Orthopalladacycles derived from α-diphenylhydrazonoketene dithioacetals and their reactivity with terminal alkynes

Article abstract of DOI:10.1016/j.jorganchem.2004.09.068

In this paper, we present the synthesis and characterization of new orthopalladated complexes derived from α-diphenylhydrazonoketene dithioacetals. From their reaction with terminal alkynes, the intermediates of the expected C_sp-C_sp2coupling reaction were isolated in stable form and their structures were confirmed by X-ray diffraction studies.

Full text of DOI:10.1016/j.jorganchem.2004.09.068

Journal of Organometallic Chemistry 690 (2005) 454–462
www.elsevier.com/locate/jorganchem
Orthopalladacycles derived from a-diphenylhydrazonoketene
dithioacetals and their reactivity with terminal alkynes
,a
a
F. Ortega-Jimenez , J.G. Lopez-Cortes , M.C. Ortega-Alfaro , A. Toscano ,
b
a
*
´
´
G. Penieres , R. Quijada , C. Alvarez
´
c
d
a,
*
a
´ ´ ´
Instituto de Quımica, Universidad Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, Coyoacan, C.P. 04510 Mexico, D.F.
´
´ ´
Facultad de Quımica, Ed. A, L-4D Universidad Nacional Autonoma de Mexico, Circuito Exterior,
´
b
´
´ ´
Ciudad Universitaria, Coyoacan, C.P. 04510 Mexico, D.F.
´ ´
Facultad de Estudios Superiores, Cuautitlan; Campo 1, Av. 1 de mayo s/n, Cuautitlan Izcalli, C.P. 54740 Estado de Mexico, Mexico
c
´
´
d
´ ´ ´ ´ ´
Departamento de Ingenierıa Quımica, Facultad de Ciencias Fısicas y Matematicas, Universidad de Chile y Centro para la Investigacion
Interdiciplinaria Avanzada en Ciencias de los Materiales (CIMAT) Santiago, Chile
Received 30 August 2004; accepted 28 September 2004
Available online 5 November 2004
Abstract
In this paper, we present the synthesis and characterization of new orthopalladated complexes derived from a-diphenyl-
hydrazonoketene dithioacetals. From their reaction with terminal alkynes, the intermediates of the expected Csp–Csp2coupling reac-
tion were isolated in stable form and their structures were confirmed by X-ray diffraction studies.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Alkynes; Palladium complex; X-ray diffraction
1. Introduction
used in supramolecular chemistry [7] and several of them
have biological activity [8].
The formation and characterization of cyclopalla-
dated compounds have been of great interest for the last
decade [1] due to the great variety of applications in or-
ganic and organometallic areas [2], i.e., in coupling and
insertion reactions [3,4] (the cyclopalladated complexes
show an enhanced reactivity towards alkynes to give
mono, bis or tris insertion reactions, according to the
complex structure [3a–c]), for enantiomeric excess deter-
mination [5], formation of new mesogenic compounds
[4], as asymmetric catalysts and more recently in polym-
erization reactions [6]. Furthermore, they have also been
An interesting synthetic route to cyclopalladated
compounds occurs when tridentate ligands, such as sem-
icarbazones [9], hydrazones [10], thiosemicarbazones
[11,12] or Schiff bases [13,14] are used. These ligands re-
act with palladium (II) to form cyclopalladated com-
plexes having a characteristic structural moiety that is
a five-five membered heterocyclic fused ring system.
Recently, we reported the syntheses of several cyclo-
palladated complexes derived from diphenylhydrazones
and their transmetallation reaction [10a], Scheme 1.
These cyclopalladated complexes have shown excellent
catalytic activity for ethylene polymerization [15].
In this paper, we present the synthesis, characteriza-
tion and reactivity with terminal alkynes of new
orthopalladated complexes derived from a-diphenyl-
hydrazonoketene dithioacetals.
*
Corresponding author. Tel.: +52 5556 224464; fax: +52
5556162203/17.
E-mail address: cecilio@servidor.unam.mx (C. Alvarez).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.09.068

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F. Ortega-Jimenez et al. / Journal of Organometallic Chemistry 690 (2005) 454–462
455
H
H3C
H3C
N
H
N
N
N
N
n-BuLi, -79˚C
THF
Pd
N
+
H
N
N
Cl
Scheme 1.
2. Discussion and results
bered tricycle. The palladium atom structure exhibits a
distorted square planar geometry. These data are in ac-
cord with those reported for related compounds
[11,14,19,20].
The a-diphenylhydrazonoketene dithioacetals ligands
1.1 and 1.2 were prepared from N,N-diphenylhydrazine
and the corresponding a-oxo ketene dithioacetal by a
condensation reaction in moderate yield. These ligands
react with Na2[PdCl4] [16], to achieve orthopalladated
complexes 2.1 and 2.2, Scheme 2.
2.1. Reactivity with terminal alkynes
In accord with our previous studies [10], we expected
that the orthopalladated complexes 2.1 and 2.2 would
react with terminal alkynes via a transmetallation reac-
tion to give the Csp–C2sp coupling. Instead this reaction
affords the unexpected new complexes 4.1 and 4.2
(Scheme 3), in which only the substitution of chlorine
by the alkyne occurs. Reductive elimination does not
take place.
The infrared spectra of 2.1 and 2.2 show an absorp-
tion band in 1588 cmꢀ1, which is assigned to the vibra-
tion of the C@N bond. We were surprised to find that
this band is no different than the one observed for the
free ligands.
In the MS-FAB+ spectra, we found the correspond-
ing molecular ion for 2.1 and 2.2 in 470 m/z and 469
m/z, respectively.
The infrared spectra of compounds 3.1, 4.1 and 4.2
show a typical band around 2000–2100 cmꢀ1 which is
assigned to the carbon–carbon triple bond stretching
The data obtained for H and 13C NMR for 2.1 and
1
2.2 are presented in Table 1. In 1H NMR spectra, we ob-
serve the typical substitution patterns of a 1,2-disubsti-
tuted aromatic ring, additionally, the chemical shift of
H11 at d 7.76 is in accord with reported values for ana-
logue our orthopalladate complexes. Similarly, the 13C
NMR data for these complexes also reveal the forma-
tion of the orthopalladated cycle since the signals for
C7 and C11 appear at higher frequencies and the signals
for C8 and C9 are presented at lower frequencies,
[10,17,18].
1
vibration. The H and 13C NMR spectra are listed in
Table 4.
The structure of the complex 3.1 was confirmed by a
single crystal X-ray diffraction analysis. An ORTEP dia-
gram of 3.1 is shown in Fig. 2. The crystal data and
bond distance and angles are presented in Tables 2
and 5. The metal center exhibits a square-planar coordi-
nation. The coordinated methylsulfanyl group and the
aromatic ring of the phenylacetylene group are disor-
dered (64:36) over two orientations, only the major con-
tributors are shown in Fig. 2.
In order to demonstrate that the complexes 3.1, 4.1
and 4.2 could be the intermediates in cross-coupling
reactions to give 5.1, 6.1 and 6.2, respectively, via a
reductive elimination (Scheme 3), we carried out differ-
ent experiments in several conditions (refluxing in ben-
zene, toluene, xylene, addition of PPh3) recovering in
all the cases the starting material. This unexpected sta-
bility in the complexes could be due to the higher trans
An appropriate monocrystal of complex 2.1 was used
to obtain the X-ray difractogram. An ORTEP diagram,
Fig. 1, shows the molecular geometry, the thermal ellip-
soids (35%) and the numbering scheme. Selected bond
distances and angles are listed in Table 3. In agreement
with the obtained structure for 2.1, the ligand 1.1 acts a
tridentate moiety (C, N, S), in the palladium complex,
where ortho carbon atom of one phenyl group, one
nitrogen atom and one sulfur atom are bonded to the
palladium atom to give an interesting six–five–six mem-
CH3
CH3
CH3
EtOH
Na2 [PdCl4]
EtOH
N
O
S
N
+
N
NH2
S
N
N
S
Reflux, 12h
S
Pd
Cl
S
R
R
S
R
R
R
R
1.1 R=CH3
1.2 R=-CH2-CH2-
2.1 R=CH3
2.2 R=-CH2-CH2-
Scheme 2.

Table 1
1H and 13C NMR data for complexes 2.1 and 2.2
H1
H10
H3
5.96 (1H,s) 2.16 (3H,s) 6.85
(2H,m)
6.87–7.05
H5
H8 H9 H10
H11
7.76
H13
H14
H15
7.35
2.1 2.46 (3H,s)
3.02 (3H,s)
6.95
7.23 (2H,t, J = 7.41) 7.50
(1H,td, J = 7.44, 1.35) (1H,dd, J = 7.41, 1.11)
(2H, d, J = 4.40) (1H,t, J = 7.68)
7.16–7.21 (3H,m)
2.2 3.61 3.98
(2H,t, J = 6.06) (2H,t, J = 6.06)
6.18 (1H,s) 2.15 (3H,s)
7.53
(1H,d, J = 7.98)
7.16–7.21 (3H,m)
C11
7.35
(2H,t, J = 7.68)
(3H, m)
C1
C10
C2
C3
C4
C5
C6
C7
C8
C9
C10
C12
C13
C14
C15
2.1
2.2
17.6
37.2
21.7
41.5
154.2
–
123.4
123.2
161.0
162.8
27.2
24.2
144.6
145.1
150.1
153.0
113.3
113.7
125.9
126.0
125.9
126.0
134.8
134.5
142.9
–
127.0
126.5
125.0
124.3
129.7
129.7
5
5
15
14
15
14
CH3
CH3
3
3
4
4
12
6
12
6
2
2
13
13
N
N
S
N
S
N
1
S
S
Pd
Cl
Pd
Cl
H3C
1
7
7
11
10
11
10
H3C
1'
1'
8
8
9
9
2.1
2.2

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F. Ortega-Jimenez et al. / Journal of Organometallic Chemistry 690 (2005) 454–462
457
influence of nitrogen and sulfur atoms over carbon
atoms.
2.2. Conclusion
New mononuclear orthopalladated complexes were
synthesized by using tridentate ligands containing car-
bon, nitrogen and sulfur. In some cases, their character-
izations were carried out by means of single-crystal
X-ray diffraction analyses. The reactivity of these ortho-
palladated complexes with terminal alkynes results in
unusual complexes with six membered rings different
to that reported in the literature, due to an interchange
between the halogen ligand and the alkyne. In these dis-
placement reactions, we propose that the trans influence
of the nitrogen and sulfur atoms over the carbon atoms
Fig. 1.
CH3
CH3
N
C-Li+
THF, 0˚C, N2
N
S
N
S
Pd
H3C
N
S
H3C
S
H3C
CH3
N
H3C
5.1
3.1
S
N
S
Pd
H3C
H3C
Cl
CH3
N
CH3
TMS
nBuLi
TMS
S
N
2.1
CH
N
N
S
Pd
S
H3C
THF, -78˚C, N2
H3C
S
H3C
H3C
TMS
6.1
4.1
C-Li+
Unresolved
Mixture
THF, 0˚C, N2
CH3
N
S
N
CH3
S
Pd
CH3
N
TMS
Cl
N
S
N
N
S
Pd
S
nBuLi
TMS
S
2.2
CH
THF, -78˚C, N2
TMS
6.2
4.2
Scheme 3.

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F. Ortega-Jimenez et al. / Journal of Organometallic Chemistry 690 (2005) 454–462
458
by reflux over sodium using benzophenone as indicator
and was freshly distilled under an argon atmosphere.
1
The H (300 MHz) y 13C (75 MHz) NMR spectra
were obtained from a JEOL ECLIPSE+300 spectrome-
ter, CDCl3 was used as solvent and TMS as internal ref-
erence (for 4.1 y 4.2 complexes TMS was not used).
The IR spectra were recorded from a FT-IR NICO-
LET MAGNA 750 spectrophotometer in solutions.
The mass spectra were obtained by using a JEOL-
AX505 spectrometer with IE and FAB+ techniques.
3.1. Ligands syntheses
The a-oxoketene dithioaketals were synthesized by
using the Larsson methodology previously described.
[21] The a-diphenylhydrazonoketene dithioaketals 1.1
and 1.2 were prepared according to literature methods
[22].
Fig. 2.
N0-(1-Methyl-3,30-bis-ethylsulfanylallylidene)-N,N-
diphenylhydrazone (1.1). C18H20N2S2, MW 328 g/mol;
yellow solid; m.p. 79 ꢁC; 60% yield. IR (CHCl3)
cmꢀ1: 1588 (C@N); 1488 (C = Car). MS (EI), m/z (%
ra): 328 [M+ (35)]; 221 [M+ ꢀ C3H7S2 (20)]; 168
[M+ ꢀ C6H10S2N (100)]; 77 [M+ ꢀ C12H15N2S2 (20)].
1H NMR (300 MHz, CDCl3) ppm: 1.83 (1H, s, H-5);
2.41 (6H, s, H-1, H-10); 6.02 (1H, s, H-3); 7.01 (2H,
gives very stable Pd–C r bonds and Csp-Csp2 coupling
does not occur.
3. Experimental
Reagents were obtained from commercial sources
and were used as received. Tetrahydrofuran was dried
Table 2
Crystal and structure refinement data for 2.1 and 3.1
2.1
3.1
Empirical formula
Formula weight
Temperature (K)
C18H19ClN2PdS2
469.32
C26H24N2PdS2 0.5 (H2O)
*
542.99
293(2)
0.71073
Triclinic
293(2)
0.71073
Triclinic
˚
Wavelength (A)
Crystal system
Space group
Unit cell dimension
ꢀ
ꢀ
P1
P1
˚
a (A)
8.878(1)
11.433(1)
8.908(1)
˚
b (A)
12.909(1)
12.977(2)
113.266(1)
93.341(1)
97.852(1)
˚
c (A)
19.433(2)
80.02(1)
a (ꢁ)
b(ꢁ)
79.58(1)
84.73(1)
1906.8(3)
c (ꢁ)
3
˚
3
˚
V (A )
1347.7(2) A
Z
4
1.635
2
1.338
Dcalc (mg/m3)
Absorption coefficient (mmꢀ1
F(000)
Crystal size/color/shape
)
1.334
944
0.860
552
0.40 · 0.26 · 0.18 mm3/orange/parallelepiped
1.96–25.00
0.396 · 0.168 · 0.132 mm/red/prism
1.72–25.00
Theta range for data collection (ꢁ)
Index ranges
Reflections collected
0 6 h 6 10, ꢀ13 6 k 6 13, ꢀ22 6 l 6 23
7195
6718 [0.0362]
ꢀ10 6 h 6 10, ꢀ15 6 k 6 15, ꢀ15 6 l 6 15
16085
4756 [0.0362]
Independent reflections [Rint
]
Completeness to theta = 25.00ꢁ
Absorption correction
99.8%
Analytical: face-indexed
0.8009 and 0.7085
Full-matrix least-squares on F2
6718/0/439
1.030
100.0 %
Analytical: face-indexed
0.9079 and 0.7806
Full-matrix least-squares on F2
4756/0/286
Maximum and minimum transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
1.010
R1 = 0.0679, wR2 = 0.2147
R1 = 0.0810, wR2 = 0.2262
Final R indices [I > 2r(I)]
R indices (all data)
R1 = 0.0438, wR2 = 0.0814
R1 = 0.0812, wR2 = 0.0944

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F. Ortega-Jimenez et al. / Journal of Organometallic Chemistry 690 (2005) 454–462
459
Table 3
was added and the mixture was stirred for 6 (2.1) or
12 h (2.2). After this time a colored solid precipiated.
It was filtered and then further purified by column chro-
matography over alumina using a hexane-CH2Cl2 sol-
vent mixture.
0
˚
Bond lengths (A) and angles (ꢁ) for Chloro-[N -(1-methyl-3,3-bis-
methylsulfanyl-allylidene)-N,N-diphenylhydrazine-C,N0,S]-palladium(II),
(2.1)
Bond lengths
Pd(1)–C(8)
Pd(1)–N(2)
Pd(1)–CI(1)
Pd(1)–S(1)
S(1)–C(3)
S(1)–C(6)
S(2)–C(3)
S(2)–C(5)
N(1)–C(7)
N(1)–N(2)
N(1)–C(13)
N(2)–C(1)
1.989(6)
2.004(4)
2.3113(17)
2.3620(17)
1.769(6)
1.812(7)
1.740(6)
1.781(6)
1.432(7)
1.438(6)
1.474(7)
1.311 (7)
Pd(2)–C(26)
Pd(2)–N(4)
Pd(2)–CI(2)
Pd(2)–S(3)
S(3)–C(21)
S(3)–C(24)
S(4)–C(21)
S(4)–C(23)
N(3)–N(4)
N(3)–C(25)
N(3)–C(31)
N(4)–C(19)
1.986(6)
2.005(4)
2.3096(18)
2.3416(17)
1.764(6)
1.819(7)
1.750(6)
1.786(7)
1.425(6)
1.432(7)
1.458(7)
1.315(7)
Chloro-[N0-(1-Methyl-3,3-bis-methylsulfanyl-allylid-
ene)-N,N-diphenylhydrazone-C,N0S]-palladium(II) 2.1.
C18H19ClN2PdS2; MW 469 g/mol; red solid; m.p. 174–
176 ꢁCdec; 80% yield. IR (CHCl3) cmꢀ1: 1585 (C@N);
1488 (C = Car). MS (FAB+), m/z (% ra): 470 [M+ + 1
(20)]; 168 [M+ ꢀ C6H10ClNPdS2 (25)]; 154 [M+ ꢀ
1
C6H10ClN2PdS2 (100)]. H NMR (300 MHz, CDCl3)
ppm: 2.16 (3H, s, H-5); 2.46 (3H, s, H-10); 3.02 (3H, s,
H-10); 5.96 (1H, s, H-3), 6.85 (2H, m, H-8, H-9); 6.95
(1H, td, J = 7.44, 1.35 Hz, H-10); 7.23 (2H, t, J = 7.41
Hz, H-13); 7.35 (1H, t, J = 7.68 Hz, H-15); 7.50 (2H,
d, H-14); 7.76 (1H, dd, J = 7.41, 1.11 Hz, H-11). 13C
NMR (75 MHz, CDCl3) ppm: 17.67 (C-1); 21.73 (C-
10); 27.18 (C-5); 113.35 (C-8); 123.45 (C-3); 125.06 (C-
14); 125.91 (C-9, C-10); 127.09 (C-13); 129.79 (C-15);
134.86 (C-11); 142.95 (C-12); 144.25 (C-6); 150.14 (C-
7); 154.20 (C-2); 161.01 (C-4).
Bond angles
C(8)–Pd(1)–N(2)
C(8)–Pd(1)–CI(1)
N(2)–Pd(1)–CI(1)
C(8)–Pd(1)–S(1)
N(2)–Pd(1)–S(1)
C(7)–N(1)–N(2)
C(7)–N(1)–C(13)
N(2)–N(1)–C(13)
C(1)–N(2)–N(1)
C(1)–N(2)–Pd(1)
N(1)–N(2)–Pd(1)
N(2)–C(1)–C(2)
N(2)–C(1)–C(4)
C(19)–N(4)–Pd(2)
81.7(2)
CI(1)–Pd(1)–S(1)
C(3)–S(1)–C(6)
87.56(6)
101.3(3)
107.0(2)
107.0(3)
105.1(3)
86.37(7)
108.1(2)
104.6(3)
103.4(3)
110.5(4)
113.0(4)
114.1(4)
114.7(5)
115.2(3)
94.99(19)
176.71(14)
176.96(18)
95.73(14)
109.9(4)
115.1(5)
112.8(5)
114.8(5)
130.1(4)
114.8(3)
124.3(5)
122.0(5)
129.8(4)
C(3)–S(1)–Pd(1)
C(6)–S(1)–Pd(1)
C(3)–S(2)–C(5)
Cl(2)–Pd(2)–S(3)
C(21)–S(3)–Pd(2)
C(24)–S(3)–Pd(2)
C(21)–S(4)–C(23)
N(4)–N(3)–C(25)
N(4)–N(3)–C(31)
C(25)–N(3)–C(31)
C(19)–N(4)–N(3)
N(3)–N(4)–Pd(2)
Chloro-{N0-[1-(1,3-dithiolan-2-yliden)]-N,N-diphenyl-
hydrazone-C,N0S}-palladium(II) 2.2. C18H17ClN2PdS2;
MW 467.34 g/mol; orange solid; m.p. 201 ꢁCdec; 40 %
yield. IR (CHCl3) cmꢀ1; 1585 (C@N); 1489 (C = Car).
MS (FAB+), m/z (% ra): 468 [M+ + 1(10)]; 391
[M+ ꢀ C12H12ClN2PdS2 (30)]; 326 [M+ ꢀ PdCl (10)];
1
168 [M+ ꢀ C6H8ClNPdS2 (55)]. H NMR (300 MHz,
CDCl3) ppm: 2.15 (3H, s, H-5); 3.61 (2H, t, J = 6.06
Hz, H-1); 3.98 (2H, t, 6.06 Hz, H-10); 6.18 (1H, s, H-
3); 6.87-7.02 (3H, m, H-8, H-9, H-10); 7.16-7.21 (3H,
m, H-13, H-15); 7.35 (2H, t, J = 7.68 Hz, H-14); 7.53
(1H, d, J = 7.98 Hz, H-11). 13C NMR (75 MHz, CDCl3)
ppm: 24. 20 (C-5); 37.15 ( C-1); 41. 57 (C-10); 113.71 (C-
8); 123.20 (C-3); 124.32 (C-14); 126.02 (C-9, C-10),
126.58 (C-13); 129.76 (C-15); 134.51 (C-11); 145.15 (C-
6); 153.06 (C-7); 162.84 (C-4).
td, J = 7.44, 1.38 Hz, H-9, H-90); 7.14 (4H, dd,
J = 7.41, 1.11 Hz, H-7, H-70); 7.27 (4H, td, J = 7.44,
1.38 Hz, H-8, H-80). 13C NMR (75 MHz, CDCl3)
ppm: 16.76 (C-1), 17.40 (C-10); 21.22 (C-5); 121.39
(C-3); 121.65 (C-7, C-70); 122.89 (C-9, C-90);
129.04(C-8, C-80); 144.17 (C-6); 148.37 (C-2); 162.46
(C-4).
N0-(2-[1,3]-dithiolan-2-ylidene-1-methylylidene)-N,N-
diphenylhydrazone (1.2). C18H13N2S2, MW 326 g/mol;
yellow solid; m.p. 152 ꢁC; 30% yield. IR (CHCl3)
cmꢀ1: 1588 (C@N); 1488 (C = Car). MS (EI), m/z (%
ra). 326 [M+ (60)]; 168 [M+ ꢀ C6H8NS2 (100)]; 77
3.3. Reactivity with alkynes
3.3.1. Synthesis of 3.1
1
[M+ ꢀ C12H13N2S2 (15)]. H NMR (300 MHz, CDCl3)
One equivalent of 2.1 in 10 mL of anhydrous THF
was dissolved under an atmosphere of N2 at 0 ꢁC, then
one equivalent of lithium phenylacetylenide (1 M) was
added. The mixture was stirred for 4 h. After this time,
the solvent was removed and the product was purified
by column chromatography over alumina by using a
Hexane-CH2Cl2 solvent mixture as eluent.
N0-(1-Methyl-3,3-bis-methylsulfanylallyliden)-N,N-
diphenylhydrazone-C, N0, S-(2-phenylethynyl) palla-
dium (II) 3.1. C26H24N2PdS2, MW 535.05 g/mol;
yellow solid; m.p. 114–116 ꢁCdes; yield 55%. IR
(CHCl3) cmꢀ1: 2108 (C„C); 1588 (C@N); 1484 (C =
Car). MS (FAB+), m/z (% ra):535 [M+ (25)]; 433
[M+ ꢀ C8H6 (15)]; 328 [M+ ꢀ C8H5Pd (10)]; 267
ppm: 1.74 (1H, s, H-5); 3.33 (4H, m, H-1, H-10); 6.16
(1H, s, H-3); 7.00 (2H, td, J = 7.00, 1.08 Hz, H-9, H-
90); 7.15 (4H, dd, J = 7.00, 1.08 Hz, H-7, H-70); 7.24
(4H, td, J = 7.00, 1.08 Hz, H-8, H-80). 13C NMR (75
MHz, CDCl3) ppm: 21.12 (C-5); 35.86 (C-1); 39.16
(C-10); 113.07 (C-3); 121.51 (C-7, C-70); 122.66 (C-9,
C-90); 128.97 (C-8, C-80); 148.57 (C-2); 165.09 (C-4).
3.2. Orthopalladacycles synthesis
In a typical procedure one equivalent of the a-
diphenylhydrazonoketene dithioaketal was dissolved in
10 mL of ethanol. Then, one equivalent of Na2[PdCl4]

Table 4
1H and 13C NMR data for complexes 3.1, 4.1 and 4.2
H8 H9 H10 H11
H13
H14
H15
H18
–
H19
H20
H21
3.1 6.87–6.91 (3H,
m)
8.11 (1H,d, J = 7.44) 7.14–7.25 (4H,m)
7.14–7.25 (4H,m)
7.32 (2H,t, J = 7.71)
7.14–7.25 (4H,m) 7.14–7.25 (4H,m) 7.32 (2H,t, J = 7.71)
4.1 6.83–6.89 (3H,
m)
8.04 (1H,d, J = 7.14) 7.27 (2H,t, J = 7.14) 7.35 (2H,d, J = 7.68) 7.12 (1H,t, J = 7.14) 0.16 (9H,s)
7.88 (1H,d, J = 8.52) 7.10–7.28 (3H,m) 7.41–7.53 (2H,m) 7.10–7.28 (3H,m) 0.17 (9H, s)
–
–
–
–
–
4.2 6.84–7.03 (3H,
m)
–7
C6
C70
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
3.1
4.1
4.2
143.0
143.2
–
150.7
150.7
150.3
113.9
113.8
114.3
123.4
125.1
125.3
125.3
125.1
125.3
138.9
138.9
138.6
141.9
141.9
–
126.1
129.5
–
126.9
126.0
124.1
125.5
129.5
129.4
106.5
111.3
–
107.7
111.3
–
–
127.4
131.4
129.6
1.33
1.44
–
–
–
–
–
–
15
15
5
CH3
15
14
5
CH3
5
CH3
14
14
3
3
3
4
4
4
12
12
12
13
13
13
N
N
N
S
2
N
S
N
S
2
N
2
1
6
S
S
6
Pd
16
Pd
16
S
6
Pd
H3C
1
H3C
1
7
7
7
11
10
11
10
11
10
H3C
H3C
16
17
1'
1'
1'
8
8
8
17
17
19
18
TMS
9
9
9
18
20
18
TMS
4.1
3.1
4.2
21

´
F. Ortega-Jimenez et al. / Journal of Organometallic Chemistry 690 (2005) 454–462
461
Table 5
CDCl3) ppm: 0.16 (9H, s, H-18); 2.04 (3H, s, H-5);
2.42 (3H, s, H-1); 3.09 (3H, s, H-10); 5.97 (1H, s, H-3);
6.83-6.89 (3H, m, H-8, H-9, H-10); 7.12 (1H, t,
J = 7.14 Hz, H-15); 7.27 (2H, t, J = 7.14 Hz, H-13);
7.35 (2H, d, J = 7.68 Hz, H-14); 8.04 (1H, d, J = 7.14
Hz, H-11). 13C NMR (75 MHz, CDCl3) ppm: 1.33 (C-
18); 17.71 (C-1); 23.24 (C-10); 26.70 (C-5); 111.33 (C-
16, C-17); 113.88 (C-8); 124.78 (C-3); 125.18 (C-9,
C-10); 126.08 (C-14); 129.55 (C-13, C-15); 138.95 (C-
11); 141.91 (C-12); 143.21 (C-6); 150.72 (C-7); 155.19
(C-2); 158.95 (C-4).
0
˚
Bond lengths (A) and angles (ꢁ) for (N -(1-methyl-3,3-bis-methylsulfa-
nyl-allylidene)-N,N-diphenylhydrazine-C,N0,S)-(2-phenylethynyl)pal-
ladium(II) (3.1)
Bond lengths
S(2)–C(5)
1.946(7) S(2)–C(3)
1.991(6) S(2B)–C(3)
2.036(5) S(2B)–C(5B)
2.315(5) N(1)–N(2)
2.377(3) N(I)–C(8)
1.733(7) N(1)–C(13)
1.765(8) N(2)–C(1)
1.758(15)
1.792(8)
1.862(9)
1.88(3)
Pd(1)–C(25)
Pd(1)–C(7)
Pd(1)–N(2)
Pd(1)–S(2B)
Pd(1)–S(2)
S(1)–C(3)
1.420(7)
1.446(8)
1.460(8)
1.310(8)
S(1)–C(6)
N0-[1-(1,3-dithiolan-2-ilyden)]-N,N-diphenyl-hydra-
zone-C,N0,S-(2-tetramethylsilyletynyl) palladium (II)
4.2. C23H26N2PdS2Si, MW 529.12 g/mol, brown solid,
m.p. 170 ꢁCdec, yield 55%. IR (CHCl3) cmꢀ1: 2041
(C„C); 1588 (C@N); 1489 (C = Car); 856 (Si(CH3)3).
MS (FAB+) m/z (% ra); 529[M+ (2)]; 326[M+ ꢀ C5H8PdSi
(20)]; 221[M+ ꢀ C8H13PdS2Si (60)]; 168[M+ ꢀ C21H12-
PdS2Si(75)]; 73[M+ ꢀ C20H18N2PdS2 (100)]. 1H NMR
(300 MHz, CDCl3) ppm: 0.17 (9H, s, H-18); 2.08 (3H, s,
H-5); 3.61 (2H, t, H-1); 4.02 (2H, t, H-10); 6.17 (1H, s,
H-3); 6.84-7.03 (3H, m, H-8, H-9, H-10); 7.10-7.28 (3H,
m, H-13, H-15); 7.41-7.53 (2H, m, H-14); 7.88 (1H, d,
J = 8.52 Hz, H-11). 13C NMR (75 MHz, CDCl3) ppm:
1.44 (C-18); 24.18 (C-5); 36.2 (C-1); 42.64 (C-10); 112.58
(C-16), 113.07 (C-17), 114.38 (C-8); 116.20 (C-3); 121.53
(C-15); 124.23 (C-14); 125.35 (C-9, C-10); 129.45 ( C-
13); 138.48 (C-11); 146.14 (C-12);147.85 (C6); 150. 33
(C-7); 154.06 (C-2); 163.24 (C-4).
Bond angles
C(25)–Pd(1)–C(7)
C(25)–Pd(1)–N(2)
C(7)–Pd(1)–N(2)
C(25)–Pd(I)–S(2B)
C(7)–Pd(1)–S(2B)
N(2)–Pd(1)–S(2B)
C(25)– Pd(1)–S(2)
C(7)– Pd(1)–S(2)
N(2)–Pd(1)–S(2)
C(3)–S(1)–C(6)
94.8(3)
176.3(2)
81.7(2)
C(5)–S(2)–C(3)
104.4(8)
C(5)–S(2)–Pd(1)
C(3)–S(2)–Pd(1)
C(3)–S(2B)–C(5B)
C(3)– S(2B)–Pd(1)
112.9(6)
104.8(3)
93.1(11)
104.9(3)
84.5(3)
166.7(2)
98.59(19) C(5B)–S(2B)–Pd(1) 103.7(12)
92.6(2)
N(2)–N(1)–C(8)
110.8(5)
113.9(5)
113.5(5)
115.8(5)
123.7(6)
121.5(6)
165.91(19) N(2)–N(1)–C(13)
91.13(16) C(8)–N(1)–C(13)
105.7(4)
129.6(4)
114.1(4)
C(1)–N(2)–N(1)
N(2)–C(1)–C(2)
N(2)–C(1)–C(4)
C(1)–N(2)–Pd(1)
N(1)–N(2)–Pd(1)
[M+ ꢀ C10H12PdS (35)]; 167 [M+ ꢀ C12H9N (55)]. H
NMR (300 MHz, CDCl3) ppm: 2.09 (3H, s, H-5);
2.45 (3H, s, H-1); 3.14 (3H, s, H-10); 6.03 (1H, s, H-
3); 6.87–6.91 (3H, m, H-8, H-9, H-10); 7.14–7.25
(4H, m, H-13, H-19); 7.32(2H, t, J = 7.71 Hz, H-15,
H-21); 7.42–7.49 (4H, m, H-14, H-20); 8.11 (1H, d,
J = 7.44 Hz, H-11). 13C NMR (75 MHz, CDCl3)
ppm: 17.74 (C-1); 23.56 (C-10); 26.86 (C-5);
106.50(C-16); 107.77 (C-17); 113.96 (C-8); 123.45 (C-
9); 124.92 (C-3); 125.35 (C-10), 125.56 (C-15); 126.14
(C-13); 126.93 (C-14); 127.47 (C-19), 129.64 (C-21);
131.45 (C-20), 138.93 (C-11); 141.91 (C-12); 143.06
(C-6); 150.74 (C-7); 155.36 (C-2); 158.95 (C-4).
1
3.4. X-ray crystal structure determination of compounds
2.1 and 3.1
Data collection and refinement parameters are sum-
marized in Table 2. The diffraction data for 2.1 was col-
lected on a Siemens P4/Pc diffractometer, while the data
for 3.1 was collected on a Bruker Smart Apex CCD dif-
˚
fractometer with Mo Ka radiation, k = 0.71069 A. Each
3.3.2. Synthesis of 4.1 and 4.2
data set was corrected for Lorentz and polarization ef-
fects. An empirical absorption corrections based on
psi-scans were applied for the structure of 2.1. The struc-
tures were solved by direct methods[23] and each struc-
ture was refined by full-matrix least-squares on F2 using
all data with all non-hydrogen atoms assigned aniso-
tropic displacement parameters. The hydrogen atoms
bound to carbon atoms were inserted at calculated posi-
tions with an isotropic temperature factor 1.2 times the
Uiso of the parent carbon atom. The program used in the
final refinements was SHELXL 97 [24].
One equivalent of TMSC„CH in 10 mL of dry THF
was dissolved under an atmosphere of N2 at ꢀ78 ꢁC,
then one equivalent of n-BuLi (1.3 M) was added. The
mixture was allowed to warm to room temperature
and then was transferred by cannula to a solution of
2.1 or 2.2 in 5 mL of dry THF at 0 ꢁC. The mixture
was stirred for 5 h at room temperature. The solvent
was removed and the product was obtained as a solid.
N0-(1-Methyl-3,3-bis-methylsufanyl-allilyden)-N,N-
diphenylhydrazine-C,N0, S-(2-tetramethylsilylethynyl) pal-
ladium (II) 4.1. C23H28N2PdS2Si, MW 531.13 g/mol,
green solid, m.p. 113–115 ꢁCdec, yield 45%. IR (CHCl3)
cmꢀ1; 2042 (C„C); 1588 (C@N); 1488 (C = Car); 857
(Si(CH3)3). MS (FAB+) m/z (% ra); 433 [M+ ꢀ C5H10Si
(10)]; 387 [M+ ꢀ C9H8N2 (8)]; 221 [M+ ꢀ C8H16PdSi
3.5. Supplementary data
Crystallographic data for the structural analysis has
been deposited with the Cambridge Crystallographic
Centre CCDC No.247998 for complex 2.1, No. 247999
for complex 3.1. Copies of this information may be
(50)];
167
[M+ ꢀ C11H20PdS2Si
(75)];
73
[M+ ꢀ C20H19N2PdS2 (100)]. 1H NMR (300 MHz,

´
F. Ortega-Jimenez et al. / Journal of Organometallic Chemistry 690 (2005) 454–462
462
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[9] (a) J.M. Vila, T. Pereira, J.M. Ortigueira, M. Lopez-Torres, A.
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Road, Cambridge, CB2 IEZ, UK (fax: +44 1223
336033; e-mail: deposit@ccdc.cam.ac.ukor www:
http://www.cdcc.cam.ac.uk).
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Acknowledgement
´
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[10] (a) F. Ortega-Jimenez, E. Gomez, P. Sharma, M.C. Ortega-
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We thank DGAPA for financial support (Project #
IN202404) and CIMAT. The technical assistance of
´
Rocio Patin˜o, Luis Velasco and Javier Perez is gratefully
acknowledged.
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