
2194 2
3586 2
Ž .
95 1
N 1
Ž .
Ž .
Ž .
Ž .
Ž .
67 1
Ž .
Ž .
Ž .
Ž .
Ž .
59 1
C 1
592 2
y128 4
2424 2
Ž .
Ž .
Ž .
Ž .
Ž .
54 1
C 2
y3 2
541 4
3130 1
Ž .
Ž .
y996 3
Ž .
Ž .
Ž .
60 1
C 3
Ž .
y716 5
3361 2
Ž .
Ž .
Ž .
Ž .
66 1
C 4
y1423 3
y2614 5
2900 2
Ž .
Ž .
y832 3
Ž .
y3290 5
Ž .
Ž .
64 1
C 5
2211 2
Ž .
Ž .
Ž .
Ž .
Ž .
66 1
C 6
158 3
y2080 5
1981 2
Ž .
Ž .
Ž .
2676 4
Ž .
Ž .
52 1
C 7
Ž .
1425 2
4180 1
Ž .
Ž .
Ž .
Ž .
66 1
C 8
1678 3
4680 4
4644 2
Ž .
Ž .
Ž .
Ž .
Ž .
77 1
C 9
2715 3
4845 6
5219 2
Ž
.
.
.
Ž .
Ž .
Ž .
Ž .
74 1
C 10
3539 3
3064 6
5351 2
Ž
Ž .
Ž .
Ž .
Ž .
64 1
C 11
3292 3
1075 5
4903 2
Ž
Ž .
2249 2
Ž .
860 4
Ž .
4319 2
Ž .
53 1
C 12
Ž
.
Ž
.
.
.
.
.
.
.
.
.
.
.
.
Ž
.
.
.
.
.
.
.
.
.
.
.
.
Ž
.
.
.
.
.
.
.
.
.
.
.
.
Ž
.
.
.
H 1N
1621 37
2629 91
2364 26
121 16
Ž
104 14
Ž
.
.
Ž
Ž
Ž
H 2N
1784 37
706 69
1745 29
Ž
Ž
Ž
Ž
Ž
101 12
H 3N
y136 34
3644 70
3525 24
Ž .
Ž
Ž
Ž
Ž .
84 9
H 4
y1406 28
y264 51
3870 23
Ž .
Ž
Ž
Ž
1867 21
Ž .
82 9
H 5
y1189 26
y4600 55
Ž .
Ž
Ž
Ž
Ž .
97 10
H 6
Ž .
523 31
y2582 62
1489 23
Ž
Ž
Ž
Ž .
Ž .
.
.
H 8
1052 24
5994 51
4551 17
66 7
80 9
Ž .
Ž
Ž
Ž
H 9
2885 29
6115 55
5560 20
Ž .
Ž
Ž
Ž
Ž
H 9
y2164 34
y3342 52
3040 21
81 10
Ž
.
Ž
Ž
Ž
Ž
93 10
H 10
4340 32
3233 55
5756 23
Ž
.
Ž
Ž
Ž
Ž .
58 7
H 11
3823 25
y154 48
4996 17
Ž
.
Ž
Ž
Ž
Ž .
59 7
H 12
2050 24
y512 49
4050 17
Equivalent isotropic U defined as one-third of the trace of the orthogonalized U tensor.
i j

(
)
188
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
Table 12
4
2
3
˚
Ž
.
Ž
.
Ž .
Atomic coordinates =10 and equivalent isotropic displacement coefficients A =10 U eq for complex V
Atom
Ž .
X
Y
Z
U
Žeq.
Ž .
6565 2
Ž .
Ž .
Ž .
35 1
Pd 1
Ž .
7913 1
6331 1
7074 2
4884 2
5596 2
7783 2
6338 3
6666 3
5816 3
4610 3
4252 3
5104 3
3691 2
3213 3
2037 3
1344 3
1819 3
2993 3
6349 2
6032 2
6883 3
8092 3
8429 2
7581 2
8944 2
9398 3
10511 3
11192 3
10755 3
y2190 1
Ž .
Ž .
Ž .
y2863 2
Ž .
49 1
N 1
Ž .
Ž .
Ž .
Ž .
Ž .
39 1
N 2
7786 2
y2553 2
Ž .
Ž .
Ž .
Ž .
y1511 2
Ž .
40 1
N 3
9255 2
Ž .
Ž .
Ž .
Ž .
Ž .
36 1
N 4
Ž .
8049 2
y1849 2
Ž .
Ž .
Ž .
y3190 2
Ž .
44 1
C 1
6202 3
Ž .
Ž .
Ž .
Ž .
Ž .
60 1
C 2
5207 3
y3636 2
Ž .
Ž .
Ž .
Ž .
y3968 2
Ž .
67 1
C 3
4971 3
Ž .
Ž .
Ž .
Ž .
Ž .
67 1
C 4
Ž .
5727 3
y3901 2
Ž .
Ž .
Ž .
y3435 2
Ž .
51 1
C 5
6672 3
Ž .
Ž .
Ž .
Ž .
Ž .
42 1
C 6
6912 3
y3045 2
Ž .
Ž .
Ž .
Ž .
y2324 2
Ž .
36 1
C 7
8497 2
Ž .
Ž .
Ž .
Ž .
Ž .
46 1
C 8
Ž .
C 10
9726 3
y2686 2
Ž .
Ž .
Ž .
y2474 2
Ž .
56 1
C 9
Ž
10385 3
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
Ž .
Ž .
Ž .
53 1
9843 3
y1915 2
Ž
Ž .
Ž .
Ž .
y1542 2
Ž .
50 1
C 11
8630 3
Ž
Ž .
Ž .
Ž .
Ž .
47 1
C 12
7945 3
y1743 2
Ž
Ž .
Ž .
Ž .
y1159 2
Ž .
36 1
C 13
9587 2
Ž
Ž .
Ž .
Ž .
Ž .
41 1
C 14
10518 3
10753 3
10073 3
y640 2
Ž
Ž .
Ž .
Ž .
y315 2
Ž .
49 1
C 15
Ž
Ž .
Ž .
Ž .
Ž .
48 1
C 16
y484 2
Ž
Ž .
Ž .
Ž .
y988 2
Ž .
42 1
C 17
9197 3
Ž
Ž .
Ž .
Ž .
Ž .
34 1
C 18
8921 2
y1353 2
Ž
Ž .
Ž .
Ž .
y2185 2
Ž .
39 1
C 19
7406 3
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
46 1
C 20
6143 3
Ž .
y2022 2
Ž
Ž .
Ž .
C 21
5515 3
y2371 2
61 1
Ž
Ž .
Ž .
Ž .
y2866 2
Ž .
C 22
6113 3
66 1
Ž
Ž .
Ž .
Ž .
Ž .
0
Ž .
C 23
7363 3
y3019 2
57 1
Ž .
Ž
Ž .
Ž .
C 24
Ž .
8015 3
9637 3
y2694 2
45 1
Ž .
Pd 2
1r2
1r2
Ž .
34 1
Ž .
Ž .
Ž .
Ž .
N 5
Ž .
3920 2
6195 2
6462 2
7316 2
y748 2
44 1
Ž .
Ž .
Ž .
Ž .
N 6
5146 2
327 2
36 1
Ž .
Ž
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
Ž .
Ž .
C 25
3780 2
y685 2
39 1
Ž
Ž .
Ž .
Ž .
Ž .
C 26
3041 3
8319 3
Ž .
y1142 2
53 1
Ž
Ž .
Ž .
y979 3
Ž .
C 27
2913 3
9424 3
56 1
Ž
Ž .
Ž .
Ž .
Ž .
C 28
3521 3
9589 2
8645 2
y338 2
50 1
Ž .
Ž
Ž .
Ž .
Ž .
103 2
C 29
4272 2
42 1
Ž
Ž .
Ž .
Ž .
Ž .
C 30
4453 2
7480 2
Ž .
y75 2
37 1
Ž
Ž .
Ž .
878 2
Ž .
C 31
5945 2
6485 2
36 1
Ž
Ž .
Ž .
Ž .
Ž .
C 32
5914 3
5947 2
5960 3
6509 3
Ž .
7035 2
7014 2
1771 2
2307 2
1987 2
1094 2
42 1
Ž .
Ž
Ž .
Ž .
Ž .
C 33
6699 3
51 1
Ž
Ž .
Ž .
Ž .
Ž .
C 34
7507 3
51 1
Ž
Ž .
Ž .
Ž .
45 1
C 35
7549 2
Ž
Ž .
Ž .
Ž .
Ž .
39 1
C 36
6778 2
0
549 2
Ž .
Ž .
40 1
Pd 3
1r2
y1r2
Ž .
Ž .
Ž .
Ž .
Ž .
41 1
N 7
y434 2
6696 2
5688 2
6873 3
7572 3
8771 3
9318 3
8680 3
7445 3
7135 2
6692 3
7132 3
7997 3
8005 3
8433 3
7466 5
6053 5
y4773 2
Ž .
Ž .
y1595 2
Ž .
Ž .
y5368 2
Ž .
46 1
N 8
Ž
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
Ž .
Ž .
Ž .
45 1
C 37
y2131 3
y5347 2
Ž
Ž .
y3232 3
Ž .
Ž .
y5644 2
Ž .
54 1
C 38
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
65 1
C 39
y3684 3
y5585 3
Ž
Ž .
Ž .
C 40
y3096 3
y5203 3
65 1
Ž
Ž .
y2046 3
Ž .
Ž .
y4907 2
Ž .
C 41
53 1
Ž
Ž .
Ž .
Ž .
Ž .
C 42
y1493 3
y5005 2
42 1
Ž
Ž .
298 3
Ž .
Ž .
y4428 2
Ž .
41 1
C 43
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
45 1
C 44
666 3
y3587 2
Ž
Ž .
Ž .
Ž .
54 1
C 45
1362 3
y3243 2
Ž
Ž .
Ž .
Ž .
y3732 3
Ž .
65 1
C 46
1714 3
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
54 1
C 48
683 3
y4928 2
Ž
Ž .
Ž .
Ž .
C 47
1374 3
y4570 3
66 1
Ž .
Ž .
Ž .
Ž .
y3705 5
Ž .
H 2
4787 5
62 1
Ž .
Ž .
Ž .
Ž .
Ž .
h 3
Ž .
4271 5
y4230 5
75 1
Ž .
Ž .
Ž .
y4174 5
Ž .
89 1
H 4
5487 5
3970 5

(
)
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
189
Ž
.
Table 12 continued
Atom
X
Y
Z
U
Žeq.
Ž .
H 5
H 8
Ž .
7213 5
10034 5
Ž .
3405 5
3663 5
Ž .
y3426 5
Ž .
59 1
Ž .
Ž .
Ž .
Ž .
y3083 5
Ž .
49 1
Ž .
Ž .
Ž .
Ž .
y2733 5
Ž .
46 1
H 9
11104 5
1758 5
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
Ž .
Ž .
Ž .
60 1
H 10
10239 5
607 5
y1827 5
Ž
Ž .
Ž .
Ž .
y1135 5
Ž .
70 1
H 11
8268 5
1333 5
Ž
Ž .
Ž .
Ž .
Ž .
70 1
H 12
7121 5
3350 5
y1446 5
Ž
Ž .
Ž .
Ž .
y520 5
Ž .
36 1
H 14
10930 5
5257 5
Ž
Ž .
Ž .
Ž .
Ž .
44 1
H 15
11308 5
6692 5
y43 5
Ž
Ž .
Ž .
Ž .
y248 5
Ž .
53 1
H 16
10271 5
8673 5
Ž
Ž .
Ž .
Ž .
Ž .
35 1
H 17
8745 5
9217 5
y1111 5
Ž
Ž .
Ž .
Ž .
y1695 5
Ž .
54 1
H 20
5712 5
8960 5
Ž
Ž .
Ž .
Ž .
Ž .
62 1
H 21
4804 5
10756 5
y2244 5
Ž
Ž .
Ž .
Ž .
y3085 5
Ž .
66 1
H 22
5648 5
11955 5
Ž
Ž .
Ž .
Ž .
Ž .
61 1
H 23
7764 5
11164 5
y3367 5
Ž
Ž .
Ž .
Ž .
y2838 5
Ž .
37 1
H 24
8871 5
9338 5
Ž
Ž .
Ž .
Ž .
Ž .
52 1
H 26
2711 5
8236 5
y1506 5
Ž
Ž .
Ž .
Ž .
y1292 5
Ž .
64 1
H 27
2456 5
10067 5
Ž
Ž .
Ž .
Ž .
Ž .
44 1
H 28
3393 5
10355 5
y194 5
Ž
Ž .
Ž .
Ž .
544 5
Ž .
41 1
H 29
4660 5
8764 5
Ž
Ž .
Ž .
Ž .
Ž .
56 1
H 32
5339 5
5556 5
2003 5
Ž
Ž .
Ž .
Ž .
Ž .
67 1
H 33
6609 5
5599 5
2906 5
Ž
Ž .
Ž .
Ž .
Ž .
55 1
H 34
7958 5
6583 5
2333 5
Ž
Ž .
Ž .
Ž .
Ž .
41 1
H 35
8076 5
7408 5
870 5
Ž
Ž .
Ž .
Ž .
Ž .
48 1
H 36
6863 5
7311 5
y87 5
Ž
Ž .
Ž .
Ž .
y5843 5
Ž .
67 1
H 38
y3663 5
7164 5
Ž
Ž .
Ž .
Ž .
Ž .
H 39
y4331 5
9197 5
Ž .
y5830 5
69 1
Ž
Ž .
y3407 5
Ž .
y5188 5
Ž .
H 40
10126 5
70 1
Ž
Ž .
Ž .
Ž .
Ž .
H 41
y1782 5
9084 5
y4624 5
94 1
Ž .
Ž
Ž .
395 5
Ž .
Ž .
y3201 5
H 44
6076 5
66 1
Ž
Ž .
Ž .
Ž .
Ž .
H 45
1530 5
6899 5
Ž .
y2681 5
73 1
Ž
Ž .
Ž .
y3507 5
Ž .
H 46
2071 5
8369 5
85 1
Ž
Ž .
Ž .
Ž .
Ž .
H 47
1632 5
8935 5
y4902 5
65 1
Ž
Ž .
Ž .
Ž .
y5549 5
Ž .
57 1
H 48
513 5
8245 5
Equivalent isotropic U defined as one third of the trace of the orthogonalized U tensor.
i j
the absence of free organic ligand and the formation of a dark blue band. It was separated by the use of column
Ž
.
chromatography 5=30 cm, silica gel, 60–80 ml of benzene . The solution was concentrated to 15–20 ml and after
addition of 5–8 ml of hexane or heptane and cooling to 5–108C gave bronze-black prismatic crystals of
w
Ž
.Ž .
x2
Ž
. Ž
.
w
Ž
.Ž .
x
Pt NPh N C6 H4
IV 159 mg, 0.28 mmol, 65% . Anal. Calcd. for Pt NPh N C6 H4 2: C, 51.71; H, 3.23; N,
10.05. Found: C, 51.87; H, 3.44; N, 10.11. IR, y cmy1: 447s, 497m, 537m, 581vs, 601vs, 631m, 664vs, 708s, 741vs,
751vs, 761vs, 852m, 935m, 1022w, 1072w, 1146m, 1193w, 1123m, 1273m, 1337m, 1460m, 1480m, 1490m, 1547m,
Ž
.
1584m, 1658m, 1671w. Complex IV can be also prepared by reaction of K2 PtCl4 with the ligand 1:2 mole ratio ;
Ž
.
however, in this case, the addition of alkali is required and the yield of final product is much lower maximum 5%
[ ( ] ( )
3.1.3. Synthesis of Pd o- NPh N C6 H4 V
2
)( )
Ž
.
Ž
.
Ž
.
To a solution of 250 mg 0.68 mmol of K2 Pd NO2 in 70 ml of mixture MeCNrH2O 1:1 were added
4
Ž
.
Ž
.
N-phenyl-o-phenylenediamine 250 mg, 1.36 mmol and LiOH 1 g at 508C. The reaction mixture was left to stay for
one day at room temperature until the formation of blue-green solution. The solvents were removed to dryness and a
Ž
.
solid residue was extracted by boiling hexane 400–600 ml . The blue solution obtained was concentrated to 100 ml
w
Ž
.Ž . x2 Ž . Ž
and, after cooling to room temperature, afforded black-blue prismatic crystals of Pd NPh N C6 H4
V
162 mg,
.
w
Ž
.Ž .
x
0.35 mmol, 51% . Anal. Calcd. for Pd NPh N C6 H4 2: C, 61.53; H, 3,85; N, 11.96. Found: C, 61.23; H, 3.84; N,
11.82. IR, y cmy1: 440m, 487m, 530w, 567s, 591s, 631s, 654vs, 706s, 754vs, 761vs, 838m, 918m, 1022w, 1072w,
1146vs, 1183w, 1266m, 1263m, 1337vs, 1383m, 1454s, 1487s, 1514w, 1584w, 1614w, 1654w, 1671w.
[(
)( )
] [
] ( )
VII
3.1.4. Synthesis of Pt2 NPh N C6 H4 O3 SCF3
4
2
Ž
.
Ž
.
A mixture of 500 mg 0.898 mml of complex IV and 230 mg 0.895 mmol of AgO3SCF3 with 2–3 ml of acetone
was ground in agate mortar at room temperature. To the product prepared, 100 ml of CH2Cl2 was added, and the
brown solution formed was filtered. After its concentration to 20–30 ml and cooling to y188C, a brown-green

(
)
190
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
Table 13
4
2
3
˚
Ž
.
Ž
.
Ž .
Atomic coordinates =10 and equivalent isotropic displacement coefficients A =10 U eq for VII
Atom
Ž .
X
Y
Z
U
Žeq.
Ž .
9524 4
Ž .
Ž .
y294 1
Ž .
37 1
Pt 1
Ž .
8487 1
9827 1
Ž .
Ž .
Ž .
161 4
Ž .
41 1
N 1
11635 4
10280 4
Ž .
Ž .
Ž .
Ž .
y1849 4
Ž .
39 1
N 2
7948 4
Ž .
Ž .
Ž .
Ž .
1315 4
Ž .
42 1
N 3
9009 4
9601 4
Ž .
Ž .
Ž .
Ž .
y559 4
Ž .
41 1
N 4
Ž .
7398 4
7978 4
Ž .
Ž .
Ž .
y685 5
Ž .
44 1
C 1
9464 5
12244 5
13559 5
14062 6
13273 6
12048 6
11468 5
Ž .
Ž .
Ž .
Ž .
y552 5
Ž .
54 1
C 2
10139 6
Ž .
Ž .
Ž .
Ž .
y1485 6
Ž .
66 1
C 3
9930 6
Ž .
Ž .
Ž .
Ž .
y2634 6
Ž .
66 1
C 4
Ž .
9023 7
Ž .
Ž .
Ž .
y2790 5
Ž .
57 1
C 5
8372 6
Ž .
Ž .
Ž .
Ž .
y1841 5
Ž .
44 1
C 6
8550 5
Ž .
Ž .
Ž .
Ž .
1467 5
Ž .
47 1
C 7
8499 5
8461 6
Ž .
Ž .
Ž .
Ž .
2552 5
Ž .
61 1
C 8
Ž .
C 10
8738 6
8101 6
Ž .
Ž .
Ž .
2587 6
Ž .
73 1
C 9
Ž
8080 7
6893 7
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
Ž .
Ž .
1513 6
Ž .
72 1
7142 7
6007 6
Ž
Ž .
Ž .
Ž .
478 5
Ž .
393 5
Ž .
60 1
C 11
6877 6
6277 6
Ž
Ž .
Ž .
Ž .
47 1
C 12
7556 5
7524 5
Ž
Ž .
Ž .
Ž .
y2943 5
Ž .
45 1
C 13
6904 5
9487 5
Ž
Ž .
Ž .
Ž .
Ž .
58 1
C 14
5705 6
9523 6
y3219 6
Ž
Ž .
Ž .
Ž .
y4252 6
Ž .
74 1
C 15
4698 6
8817 6
Ž
Ž .
Ž .
Ž .
Ž .
79 1
C 16
4899 7
8085 6
y5017 6
Ž
Ž .
Ž .
Ž .
y4751 6
Ž .
78 1
C 17
6074 7
8037 6
Ž
Ž .
Ž .
Ž .
Ž .
64 1
C 18
7105 6
8741 6
y3691 6
Ž
Ž .
Ž .
Ž .
y1651 5
Ž .
44 1
C 19
6429 5
7103 5
Ž
Ž .
Ž .
Ž .
Ž .
C 20
6773 6
6309 6
y2215 6
59 1
Ž
Ž .
Ž .
Ž .
y3230 6
Ž .
C 21
5836 7
5437 6
70 1
Ž
Ž .
Ž .
Ž .
y3643 6
Ž .
C 22
4598 7
5363 6
72 1
Ž .
Ž
Ž .
Ž .
Ž .
y3096 6
C 23
4263 6
Ž .
6150 6
Ž .
65 1
Ž
Ž .
y2084 5
Ž .
C 24
5186 6
7049 5
54 1
Ž .
Ž .
Ž .
Ž .
y3459 2
Ž .
S 1
y427 2
y2981 2
64 1
Ž .
Ž .
Ž .
Ž .
y3104 8
Ž .
O 1
Ž .
y243 7
y1815 6
191 1
Ž .
Ž .
Ž .
Ž .
y2447 6
O 2
y329 7
y3476 7
163 1
Ž .
Ž .
Ž .
Ž .
y4497 5
Ž .
O 3
y1426 6
y3674 7
140 1
Ž .
Ž .
Ž .
Ž .
y2824 6
Ž .
F 1
2100 5
Ž .
y2146 7
194 1
Ž .
Ž .
Ž .
y4595 7
Ž .
F 2
Ž .
1135 7
y2432 9
273 1
Ž .
Ž .
Ž .
Ž .
y3932 8
F 3
1025 7
y3850 8
310 1
Ž
.
Ž .
Ž .
Ž .
y3637 7
Ž .
C 25
1052 8
y2760 9
142 1
Ž
.
.
.
.
.
.
Ž .
Ž .
Ž .
180 9
Ž .
C 1B
3977 9
Ž .
8346 9
Ž .
257 1
Ž
Ž .
214 8
Ž .
C 2B
3196 8
7318 8
143 1
Ž .
197 1
Ž
Ž .
Ž .
Ž .
956 9
C 3B
3479 9
6883 9
Ž
Ž .
Ž .
Ž .
1751 9
Ž .
C 4B
4735 9
7378 9
188 1
Ž .
121 1
Ž
Ž .
Ž .
Ž .
1916 8
C 5B
5707 8
8505 8
Ž
Ž .
Ž .
Ž .
1225 8
Ž .
199 1
C 6B
5482 8
8859 9
Ž .
Ž
.
.
Ž
.
.
.
.
Ž .
361 10
Ž .
50 1
H 2
10661 10
10322 10
14105 10
14850 10
13766 10
11727 10
8691 10
6566 10
5180 10
5651 10
9725 10
8836 10
7442 10
7522 10
8703 10
6359 10
4957 10
4734 10
Ž .
Ž
Ž
Ž
.
.
.
Ž .
50 1
H 3
y1466 10
Ž .
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž
Ž
y3254 10
Ž .
50 1
H 4
Ž .
8934 10
7929 10
9425 10
8297 10
6762 10
6225 10
5293 10
3877 10
4254 10
6334 10
7965 10
7653 10
6271 10
3937 10
3395 10
4949 10
Ž
Ž
Ž
Ž .
50 1
H 5
y3555 10
Ž .
Ž
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž
.
.
.
.
Ž .
50 1
H 8
3329 10
Ž .
Ž
Ž
Ž
Ž .
50 1
H 9
3244 10
1616 10
Ž
.
Ž
Ž
Ž
Ž
Ž .
50 1
H 10
Ž
.
.
.
.
.
.
.
.
.
.
.
Ž
Ž
Ž .
80 1
H 11
y222 10
Ž
Ž
Ž
Ž
.
.
.
.
.
.
.
.
.
.
Ž .
50 1
H 14
y2849 10
Ž
Ž
Ž
Ž
y4456 10
Ž .
80 1
H 15
Ž
Ž
Ž
Ž
Ž .
51 1
H 16
y5818 10
Ž
Ž
Ž
Ž
Ž .
H 17
y5374 10
51 1
Ž
Ž
Ž
Ž
Ž .
H 18
y3488 10
80 1
Ž
Ž
Ž
Ž
Ž .
H 20
y1904 10
80 1
Ž
Ž
Ž
Ž
y3595 10
Ž .
51 1
H 21
Ž
Ž
Ž
Ž
Ž
Ž .
81 1
H 22
y4365 10
Ž
Ž
Ž
Ž .
51 1
H 23
6266 10
7618 10
y3402 10
Ž
Ž
Ž
Ž
y1678 10
Ž .
80 1
H 24
Equivalent isotropic U defined as one third of the trace of the orthogonalized U tensor.
i j

(
)
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
191
crystalline precipitate was separated, washed with benzene and hexane and dried in vacuo. Yield of
w
Ž
.Ž
.
x w
x2
Ž
. Ž .
VII is 450 mg 0.319 mmol, 70.9% . Anal.: Calcd. for
Pt NPh N C 6 H 4 O 3 SCF3
4
2w
Ž
.Ž .
x w
x
Pt2 NPh N C6 H4 O3SCF3 2: C, 42.49; H, 2,55; N, 7.93. Found: C, 42.55; H, 2.44; N, 7.87. IR, y cmy1: 440w,
4
497w, 527m, 561s, 597s, 644vs, 694s, 751s, 831m, 875w, 918w, 999m, 1025s, 1076w, 1159vs, 1230vs, 1260vs,
1286vs, 1367vs, 1447s, 1497s, 1510vs, 1531s, 1561w, 1594m, 1631w, 1671w, 1694w. Single crystals of VII for the
X-ray investigation were obtained as a benzene solvate by slow evaporation of a CH2Cl2—benzene 5:1 solution
Ž
.
Ž
.
caved by the layer of hexane from ampule 7=150 mm .
[( )
)(
)
]
(
3.1.5. Synthesis of Pt NPh NH C6 H4 Br2 VIII
Ž
.
Ž
.
A mixture of 250 mg 0.449 mml of complex IV and 110 mg 0.5 mmol of CuBr2 with 2–3 ml of acetone
Ž
.
containing 2–5% of H2O was ground in agate mortar at room temperature. To the product prepared, 50 ml of
CH2Cl2 was added, and the black-red solution was filtered. After the concentration to 20–30 ml and cooling of the
solution to y188C, the black-red needle-shaped crystals were separated, washed with ether and hexane and dried in
w
Ž
.Ž
.
x
Ž
.
Ž
.
vacuo. Yield of Pt NPh NH C6 H4 Br2 VIII is 210 mg 0.393 mmol, 57.5% . Anal.: Calcd. for
w
Ž
.Ž
.
x
Pt NPh NH C6 H4 Br2: C, 26.92; H, 1.87; N, 5.23; Br, 33.64. Found: C, 27.02; H, 1.72; N, 5.47; Br, 33.23. IR, y
cmy1: 472m, 490m, 501w, 594s, 648s, 681w, 698s, 751s, 798s, 825m, 842w, 865w, 895m, 952w, 979w, 1025m,
1072m, 1139w, 1163m, 1189w, 1219w, 1233w, 1266w, 1290w, 1380w, 1400m, 1447m, 1490m, 1531s, 1564w,
1594m, 1624w, 1674w, 1648m. Single crystals suitable for X-ray investigation were prepared by slow evaporation of
Ž
.
a CH2Cl2 solution of VIII from ampule 15=120 mm at room temperature.
3.1.6. Oxidation of V or VII by AgO3 SCF3— synthesis of IX
Ž
.
Ž
Ž
.
To a solution of complex IV 200 mg, 0.359 mmol in 20 ml of acetone was added AgO3SCF3 approx. 6 eqiv. at
room temperature until the starting complex IV and intermediately formed VII were consumed TLC monitoring .
Removal of the solvent in vacuo left a brown oilish residue, which was dissolved in CH2Cl2 to form a brown-green
.
Ž
.
solution. The solution was chromatographed on silica gel 5=35 cm, 50–70 ml of mixture CH2Cl2rTHF 1:1 , and a
Ž
.
yellow-orange band Rf s0.4–0.5 was separated. The orange eluate was concentrated to dryness and oilish
Ž
.
brown-red residue was solved in a mixture of benzene and hexane 1:5 . The cooling of this solution to y5–y108C
Ž
.
led to the formation of needle-shaped crystals of heterotricyclic compound IX 100 mg, 0.249 mmol, 69.3% . Anal.
Calcd for C27 H22 N4: C, 80.60; H, 5.47; N, 13.93. Found: C, 80.55; H, 5.65; N, 13.65. IR, y cmy1: 474w, 561w,
Table 14
4
2
3
˚
Ž
.
Ž
.
Ž .
Atomic coordinates =10 and equivalent isotropic displacement coefficients A =10 U eq for complex VIII
Atom
X
Y
Z
U
Žeq.
Ž .
Br 1
Ž .
4708 1
2965 2
Ž .
15707 1
14266 2
Ž .
40 1
Pt 1
Ž .
1r4
1r4
1r4
1r4
1r4
1r4
1r4
1r4
1r4
1r4
1r4
1r4
Ž .
Ž .
Ž .
49 1
Ž .
Ž .
Ž .
Ž .
71 1
Br 2
3248 3
17320 2
Ž .
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
35 2
N 1
5964 12
14527 12
Ž .
Ž
Ž
Ž .
43 2
N 2
Ž .
6321 15
16659 12
Ž
Ž
Ž .
58 2
C 1
7115 19
14840 16
Ž .
Ž
Ž
Ž .
67 2
C 2
8288 20
14051 16
Ž .
Ž
Ž
Ž .
67 2
C 3
9353 18
14577 18
Ž .
Ž
Ž
Ž .
58 2
C 4
9542 17
15773 18
Ž .
C 5
Ž
Ž
Ž .
64 2
8728 19
16512 18
Ž .
Ž
Ž
Ž .
C 6
7357 16
16070 14
37 2
Ž .
Ž
Ž
Ž .
C 7
6417 17
17992 14
46 2
Ž .
Ž
Ž
.
.
Ž
Ž .
C 8
Ž .
6481 18
4287 21
18582 12
86 2
Ž
Ž
Ž
Ž .
107 2
C 9
6601 19
4278 24
19782 14
Ž
.
Ž
Ž
Ž .
89 2
C 10
6641 20
1r4
1r4
1r4
1r4
1r4
1r4
5518 30
5544 30
2489 30
20373 16
Ž
.
Ž
Ž
Ž .
83 3
H 1N
5839 29
13938 29
Ž .
Ž
Ž
Ž .
81 3
H 2
8006 29
13241 29
Ž .
Ž
Ž
Ž .
81 3
H 3
9933 29
14115 29
Ž .
Ž
.
Ž
Ž .
H 4
Ž .
10427 29
16036 29
83 3
Ž
.
.
.
.
Ž
Ž .
H 5
8710 29
17336 29
81 3
Ž .
Ž
Ž
.
.
.
Ž
Ž .
H 8
6430 29
18161 29
83 3
Ž .
Ž
Ž
Ž
Ž .
86 3
H 9
6612 29
20239 29
Ž
.
Ž
Ž
Ž
21233 29
Ž .
84 3
H 10
6716 29

(
)
192
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
591w, 617w, 634w, 704m, 755s, 768w, 819m, 848w, 1029w, 1076w, 1153w, 1216w, 1250m, 1320m, 1360m, 1400w,
1440w, 1474m, 1497m, 1547m, 1574s, 1601m, 1641s, 2845w, 2864w, 2926m, 2963w, 2987w. Compound IX was
prepared by same way using VII as a starting material and 3–4 equivalents of AgOSCF3.
Table 15
4
2
3
˚
Ž
.
Ž
.
Ž .
Atomic coordinates =10 and equivalent isotropic displacement coefficients A =10 U eq for compound IX
Atom
Ž .
X
Y
Z
U
Žeq.
Ž .
Ž .
Ž .
Ž .
60 1
N 1
5382 1
4909 1
5833 1
5331 1
5394 1
5645 1
5617 1
5352 1
5099 1
5119 1
5820 1
5570 1
5567 2
5799 2
6036 2
6051 2
1718 1
1087 1
12038 3
13251 2
9790 2
11378 2
11755 3
10828 3
10686 3
11471 3
12378 3
12504 3
9678 3
10494 3
10413 3
9555 3
8769 4
8813 3
Ž .
Ž .
Ž .
Ž .
Ž .
53 1
N 2
Ž .
Ž .
Ž .
Ž .
Ž .
47 1
N 3
746 1
Ž .
Ž .
Ž .
Ž .
Ž .
46 1
N 4
Ž .
20 1
Ž .
Ž .
Ž .
Ž .
48 1
C 1
1332 1
1274 1
Ž .
Ž .
Ž .
Ž .
Ž .
48 1
C 2
Ž .
Ž .
Ž .
Ž .
Ž .
42 1
C 3
839 1
Ž .
Ž .
Ž .
Ž .
Ž .
42 1
C 4
Ž .
438 1
Ž .
Ž .
Ž .
Ž .
44 1
C 5
503 1
Ž .
Ž .
Ž .
Ž .
Ž .
43 1
C 6
928 1
Ž .
Ž .
Ž .
Ž .
Ž .
46 1
C 7
308 1
Ž .
Ž .
Ž .
Ž .
Ž .
47 1
C 8
Ž .
C 10
y50 1
Ž .
Ž .
Ž .
Ž .
57 2
C 9
Ž
y486 2
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
Ž .
y573 2
Ž .
Ž .
66 2
Ž
Ž .
Ž .
Ž .
Ž .
66 2
C 11
y221 2
Ž
Ž .
Ž .
208 2
Ž .
Ž .
59 2
C 12
Ž
Ž .
Ž .
Ž .
Ž .
57 2
C 13
5078 2
4662 2
5372 2
1609 2
1692 2
1921 2
13022 3
12731 4
14001 3
Ž
Ž .
Ž .
Ž .
Ž .
C 14
77 2
Ž
Ž .
Ž .
Ž .
Ž .
C 15
78 2
Ž
Ž .
Ž .
Ž .
Ž .
C 16
4672 1
Ž .
835 1
Ž .
14247 3
Ž .
49 1
Ž .
Ž
C 17
4898 2
678 2
14963 3
66 2
Ž
Ž .
Ž .
Ž .
Ž .
C 18
4666 2
4220 2
430 2
15935 3
16178 4
75 2
Ž
Ž .
Ž .
Ž .
Ž .
C 19
350 2
77 2
Ž
Ž .
Ž .
Ž .
Ž .
C 20
3992 2
Ž .
499 2
Ž .
15475 4
Ž .
73 2
Ž .
Ž
C 21
4213 2
741 2
14505 3
64 2
Ž
Ž .
Ž .
Ž .
Ž .
C 22
6050 1
5775 2
1106 1
1050 2
8917 3
7974 3
49 1
Ž
Ž .
Ž .
Ž .
Ž .
C 23
63 2
Ž
Ž .
Ž .
Ž .
Ž .
C 24
5978 2
Ž .
1386 2
Ž .
7115 4
Ž .
80 2
Ž .
Ž
C 25
6436 2
1766 2
7221 4
87 2
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
Ž
Ž
Ž .
C 26
6704 2
6502 2
5829 10
4895 10
5366 13
5780 10
6187 11
6172 8
4479 12
4516 13
4806 12
5699 13
5516 12
5212 11
5226 11
4855 13
4092 12
3692 12
4052 11
5434 10
5807 17
6624 12
7043 12
6669 10
1819 2
1476 2
1553 10
192 10
8173 4
9017 3
10311 19
12807 18
10987 22
9457 20
8318 20
8348 17
12136 22
13253 23
12435 22
14081 23
13786 22
14527 20
14779 21
16523 23
16756 21
15655 21
14116 20
7908 19
6452 26
6672 22
8220 21
Ž
9600 19
82 2
Ž
Ž .
Ž .
C 27
67 2
Ž
.
Ž
.
.
.
.
.
Ž
.
.
.
.
.
Ž .
H 2A
42 3
Ž .
Ž
.
.
Ž
Ž
H 5A
42 3
Ž
Ž
Ž
.
.
.
Ž
Ž .
H 9A
y751 13
92 3
Ž
.
.
.
.
Ž
Ž
Ž
.
.
.
Ž .
57 3
H 10A
y903 11
Ž
Ž
Ž
Ž
Ž .
61 3
H 11A
y286 11
Ž
Ž .
Ž .
421 8
Ž
Ž .
23 3
H 12A
Ž
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž
.
.
.
.
.
.
.
.
.
.
.
Ž .
80 3
H 14A
1516 12
1655 13
2082 12
1858 13
2269 13
1831 11
732 11
364 13
185 12
441 11
828 11
782 10
1340 17
2038 13
2137 12
1509 10
Ž
.
.
Ž
Ž
Ž
Ž .
87 3
H 14B
Ž
Ž
Ž
Ž
Ž .
76 3
H 14C
Ž
.
Ž
Ž
Ž
Ž .
91 3
H 15A
Ž
.
Ž
Ž
Ž
Ž .
87 3
H 15B
Ž
.
Ž
Ž
Ž
Ž .
58 3
H 15C
Ž
.
.
.
.
.
.
.
.
.
.
Ž
Ž
Ž
Ž .
62 3
H 17A
Ž
Ž
Ž
Ž
Ž .
95 3
H 18A
Ž
Ž
Ž
Ž
Ž .
H 19A
71 3
Ž
Ž
Ž
Ž
Ž .
H 20A
74 3
Ž
Ž
Ž
Ž
Ž .
H 21A
62 3
Ž
Ž
Ž
Ž
.
.
.
.
.
Ž .
50 3
H 23A
Ž
Ž
Ž
Ž
Ž .
156 3
H 24A
Ž
Ž
Ž
Ž
Ž .
88 3
H 25A
Ž
Ž
Ž
Ž
Ž .
80 3
H 26A
Ž
Ž
Ž
Ž .
52 3
H 27A
Equivalent isotropic U defined as one-third of the trace of the orthogonalized U tensor.
i j

(
)
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
193
3.1.7. Crystal structure determinations
The crystals were all mounted in air on glass fibers using 5 min epoxy resin. The unit cells were determined and
Ž
.
Ž
.
refined from 24 equivalent reflections with 2Q)22–288 and obtained from Syntex P21 for II , CAD-4 for VII–IX ,
Ž
.
and Siemens R3vrm for IV, V, and N-phenyl-o-phenylenediamine four-circle diffractometers at room temperature.
Intensity data sets were corrected for the Lorentz and polarization effects. Backgrounds were scanned for 25 of the
peak widths on each end of the scan. Three reflections were monitored periodically for each compound as a check for
crystal decomposition or movement. No significant variation in these standards was observed, so no correction was
applied. Details of crystal parameters, data collection and structure refinement are given in Table 8.
All structures were solved by a direct method to locate the platinum or palladium atoms for II, IV, V, VII, and
VIII. For IX at this stage, all nonhydrogen atoms were found. The other atoms in II, IV, V, VII, and VIII were located
w
x
in the subsequent difference Fourier maps. The DIFABS method 27 was used for the absorption correction of IV, V,
VII, and VIII at the stage of the isotropic approximation. An anisotropic refinement was applied to all nonhydrogen
atoms, and all hydrogen atoms in the structures were found from the difference Fourier maps and refined in the
Ž
.
isotropic approximation for, IV, V, VII, VIII and the initial ligand . For II, the H atoms were included in calculations
2
˚
as fixed contributions with the constant isotropic temperature factor uiso s0.08 A . The computations were performed
w
x
using the SHELXTL PLUS program package 28 on a Pentium 100r16 computer. Selected bond lengths and angles
for investigated complexes are given in Tables 1–7 and the positional parameters and the equivalent thermal
parameters are listed in Tables 9–15. Complete lists of the bond lengths and angles and the tables of thermal
parameters have been deposited at the Cambridge Crystallographic Data Centre.
4. Conclusion
The results obtained in this work demonstrated that nitrene ligands can be involved into the chemistry of palladium
Ž
.
and platinum. Unlike some other VIII group metals e.g., Fe, Co, Ru, Os , these elements normally form the more
labile nitrene complexes, which can further react by inserting the nitrene ligand to the C–H bond of an arene molecule
to produce observable products like complex II or polyheterocyclic compound IX. Nevertheless, the data available
seem to be encouraging to the search for the stable nitrene complexes of platinum group metals.
Acknowledgements
We are grateful to T.V. Chernysheva for help in the experiments, N.A. Minaeva for providing the IR spectra, and
S.G. Sakharov for assistance with the NMR spectra. We are also thankful to the Russian Foundation for Basic
Ž
.
Research Projects No. 96-15-96994, 96-03-33581, and 96-03-34389 for financial support.
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