New thiocarbamate and thioureate palladium and platinum complexes: Synthesis and use as metalloligands. Unprecedented coordination of the thioureate ligand in [(C6F5) 2Pd{μ2,η2-SC(NMe2)NPh} Pd(C6F5)(bpzm)]

Article abstract of DOI:10.1016/j.ica.2004.01.010

The di-μ-hydroxo complexes [NBu₄]₂[{(C ₆F₅)₂M(μ-OH)}₂] (M=Pd, Pt) react with PhNCS in alcohol ROH solution to yield the N,S-chelating thiocarbamate metal complexes [NBu₄][(C₆F₅) ₂M{η²-SC(OR)NPh}] (R=Me, Et or Prⁿ). [NBu₄]₂[{(C₆F₅)₂Pd(μ- OH)}₂] also reacts with PhNCS in the presence of dialkylamines R ₂NH to yield the N,S-chelating thioureate (1-) palladium complexes [NBu₄][(C₆F₅)₂Pd{η²- SC(NR₂)NPh}] (R=Me or Et). [NBu₄][(C₆F ₅)₂M{η²-SC(X)NPh}] (M=Pd or Pt; X=OMe or NR₂) reacts with [(C₆F₅)Pd(bpzm)(acetone)] ClO₄ to yield the dinuclear complexes [(C₆F ₅)₂M{(μ₂,η²-{SC(X)NPh} Pd(C₆F₅)(bpzm)] (M=Pd or Pt, X=OMe or NR₂; bpzm=bis(3,5-dimethylpyrazol-1-yl)methane). The single-crystal structures of [NBu₄][(C₆F₅)₂Pd{η²- SC(OMe)NPh}] and [(C₆F₅)₂Pd{μ₂, η²-SC(NMe₂)NPh}Pd(C₆F₅)(bpzm)] have been established by X-ray diffraction.

Full text of DOI:10.1016/j.ica.2004.01.010

Inorganica Chimica Acta 357 (2004) 2331–2338
www.elsevier.com/locate/ica
New thiocarbamate and thioureate palladium and
platinum complexes: synthesis and use as
metalloligands. Unprecedented coordination of the thioureate
ligand in [(C6F5)2Pd{l2,g2-SC(NMe2)NPh}Pd(C6F5)(bpzm)]
a,
Jose Ruiz , Venancio Rodrıguez , Concepcion de Haro , Jose Perez ,
a
a
b
*
ꢀ
ꢀ
Gregorio Lopez
ꢀ
ꢀ ꢀ
a
ꢀ
a
Departamento de Quꢀımica Inorgꢀanica, Universidad de Murcia, Campus de Espinardo, 30071 Murcia, Spain
b
ꢀ
Departamento de Ingenierꢀıa Minera, Geolꢀogica y Cartogrꢀafica (Area de Quꢀımica Inorgꢀanica), Universidad Politꢀecnica de Cartagena,
30203 Cartagena, Spain
Received 11 December 2003; accepted 18 January 2004
Available online 8 February 2004
Abstract
The di-l-hydroxo complexes [NBu4]2[{(C6F5)2M(l-OH)}2] (M ¼ Pd, Pt) react with PhNCS in alcohol ROH solution to yield the
N,S-chelating thiocarbamate metal complexes [NBu4][(C6F5)2M{g2-SC(OR)NPh}] (R ¼ Me, Et or Prn). [NBu4]2[{(C6F5)2Pd(l-
OH)}2] also reacts with PhNCS in the presence of dialkylamines R2NH to yield the N,S-chelating thioureate (1)) palladium
complexes [NBu4][(C6F5)2Pd{g2-SC(NR2)NPh}] (R ¼ Me or Et). [NBu4][(C6F5)2M{g2-SC(X)NPh}] (M ¼ Pd or Pt; X ¼ OMe or
NR2) reacts with [(C6F5)Pd(bpzm)(acetone)]ClO4 to yield the dinuclear complexes [(C6F5)2M{(l2,g2-{SC(X)NPh}Pd(C6F5)(bpzm)]
(M ¼ Pd or Pt, X ¼ OMe or NR2; bpzm ¼ bis(3,5-dimethylpyrazol-1-yl)methane). The single-crystal structures of [NBu4]-
[(C6F5)2Pd{g2-SC(OMe)NPh}] and [(C6F5)2Pd{l2,g2-SC(NMe2)NPh}Pd(C6F5)(bpzm)] have been established by X-ray
diffraction.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Palladium; Platinum; Thioureate; Thiocarbamate; Phenylisothiocyanate
1. Introduction
are formed to give the corresponding dithiocarbamate
complexes [(C6F5)2M(S2CNR2)]ꢀ (M ¼ Pd, Pt) [2].
Platinum–thiourea complexes have attracted interest
for their biological activity [3,4]. Metal cluster complexes
with coordinated thiourea monoanions are also well
known [5–7]. However, there are relatively few examples
of metal complexes of simple alkyl- or aryl-substituted
thiourea monoanions, containing N,S-chelated ligands.
For palladium and platinum, the thiourea monoanion
complexes [Pd{SC(NHtol)NTol}2(dppm)], [Pd2(l-S)(l-
dppm){SC(NHTol)NTol}2] [8] and [Pt{SC- (NHEt)-
NEt}(PPh3)2]OTs (OTs ¼ p-toluenesulfonate) [9] have
been described. The azo dye-derived complex [Pt{SC-
(N(CH2CH2)2O)NNC6H4N@NC6H4NMe2}(PPh3)2]B-
Ph4 and trans-[Pt{SC(NHMe)NCN}2(PPh3)2] have also
been recently reported [10]. On the other hand, the
The chemistry of heterocumulenes such as CS2,
PhNCO and PhNCS with transition-metal complexes is
still of current interest. We have recently reported the
preparation of carbamato, thiocarbamate and thioure-
ate complexes of palladium(II) of the type [(C6F5)Pd(N–
N)X] (X ¼ PhNCO2R, PhNCSOR, PhNCSNR2) by
insertion of PhNCO or PhNCS into Pd–OR or Pd–NR2
bonds under appropriate conditions (Scheme 1) [1]. We
have also reported that in the reaction of [(C6F5)4M2(l-
OH)2]2ꢀ with amines in the presence of CS2, C–N bonds
* Corresponding author. Tel.: +34-968-36-74-55; fax: (internat.) +34-
968-36-41-48.
E-mail address: jruiz@um.es (J. Ruiz).
0020-1693/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.01.010

2332
J. Ruiz et al. / Inorganica Chimica Acta 357 (2004) 2331–2338
N
_
2
H
O
N
Pd OH
C6F5
C6F5
C6F5
C6F5
M
M
PhNCS/ROH
PhNCO/
ROH
C6F5
PhNCS/Et2NH
O
H
N
N
N
N
Pd SC(=NPh)OR
C6F5
N
Pd SC(=NPh)NEt2}
C6F5
N
Pd N(Ph)C(=O)OR
C6F5
PhNCS/ROH
Scheme 1.
phenyl-O-alkylthiocarbamate palladium complexes
[Pd{SC(OR)NPh}2] (R ¼ Me, Ph) [11,12] and
[Pd{SC(OMe)NPh}2(PPh3)] [13] have been prepared
from the corresponding thiocarbamic esters.
_
C6F5
C6F5
S
The present work concerns the reactivity of the di-
meric hydroxo complexes of palladium and platinum
[NBu4]2[{(C6F5)2M(l-OH)}2] towards the heterocumu-
lene phenylisothiocyanate PhNCS in the presence of
alcohols or amines to yield the N,S-chelated thiocarba-
mate or thioureate metal complexes [NBu4][(C6F5)2-
M{g2-SC(X)NPh}] (X ¼ OR or NR2), and their use as
metalloligands. We report herein the first crystal struc-
ture of a chelating thiocarbamate complex (3D Search
using the Cambridge Structural Database, CSD version
5.24, July 2003 release) and unprecedented l2,g2-coor-
dination mode of the thioureate ligand.
M
C OR
2
N
Ph
M = Pd; R = Me (1), Et (2), nPr (3)
M = Pt; R = Me (4), Et (5)
Scheme 2.
characteristic of the cis-M(C6F5)2 fragment [16,17] and
1
behaves like a m(M–C) band [18]. The H NMR spectra
of complexes 1–5 show the characteristic resonances of
the N-phenyl-O-alkylthiocarbamate group. The obser-
vation of three or two signals for the aromatic protons
of the PhN groups indicates that rotation of the aryl
group about the C–N bond is rapid on the NMR time
scale. The 19F NMR spectra of complexes 1–5 show the
presence of two nonequivalent freely rotating C6F5
groups, one trans to S and one trans to NPh, with two
2:2 resonances in the o-and m-fluorine regions, and two
1:1 resonances in the p-fluorine region. As expected, the
o-fluorine signals of complexes 4 and 5 are flanked by
the satellites due to the coupling to 195Pt.
The reaction of [NBu4]2[{(C6F5)2M(l-OH)}2]
(M ¼ Pd, Pt) with alcohols ROH should give the corre-
sponding alkoxo complex [NBu4]2[{(C6F5)2M(l-OR)}2]
followed by insertion of PhNCS into the M–OR bond. In
fact, the synthesis of the methoxo platinum complex
[NBu4]2[{(C6F5)2Pt(l-OMe)}2] [19] and the related aryl-
oxo complexes [NBu4]2[{(C6F5)2M(l-OAr)}2] (M ¼ Pd,
Pt) [20] have been previously reported. External attack by
ORꢀ of the coordinated heterocumulene is an alternative
pathway to the formation of 1–5. The reaction of the
hydroxo-nickel complex [NBu4]2[{(C6F5)2Ni(l-OH)}2]
with alcohols in the presence of carbon disulfide to lead to
the formation of the corresponding xanthate nickel
complexes [NBu4][(C6F5)2Ni(S2C–OR)] has also been
described [21].
2. Results and discussion
2.1. Monomeric thiocarbamate complexes 1–5
The di-l-hydroxo complexes [NBu4]2[{(C6F5)2M(l-
OH)}2] (M ¼ Pd, Pt) react with PhNCS in alcohol ROH
solution to yield the N-phenyl-O-alkylthiocarbamate
metal complexes [NBu4][(C6F5)2M{SC(OR)NPh}] (1)–
(5) shown in Scheme 2. The complexes are air-stable,
both in the solid state and in solution. The new com-
plexes have been characterized by partial elemental
1
analyses and spectroscopic (IR and H and 19F NMR)
methods. In acetone solution, these complexes behave as
1:1 electrolytes [14]. The presence of the thiocarbamate
ligand is supported by the IR spectra, which show a
band at ca. 1530 cmꢀ1 assignable to m(C@N), a lower
value than that observed in [(N–N)Pd(C6F5){SC-
(@NPh)OR}] (m(C@N) at ca. 1580 cmꢀ1) where the
thiocarbamate ligand is coordinated to the metal only
through the S atom [1]. The IR spectra of complexes 1–5
show also the characteristic absorptions of the C6F5
group [15] at 1630, 1490, 1450, 1050, 950 cmꢀ1 and a
split band at ca. 800 cmꢀ1, derived from the so-called X-
sensitive mode in C6F5–halogen molecules, which is

J. Ruiz et al. / Inorganica Chimica Acta 357 (2004) 2331–2338
2333
Fig. 1 shows the X-ray structure of complex 1, with
selected bond lengths and angles listed in Table 1. The
metal is coordinated in a distorted square-planar ar-
rangement. The thiocarbamate is bonded in N,S-che-
lating mode. The main distortion is the S(1)–Pd–N(1)
bite angle, which is 69.18(5)°. This is due to the geo-
metrical constraint set by the ligand. The angle between
the two C6F5 rings is 86.53(8)°. The four-membered
metallacycle N(1)–Pd(1)–S(1)–C(19) is essentially planar
(with no atom deviating from the least-square plane by
around the C(19) atom (124–115°) and the total of the
surrounding three bond angles (360.0°) clearly confirm
also the sp2 hybridization of the C(19) atom. The Pd–S
ꢁ
bond distance (2.3824(6) A) is similar to those found
in [(C6F5)Pd(SC6H5)(o-Ph2PC6H4CHNiPr)] (2.357(2)
n
ꢁ
A) [24] and [(CH2CH2CH2CH2NCS2)Pd(PEt3)( Pr)]
ꢁ
(2.384(2) and 2.406(1) A) [25], and a little longer to that
found in [(C6F5)Pd(N–N){SC(OMe)NPh}] (2.3099(10)
ꢁ
ꢁ
A) [1]. The Pd–C6F5 distances (2.005(2) and 2.019(2) A)
are in the range found in the literature [1,27].
ꢁ
more than 0.005(1) A, for C(19)). The Pd–N(1) bond
ꢁ
distance value (2.1081(18) A) lies within the range re-
2.2. Monomeric thioureate complexes 6 and 7
ported in complexes containing the {(C6F5)2PdN2}
moiety such as [(C6F5)2Pd(pzꢁ ꢁ ꢁHꢁ ꢁ ꢁpz)] (pz ¼ pyrazo-
We have also investigated the reaction of
[NBu4]2[{Pd(C6F5)2(l-OH)}2] with PhNCS in the pres-
ence of dialkylamines R2NH to yield the thioureido (1))
palladium complexes [NBu4][(C6F5)2Pd{SC(NR2)-
NPh}] (6) and (7) shown in Scheme 3. The IR spectra of
complexes 6 and 7 exhibit a strong absorption at 1555–
1535 cmꢀ1, which are in the range found for the thio-
ureido-complexes [(C6F5)Pd(N–N){SC(NR2)NPh}] [1]
and [(C5Me5)RhCl{PhNC[N(C6H4Me-p)CH@NC6H4-
Me-p]S}] [26] and are dependent on the double-bond
2
ꢀ
ꢁ
late) (2.103(5) A) [16] and [(C6F5)2Pd(g -PhNNNPh)]
ꢁ
(2.095(4), 2.117(4) A) [22]. The C(19)–O(1) bond dis-
ꢁ
tance (1.342(3) A) is similar to that found in
[Pd{SC(OMe)NPh}2(PPh3)] [13]. The N(1)–C(19) bond
ꢁ
length (1.300(3) A) and the C(19)–N(1)–C(13) angle
(126.12(19)°) indicate that N(1) is sp2-hybridized and a
high N–C double bond character [23]. Bond angles
1
character of the C–N. The H NMR spectra show the
resonance signals of the R2N and PhN groups. The 19F
NMR spectra of 6 and 7 reveal the presence of two
different types of C6F5 groups.
The reaction of [NBu4]2[{(C6F5)2M(l-OH)}2] (M ¼
Pd, Pt) with amines R2NH should give the amide
complex [NBu4]2[{(C6F5)2M(l-NR2)}2] [27] followed
by insertion of PhNCS into the M–NR2 bond. The
_
2
H
C6F5
C6F5
O
C6F5
C6F5
Pd
Pd
O
H
Fig. 1. An ORTEP drawing of the [(C6F5)2Pd{SC(OMe)NPh}]ꢀ
anion.
PhNCS/R2NH in THF
Table 1
ꢁ
Selected bond lengths (A) and angles (°) for complex 1
Bond lengths
Bond angles
Pd(1)–C(1)
Pd(1)–C(7)
Pd(1)–N(1)
Pd(1)–S(1)
N(1)–C(19)
S(1)–C(19)
O(1)–C(19)
2.005(2)
2.019(2)
2.1081(18)
2.3824(6)
1.300(3)
1.721(2)
1.342(3)
C(1)–Pd(1)–C(7)
C(1)–Pd(1)N(1)
C(7)–Pd(1)–N(1)
C(1)–Pd(1)–S(1)
C(7)–Pd(1)–S(1)
N(1)–Pd(1)–S(1)
O(1)–C(19)–N(1)
O–C(19)–S(1)
86.53(8)
170.78(8)
102.65(8)
101.65(6)
171.75(6)
69.18(5)
_
C6F5
S
N
Pd
C NR2
2
C6F5
Ph
121.1(2)
123.83(17)
115.08(17)
126.12(19)
R = Me (6), Et (7)
N(1)–C(19)–S(1)
C(19)–N(1)–C(13)
Scheme 3.

2334
J. Ruiz et al. / Inorganica Chimica Acta 357 (2004) 2331–2338
synthesis of the thioureido complex [(C5Me5)RhCl-
{PhNC[N(C6H4Me-p)CH@NC6H4Me-p]S}], arising
from the insertion of PhNCS into the Rh–N bond, has
been reported [26]. External attack by NRꢀ2 of the co-
ordinated heterocumulene is an alternative pathway to
the formation of 6 and 7.
methylene protons are magnetically nonequivalent and
give the NMR pattern corresponding to two diastereo-
topic protons: two doublets at d 7.7 and 6.0 with
1
2JHAHB ¼ 15 Hz. The H NMR spectrum of complex 9
shows two broad signals for the NMe2 of the thioureate
ligand (at d 3.13 and 1.97) that sharpen at )10 °C. The
19F NMR spectra of complexes 8–10 at room tempera-
ture show hindered rotation of the C6F5 ring around the
M–C bond. As expected, the o-fluorine signals of the
pentafluorophenyl groups bound to Pt in complex 10 are
flanked by the satellites due to the coupling to 195Pt.
Fig. 2 shows the X-ray structure of complex 9, with
selected bond lengths and angles listed in Table 2. The
crystal structure of compound 9 shows two independent
molecules in the asymmetric unit with the palladium
atoms in slightly distorted square-planar geometries.
The main distortion for Pd(2) is the S(1)–Pd(2)–N(6)
bite angle, which is 68.45(12)°. This is due to the geo-
metrical constraint set by the ligand. The angle between
the two C6F5 rings is 88.02(18)°. The four-membered
metallacycle N(6)–Pd(2)–S(1)–C(18) is essentially planar
(with no atom deviating from the least-square plane by
2.3. Binuclear thiocarbamate and thioureate complexes
8–10
The reaction of [(C6F5)Pd(bpzm)(acetone)]ClO4
(bpzm ¼ bis(3,5-dimethylpyrazol-1-yl)methane with the
corresponding monomeric thiocarbamate or thioureate
complex [NBu4][(C6F5)2M{g2-SC(X)NPh}] (M ¼ Pd or
Pt, X ¼ OMe or NR2) in a 1:1 molar ratio yields the
asymmetric dinuclear complexes 8–10 (Scheme 4). The
new complexes have been characterized on the basis of
partial elemental analyses and spectroscopic data. Two
1
sets of H resonances are observed for the C3HMe2N2
rings corresponding to one pyrazolate ligand trans to the
S-bound thiocarbamate or thioureate metalloligand and
one pyrazolate ligand trans to C6F5; the lower field set is
assigned to the pyrazolate ligand trans to C6F5. The
proton resonances of the bridging methylene of the
bis(pyrazol-1-yl)methane ligand in complexes 8–10 show
that the boat-to-boat inversion usually observed in this
type of complexes [1] is frozen at room temperature; the
ꢁ
more than 0.048(3) A, for C(18)). The Pd(2)–N(6) bond
ꢁ
distance value (2.073(4) A) is a bit shorter than that
found in complex 1. Examination of the S–C and C–N
bond lengths of 9 strongly suggests considerable elec-
tronic delocalization in the thioureato ligand [6,9]. The
ꢁ
Pd(2)–S(1) bond distance (2.4198(11) A) is longer
than that observed in complex 1. The distance Pd(1)–
ꢁ
S(1) is 2.3041(11) A and the angle Pd(1)–S(1)–Pd(2)
+
Me
Pd
Me
C
ꢁ
is 96.30(4)°. The distance Pd(1)ꢁ ꢁ ꢁPd(2) is 3.520 A.
_
C6F5
solv
H
H
C6F5
C6F5
S
N
N
N
N
The bite angle N(1)–Pd(1)N(4) (85.21(16)°) is a bit
higher than that observed in [(C6F5)2Pd(bpz*mFec)]
[bpz*mFec ¼ bis(3,5-dimethylpyrazol-1-yl)ferrocenylme-
M
C X
+
N
Ph
Me
Me
solv = acetone
H
H
5'
3'
5
Me
Me
C
N
N
N
4'
4
N
S
3
Me
Me
Pd
C6F5
C6F5
C6F5
M
C
X
N
Ph
M = Pd; X = OMe (8), NMe2 (9)
M = Pt; X = OMe (10)
Fig. 2. An ORTEP drawing of [(C6F5)2Pd{l2,g2-SC(NMe2)-
NPh}Pd(C6F5)(bpzm)].
Scheme 4.

J. Ruiz et al. / Inorganica Chimica Acta 357 (2004) 2331–2338
2335
spectra of the ionic compounds, the signals of the NBu4þ
cation have been omitted. Infrared spectra were re-
corded on a Perkin-Elmer 1430 spectrophotometer using
Nujol mulls between polyethylene sheets.
The starting complexes [NBu4]2[{(C6F5)2M(l-OH)}2]
(M ¼ Pd [29], Pt [30]) and [(C6F5)Pd(N–N)(ace-
tone)]ClO4 [1] were prepared by procedures described
elsewhere. The commercially available chemicals were
purchased from Aldrich Chemical Co. and were used
without further purification. Solvents were dried by the
usual methods.
Table 2
Selected bond lengths (A) and angles (°) for complex 9
ꢁ
Bond lengths
Bond angles
Molecule 1
Pd(1)–C(1)
Pd(1)–N(1)
Pd(1)–N(4)
Pd(1)–S(1)
Pd(2)–C(33)
Pd(2)–C(27)
Pd(2)–N(6)
Pd(2)–S(1)
Pd(1)ꢁ ꢁ ꢁPd(2)
S(1)–C(18)
N(6)–C(18)
N(5)–C(18)
1.987(6)
2.080(4)
2.089(5)
2.3041(11)
1.992(5)
2.013(5)
2.073(4)
2.4198(11)
3.520
C(1)–Pd(1)–N(1)
C(1)–Pd(1)–N(4)
N(1)–Pd(1)–N(4)
C(1)–Pd(1)–S(1)
N(1)–Pd(1)–S(1)
N(4)–Pd(1)–S(1)
C(33)–Pd(2)–C(27)
C(33)–Pd(2)–N(6)
C(27)–Pd(2)–N(6)
C(33)–Pd(2)–S(1)
C(27)–Pd(2)–S(1)
N(6)–Pd(2)–S(1)
Pd(1)–S(1)–Pd(2)
N(6)–C(18)–N(5)
N(6)–C(18)–S(1)
N(5)–C(18)–S(1)
87.82(19)
172.9(2)
85.21(16)
94.43(16)
172.78(11)
92.34(12)
88.02(18)
95.68(17)
174.3(2)
Safety note: Perchlorate salts of metal complexes with
organic ligands are potentially explosive. Only small
amounts of material should be prepared and these
should be handled with great caution.
1.814(4)
1.282(6)
1.329(6)
163.78(12)
107.55(14)
68.45(12)
96.30(4)
129.9(4)
109.3(3)
120.8(3)
3.2. Preparation of [NBu4][(C6F5)2Pd{SC(OR)NPh}]
[R ¼ Me (1), Et (2), Prn (3)]
Molecule 2
Pd(3)–C(39)
Pd(3)–N(7)
Pd(3)–N(10)
Pd(3)–S(2)
1.987(6)
2.080(4)
2.090(5)
2.3024(11)
1.998(4)
2.021(5)
2.068(4)
2.4192(11)
3.519
C(39)–Pd(3)–N(7)
C(39)–Pd(3)–N(10)
N(7)–Pd(3)–N(10)
C(39)–Pd(3)–S(2)
N(7)–Pd(3)–S(2)
N(10)–Pd(3)–S(2)
C(71)–Pd(4)–C(65)
C(71)–Pd(4)–N(12)
C(65)–Pd(4)–N(12)
C(71)–Pd(4)–S(2)
C(65)–Pd(4)–S(2)
N(12)–Pd(4)–S(2)
Pd(3)S(2)–Pd(4)
87.96(19)
172.8(2)
To a solution of [NBu4]2[{Pd(C6F5)2(l-OH)}2] (100
mg, 0.071 mmol) in the corresponding alcohol (8 cm3)
was added phenylisothiocyanate PhNCS (17.1 ll, 0.143
mmol). The solution was stirred at room temperature
for 8 h. Then, the solvent was partially evaporated under
reduced pressure. Addition of water caused the precip-
itation of a solid, which was filtered off and air-dried.
84.98(15)
94.41(16)
172.69(11)
92.42(12)
88.09(18)
95.47(17)
174.3(2)
Pd(4)–C(71)
Pd(4)–C(65)
Pd(4)–N(12)
Pd(4)–S(2)
Pd(3)ꢁ ꢁ ꢁPd(4)
S(2)–C(56)
1.819(4)
1.297(6)
1.320(6)
163.79(12)
107.49(15)
68.65(12)
96.34(4)
N(12)–C(56)
N(11)–C(56)
3.2.1. [NBu4][(C6F5)2Pd{SC(OMe)NPh}] (1)
Yield: 103 mg, 85%. Anal. Calc. for C36H44-
F10N2OPdS: C, 50.9; H, 5.2; N, 3.3; S, 3.8. Found: C,
51.0; H, 5.3; N, 3.4; S, 3.6%. M.p.: 194 dec. KM ¼ 108
S cm2 molꢀ1. IR (Nujol, cmꢀ1): 1530 m(C@N), 790, 775
(Pd–C6F5). 1H NMR ((CD3)2CO): d 6.98 (dd, 2Hm,
Jom ¼ Jmp ¼ 7:6 Hz), 6.81 (m, 1Hp + 2Ho), 3.84 (s, 3H,
OCH3). 19F NMR ((CD3)2CO): d )112.6 (d, 2Fo,
Jom ¼ 28:8 Hz), )113.2 (d, 2Fo, Jom ¼ 27:7 Hz), )165.4
(t, 1Fp, Jpm ¼ 19:8 Hz), )166.0 (t, 1Fp, Jpm ¼ 19:8 Hz),
)166.5 (m, 2Fm), )167.2 (m, 2Fm).
N(12)–C(56)–N(11)
N(12)–C(56)–S(2)
N(11)–C(56)–S(2)
130.2(4)
108.5(3)
121.2(3)
thane] [28]. The distances Pd(1)–N are shorter than
those observed in [(C6F5)2Pd(bpz*mFec)]. The crystal
structures of the l3,g2-diphenylthioureato complexes
[(l2-H)Ru6(CO)16(l5-S)(l3,g2-SCNHPhNPh)] and [(l-
H)6Ru6(CO)14(l3,g2-SCNHPhNPh)] have been previ-
ously reported [6,7].
3.2.2. [NBu4][(C6F5)2Pd{SC(OEt)NPh}] (2)
Yield: 104 mg, 84%. Anal. Calc. for C37H46-
F10N2OPdS: C, 51.5; H, 5.4; N, 3.3; S, 3.7. Found: C,
51.3; H, 5.4; N, 3.2; S, 3.5%. M.p.: 205 dec. KM ¼ 105
S cm2 molꢀ1. IR (Nujol, cmꢀ1): 1520 m(C@N), 790, 775
(Pd–C6F5). 1H NMR ((CD3)2CO): d 6.98 (dd, 2Hm,
Jom ¼ Jmp ¼ 6:8 Hz), 6.81 (m, 1Hp + 2Ho), 4.34 (q, 2H,
OCH2, J ¼ 6:9 Hz), 1.29 (t, 3H, OCH2CH3, J ¼ 6:9
3. Experimental
3.1. Materials and physical measurements
C, H, and N analyses were performed with a Carlo
Erba model EA 1108 microanalyzer. Decomposition
temperatures were determined with a Mettler TG-50
thermobalance at a heating rate of 5 °C minꢀ1 and the
solid samples under nitrogen flow (100 ml minꢀ1 ).
Molar conductivities were measured in acetone solution
(c ꢂ 5 ꢃ 10ꢀ4 mol lꢀ1) with a Crison 525 conductimeter.
The NMR spectra were recorded on a Bruker AC 200E
or Varian Unity 300 spectrometer, using SiMe4 and
Hz). 19F NMR ((CD3)2CO):
d )112.6 (d, 2Fo,
Jom ¼ 27:4 Hz), )113.1 (d, 2Fo, Jom ¼ 29:1 Hz), )165.5
(t, 1Fp, Jpm ¼ 20:0 Hz), )166.1 (t, 1Fp, Jpm ¼ 20:0 Hz),
)166.4 (m, 2Fm), )167.2 (m, 2Fm).
3.2.3. [NBu4][(C6F5)2Pd{SC(OPrn)NPh}] (3)
Yield: 104 mg, 83%. Anal. Calc. for C38H48-
F10N2OPdS: C, 52.0; H, 5.5; N, 3.2; S, 3.7. Found: C,
51.8; H, 5.6; N, 3.3; S, 3.8%. M.p.: 206 dec. KM ¼ 108
1
CFCl3 as the standard, respectively. In the H NMR

2336
J. Ruiz et al. / Inorganica Chimica Acta 357 (2004) 2331–2338
S cm2 molꢀ1. IR (Nujol, cmꢀ1): 1535 m(C@N), 790, 775
(Pd–C6F5). 1H NMR ((CD3)2CO): d 6.99 (dd, 2Hm,
Jom ¼ Jmp ¼ 6:9 Hz), 6.84 (m, 1Hp + 2Ho), 4.25 (t, 2H,
OCH2, J ¼ 6:5 Hz), 1.68 (m, 3H, OCH2CH2), 0.93 (t,
3H, OCH2CH2CH3, J ¼ 7:4 Hz). 19F NMR
((CD3)2CO): d )112.5 (d, 2Fo, Jom ¼ 26:5 Hz), )113.1
(d, 2Fo, Jom ¼ 27:7 Hz), )165.5 (t, 1Fp, Jpm ¼ 19:8 Hz),
)166.1 (t, 1Fp, Jpm ¼ 19:8 Hz), )166.5 (m, 2Fm), )167.2
(m, 2Fm).
of water yielded a precipitate, which was filtered off and
air-dried.
3.3.4. [NBu4][(C6F5)2Pd{SC(NMe2)NPh}] (6)
Yield: 100 mg, 81%. Anal. Calc. for C37H47F10N3PdS:
C, 51.5; H, 5.5; N, 4.9; S, 3.7. Found: C, 51.3; H, 5.5; N,
5.0; S, 3.6%. M.p.: 207 dec. KM ¼ 114 S cm2 molꢀ1. IR
1
(Nujol, cmꢀ1): 1555 m(C@N), 780, 770 (Pd–C6F5). H
NMR ((CD3)2CO): d 6.92 (dd, 2Hm, Jom ¼ Jmp ¼ 7:8
Hz), 6.69 (t, 1Hp, Jmp 7.5 Hz), 6.49 (d, 2Ho, Jom 7.3 Hz),
2.74 (s, 6H, NCH3). 19F NMR ((CD3)2CO): d )111.7 (d,
2Fo, Jom ¼ 28:8 Hz), )112.9 (d, 2Fo, Jom ¼ 28:8 Hz),
)166.3 (t, 1Fp, Jpm ¼ 20:0 Hz), )166.8 (m, 1Fp + 2Fm),
)167.5 (m, 2Fm).
3.3. Preparation of [NBu4][(C6F5)2Pt{SC(OR)NPh}]
[R ¼ Me (4), Et (5)]
To a solution of [NBu4]2[{Pt(C6F5)2(l-OH)}2] (100
mg, 0.063 mmol) in the corresponding alcohol (10 cm3)
was added phenylisothiocyanate PhNCS (30.4 ll, 0.254
mmol). The solution was boiled under reflux for 7 h.
Then, the solvent was partially evaporated under re-
duced pressure. Addition of water caused the precipi-
tation of a solid, which was filtered off and air-dried.
3.3.5. [NBu4][(C6F5)2Pd{SC(NEt2)NPh}] (7)
Yield: 104 mg, 82%. Anal. Calc. for C39H51F10N3PdS:
C, 52.6; H, 5.8; N, 4.7; S, 3.6. Found: C, 52.4; H, 5.8; N,
4.6; S, 3.4%. M.p.: 224 dec. KM ¼ 101 S cm2 molꢀ1. IR
1
(Nujol, cmꢀ1): 1535 m(C@N), 785, 775 (Pd–C6F5). H
NMR ((CD3)2CO): d 6.92 (dd, 2Hm, Jom ¼ Jmp ¼ 7:6
Hz), 6.71 (t, 1Hp, Jmp 7.2 Hz), 6.55 (d, 2Ho, Jom 7.8 Hz),
3.22 (q, 4H, NCH2, J ¼ 7.1 Hz), 0.98 (t, 6H, NCH2CH3,
J ¼ 7.1 Hz). 19F NMR ((CD3)2CO): d )111.6 (d, 2Fo,
Jom ¼ 27:4 Hz), )113.0 (d, 2Fo, Jom ¼ 29:1 Hz), )166.5
(t, 1Fp, Jpm ¼ 19:8 Hz), )166.9 (m, 1Fp + 2Fm), )167.6
(m, 2Fm).
3.3.1. [NBu4][(C6F5)2Pt{SC(OMe)NPh}] (4)
Yield: 103 mg, 87%. Anal. Calc. for C36H44-
F10N2OPtS: C, 46.1; H, 4.7; N, 3.0; S, 3.4. Found: C,
46.0; H, 4.7; N, 2.9; S, 3.5%. M.p.: 230 dec. KM ¼ 107
S cm2 molꢀ1. IR (Nujol, cmꢀ1): 1525 m(C@N), 805, 790
(Pt–C6F5). 1H NMR ((CD3)2CO): d 7.01 (dd, 2Hm,
Jom ¼ Jmp ¼ 7:5 Hz), 6.84 (m, 1Hp + 2Ho), 3.84 (s, 3H,
OCH3). 19F NMR ((CD3)2CO): d )116.4 (d, 2Fo,
3.4. Preparation of [(C6F5)2M{l2,g2-SC(X)NPh}-
Pd(C6F5)(bpzm)] [M ¼ Pd, X ¼ MeO (8), NMe2 (9);
M ¼ Pt, X ¼ MeO (10)]
Jom ¼ 29:1 Hz, JPtFo ¼ 502:3 Hz), )116.9 (d, 2Fo, Jom
¼
27:7 Hz, JPtFo ¼ 476:9 Hz), )167.5 (t, 1Fp, Jpm ¼ 19:8
Hz), )167.8 (m, 2Fm), )168.3 (t, 1Fp, Jpm ¼ 18:3 Hz),
)168.6 (m, 2Fm).
To a solution of [(C6F5)Pd(bpzm)(acetone)]ClO4 (100
mg, 0.157 mmol) in acetone (20 ml) was added the
corresponding monomeric thiocarbamate or thioureate
complex [NBu4][(C6F5)2M{g2-SC(X)NPh}] (M ¼ Pd or
Pt, X ¼ OMe or NR2) (0.157 mmol). The resulting so-
lution was stirred for 1 h and concentrated under vac-
uum to dryness. The residue was treated with 20 ml of
CH2Cl2 and then filtered through a small column
packed with florisil. The solvent was partially evapo-
rated under reduced pressure. The addition of hexane
caused the precipitation of a yellow solid, which was
collected by filtration and air-dried. Complexes were
recrystallized from dry toluene/CH2Cl2/hexane.
3.3.2. [NBu4][(C6F5)2Pt{SC(OEt)NPh}] (5)
Yield: 103 mg, 85%. Anal. Calc. for C37H46-
F10N2OPtS: C, 46.7; H, 4.9; N, 2.9; S, 3.4. Found: C,
46.7; H, 4.8; N, 3.0; S, 3.6%. M.p.: 221 dec. KM ¼ 115
S cm2 molꢀ1. IR (Nujol, cmꢀ1): 1525 m(C@N), 800, 790
(Pt–C6F5). 1H NMR ((CD3)2CO): d 7.00 (dd, 2Hm,
Jom ¼ Jmp ¼ 7:5 Hz), 6.85 (m, 1Hp + 2Ho), 4.33 (q, 2H,
OCH2, J ¼ 6:9 Hz), 1.33 (t, 3H, OCH2CH3, J ¼ 6:9
Hz). 19F NMR ((CD3)2CO): d )116.3 (d, 2Fo, Jom
¼
24:6 Hz, JPtFo ¼ 499:5 Hz), )116.9 (d, 2Fo, Jom ¼ 25:9
Hz, JPtFo ¼ 471:3 Hz), )167.7 (m, 1Fp + 2Fm), )168.4
(m, 1Fp + 2Fm).
3.4.1. [C6F5)2Pd{l2,g2-SC(OMe)NPh}Pd(C6F5)-(bpzm)]
(8)
3.3.3. Preparation of [NBu4][(C6F5)2Pd{SC(NR2)-
NPh}] [R ¼ Me (6), Et (7)]
Yield: 119 mg, 70%. Anal. Calc. for C37H24-
N5F15OSPd2: C, 41.0; H, 2.2; N, 6.5; S, 3.0. Found: C,
41.1; H, 2.1; N, 6.5; S, 2.8%. M.p. 184 dec. IR (Nujol,
cmꢀ1): 1582 m(C@N), 794, 782 (Pd–C6F5). 1H NMR
(CDCl3): d 7.74 (d, 1H, CH, Jab ¼ 15:0 Hz), 7.02 (m,
3H, NC6H5), 6.50 (d, 2H, NC6H5, J ¼ 7:2 Hz), 6.01 (d,
1H, CH, Jab ¼ 15:0 Hz), 5.88 (s, 1H, H40), 5.57 (s, 1H,
H4), 3.97 (s, 3H, OCH3), 2.44 (s, 3H, Me30), 2.28 (s, 3H,
To a solution of [NBu4]2[{Pd(C6F5)2(l-OH)}2] (100
mg, 0.071 mmol) in dichloromethane (6 cm3) was added
the corresponding amine (0.143 mmol) and phenyliso-
thiocyanate PhNCS (17.1 ll, 0.143 mmol). The solution
was stirred at room temperature for 8 h. Then, the sol-
vent was completely evaporated under reduced pressure
and the residue was treated with isopropanol. Addition

J. Ruiz et al. / Inorganica Chimica Acta 357 (2004) 2331–2338
2337
Me5), 2.20 (s, 3H, Me50), 1.83 (s, 3H, Me3). 19F NMR
Table 3
Crystal structure determination details
(CDCl3): d )113.1 (br, 2Fo), )114.8 (br, 1Fo), )115.2
(br, 1Fo), )116.3 (br, 1Fo), )116.6 (m, 1Fo), )157.6 (t,
1Fp, Jmp ¼ 19:8 Hz), )160.0 (m, 1Fm), )161.6 (t, 1Fp,
Jmp ¼ 19:8 Hz), )162.6 (t, 1Fp, Jmp ¼ 19:8 Hz), )163.1
(m, 1Fm), )164.2 (m, 4Fm).
1
9
Formula
C36H44F10N2OPdS C38H27F15N6Pd2S
1097.52
triclinic
Formula weight
Crystal system
Unit cell dimensions
849.19
monoclinic
ꢁ
a (A)
11.3637(7)
17.1551(9)
19.5975(14)
90
12.2326(7)
12.2301(7)
15.4956(9)
96.3470(10)
96.3510(10)
119.0200(10)
1978.4(2)
3.4.2.
(bpzm)] (9)
[C6F5)2Pd{l2,g2-SC(NMe2)NPh}Pd(C6F5)-
ꢁ
b (A)
ꢁ
c (A)
a (°)
b (°)
c (°)
Yield: 112 mg, 65%. Anal. Calc. for C38H27-
N6F15SPd2: C, 41.6; H, 2.5; N, 7.7; S, 2.9. Found: C,
41.7; H, 2.4; N, 7.6; S, 2.8%. M.p.: 227 dec. IR (Nujol,
cmꢀ1): 1602, 1590 m(C@N), 792, 778 (Pd–C6F5). 1H
NMR (CDCl3): d 7.84 (d, 1H, CH, Jab ¼ 15:0 Hz), 6.90
(m, 3H, NC6H5), 6.44 (d, 2H, NC6H5, J ¼ 7:8 Hz), 6.00
(d, 1H, CH, Jab ¼ 15:0 Hz), 5.87 (s, 1H, H40), 5.52 (s,
1H, H4), 3.13 (br, 3H, NCH3), 2.44 (s, 3H, Me30), 2.26
(s, 3H, Me5), 2.21 (s, 3H, Me50), 1.97 (br, 3H, NCH3),
1.81 (s, 3H, Me3). 19F NMR (CDCl3): d )112.9 (br,
2Fo), ) 113.7 (m, 1Fo), )115.5 (m, 2Fo), )116.8 (m,
1Fo), )159.2 (t, 1Fp, Jmp ¼ 20:7 Hz), )161.5 (m, 1Fm),
)162.9 (t, 1Fp, Jmp ¼ 20:7 Hz), )163.6 (t, 1Fp,
Jmp ¼ 20:7 Hz), )163.9 (m, 1Fm), )164.7 (m, 2Fm),
)165.2 (m, 2Fm).
91.211(5)
90
3
ꢁ
Unit cell volume (A )
3819.6(4)
173(2)
P21=n
4
0.620
Temperature
Space group
Z
100(2)
ꢂ
P1
2
l (mmꢀ1
)
Reflections collected
1.071
23 208
16 795
0.0176
0.0353
0.0774
7100
Independent reflections 6719
Rint
0.0110
0.0256
0.0589
a
R1½I > 2rIÞꢄ
wR2 (all data)b
P
P
a R1 ¼ jjFoj ꢀ jFcjj= jFoj for reflections with I > 2rI.
P
P
2
2
1=2
b wR2 ¼ f ½wðFo2 ꢀ Fc2Þ ꢄ= ½wðFo2Þ ꢄg
for all reflections; wꢀ1
¼
2
r2ðF 2Þ þ ðaPÞ þ bP, where P ¼ ð2Fc2 þ Fo2Þ=3 and a and b are con-
stants set by the program.
3.4.3. [C6F5)2Pt{l2,g2-SC(OMe)NPh}Pd(C6F5)-(bpzm)]
(10)
Data collection for 9 was performed on a Bruker Smart
CCD diffractometer with a nominal crystal to detector
distance of 4.5 cm. Diffraction data were collected based
on a x scan run. A total of 2524 frames were collected at
0.3° intervals and 10 s per frame. The diffraction frames
were integrated using the SAINT package [31] and cor-
rected for absorption with SADABS [32]. The structure
was solved by Patterson (compound 1) and direct
(compound 9) methods [33] and refined anisotropically
on F 2 [33]. Hydrogen atoms were introduced in calcu-
lated positions.
Yield: 135 mg, 73%. Anal. Calc. for C37H24-
N5F15OSPdPt: C, 37.9; H, 2.1; N, 6.0; S, 2.7. Found: C,
38.2; H, 2.1; N, 5.7; S, 2.8%. M.p.: 185 °C dec. IR
((Nujol, cmꢀ1): 1582 cm m(C@N), 808, 794 (M–C6F5).
1H NMR (CDCl3): d 7.73 (d, 1H, CH, Jab ¼ 15:0 Hz),
7.03 (m, 3H, NC6H5), 6.50 (d, 2H, NC6H5, J ¼ 6:9 Hz),
5.95 (d, 1H, CH, Jab ¼ 15:0 Hz), 5.86 (s, 1H, H40), 5.57
(s, 1H, H4), 3.93 (s, 3H, OCH3), 2.43 (s, 3H, Me30), 2.28
(s, 3H, Me5), 2.25 (s, 3H, Me50), 1.80 (s, 3H, Me3). 19F
NMR (CDCl3): d )115.2 (br, 1Fo), )116.5 (m, 1Fo),
)117.1 (br, 2Fo), )118.1 (m, 1Fo), )120.2 (d, 1Fo,
JPtFo ¼ 506, Jom ¼ 28.2), )157.2 (t, 1Fp, Jmp ¼ 19:8 Hz),
)159.9 (m, 1Fm), )162.9 (m, 1Fm + 1Fp), )164.3 (t, 1Fp,
Jmp ¼ 19:8 Hz), )163.1 (m, 1Fm), )165.3 (m, 4Fm).
4. Supplementary material
Crystallographic data (excluding structure factors)
reported in this paper have been deposited with Cam-
bridge Crystallographic Data Centre as supplementary
publication nos. CCDC-223557 (1) and CCDC-223558
(9). Copies of the data can be obtained free of charge on
application to CCDC, 12 Union Road, Cambridge, CB2
1EZ, UK [Fax: (internat.) +44-1223/336-033; E-mail:
deposit@ccdc.cam.ac.uk].
3.5. Crystal structure determination of [NBu4][(C6F5)2-
Pd{SC(OMe)NPh}] (1) and [(C6F5)2Pd{l2,g2-SC-
(NMe2)NPh}Pd(C6F5)(bpzm)] (9)
Suitable crystals for the X-ray diffraction study of
compounds 1 and 9 were grown from a dry dichlorom-
ethane/hexane or dichloromethane/toluene/hexane solu-
tion, respectively. Data collection for 1 was carried out
on a Siemens P4 diffractometer. The crystallographic
data are shown in Table 3. An empirical w-scan mode
absorption correction was made. Data were collected
using a single crystal of approximate dimensions
0.4 ꢃ 0.4 ꢃ 0.3 mm3. The range of hkl was 0 6 h 6 13,
ꢀ206 k 6 1, ꢀ23 6 l6 23, corresponding to 2hmax ¼ 50°.
Acknowledgements
ꢀ
This work was supported by the Direccion General
ꢀ
ꢀ
de Investigacion del Ministerio de Ciencia y Tecnologıa
(Project No. BQU2001-0979-C02-01), Spain, and the

2338
J. Ruiz et al. / Inorganica Chimica Acta 357 (2004) 2331–2338
ꢀ ~ ꢀ
[17] E. Alonso, J. Fornies, C. Fortuno, M. Tomas, J. Chem. Soc.,
ꢀ
Fundacion Seneca de la Comunidad Autonoma de la
Region de Murcia (Project No. PI-72-00773-FS-01).
ꢀ
ꢀ
Dalton Trans. (1995) 3777.
[18] E. Maslowski, Vibrational Spectra of Organometallic Com-
pounds, Wiley, New York, 1977, p. 437.
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