Synthesis, characterization and crystal structures of cyclometallated palladium (II) compounds containing difunctional ligands with [P,P], [As,As], [N,N], [P,As], [P,N] and [P,O] donor atoms

Article abstract of DOI:10.1016/j.jorganchem.2008.08.023

Treatment of the chloro-bridged dinuclear complex [Pd{3,4-(MeO)₂C₆H₂C(H){double bond, long}N(Cy)-C6,N}(μ-Cl)]₂ (1) with homobidentate [P,P], [As,As], [N,N], and heterobidentate [P,As], [P,N] ligands in a 1:1 molar ratio gave the dinuclear complexes [{Pd[3,4-(MeO)₂C₆H₂C(H){double bond, long}N(Cy)-C6,N](Cl)}₂{μ-L}] (L = Ph₂PC₄H₆(NH)CH₂PPh₂ (2); Ph₂As(CH₂)₂AsPh₂ (3); 1,3-(NH₂CH₂)₂C₆H₄ (4); Ph₂P(CH₂)₂AsPh₂ (5); Ph₂P(CH₂)₂NH₂ (6)), with the bidentate ligands bridging the two cyclometallated fragments. The reaction with the homobidentate ligands in a 1:2 molar ratio in the presence of NaClO₄ afforded the mononuclear compounds [[Pd{3,4-(MeO)₂C₆H₂C(H){double bond, long}N(Cy)-C6,N}{L-P,P}][ClO₄] (L = Ph₂PC₄H₆(NH)CH₂PPh₂ (7); (o-Tol)₂P(CH₂)₂P(o-Tol)₂ (8)), [Pd{3,4-(MeO)₂C₆H₂C(H){double bond, long}N(Cy)-C6,N}{Ph₂As(CH₂)₂AsPh₂-As,As}][ClO₄] (9) and [Pd{3,4-(MeO)₂C₆H₂C(H){double bond, long}N(Cy)-C6,N}{L-N,N}][ClO₄] (L = NH₂(CH₂)₃NH₂ (10); NH₂(C₆H₈)CH₂(C₆H₈)NH₂ (11); 1,3-(NH₂CH₂)₂C₆H₄ (12); 1,3-(NH₂)₂C₅H₃N (13); NH₂(C₆H₄)O(C₆H₄)NH₂ (14); NMe₂(CH₂)₂NMe₂ (15)), in which the chloro ligands are absent and the bidentate ligands are chelated to the palladium atom. Reaction of 1 with Ph₂P(CH₂)₂AsPh₂ in 1:2 molar ratio in acetone in the presence of NH₄PF₆ afforded the analogous mononuclear compound [Pd{3,4-(MeO)₂C₆H₂C(H){double bond, long}N(Cy)-C6,N}{Ph₂P(CH₂)₂AsPh₂-P,As}][PF₆] (16); whereas reaction with Ph₂P(CH₂)₃NH₂ gave [Pd{3,4-(MeO)₂C₆H₂C(H){double bond, long}N(Cy)-C6,N}{Ph₂P(CH₂)₃N(C{double bond, long}Me₂)-P,N}][PF₆] (17), derived from intermolecular condensation between the aminophosphine and acetone. Condensation of the NH₂ group was precluded by change of solvent, using dichloromethane. Iminophoshines also reacted with 1 in 1:2 molar ratio in acetone to give a new series of mononuclear cyclometallated complexes: [Pd{3,4-(MeO)₂C₆H₂C(H){double bond, long}N(Cy)-C6,N}{L-P,N}][ClO₄] (L = Ph₂PC₆H₄C(H){double bond, long}NCy (20); Ph₂PC₆H₄C(H){double bond, long}NC(CH₃)₃ (21); Ph₂PC₆H₄C(H){double bond, long}NNMe₂ (22); Ph₂PC₆H₄C(H){double bond, long}NNHMe (23); Ph₂PC₆H₄C(H){double bond, long}NNHPh (24)). Analogous complexes with a stable P,O-chelate were obtained using bidentate [P,O] donor ligands: [Pd{3,4-(MeO)₂C₆H₂C(H){double bond, long}N(Cy)-C6,N}{L-P,O}][Cl] (L = 2-(Ph₂P)C₆H₄CHO (25); Ph₂PN(Me)C({double bond, long}O)Me (26)). The crystal structures of compounds 1, 5, 15, 16, 18, 20 have been determined by X-ray crystallography.

Full text of DOI:10.1016/j.jorganchem.2008.08.023

Journal of Organometallic Chemistry 693 (2008) 3655–3667
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis, characterization and crystal structures of cyclometallated palladium
(II) compounds containing difunctional ligands with [P,P], [As,As], [N,N], [P,As],
[P,N] and [P,O] donor atoms
Raquel Ares a, Digna Vázquez-García a, Margarita López-Torres a, Alberto Fernández a, Nina Gómez-Blanco a,
a
José M. Vila b, , Jesús J. Fernández
*
*
a Departamento de Química Fundamental, Universidade da Coruña, 15071 A Coruña, Spain
b Departamento de Química Inorgánica, Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spain
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 13 June 2008
Received in revised form 18 August 2008
Accepted 19 August 2008
Available online 24 August 2008
Treatment of the chloro-bridged dinuclear complex [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}(l-Cl)]2 (1)
with homobidentate [P,P], [As,As], [N,N], and heterobidentate [P,As], [P,N] ligands in a 1:1 molar ratio gave
the dinuclear complexes [{Pd[3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N](Cl)}2{ -L}] (L = Ph2PC4H6(NH)CH2PPh2
l
(2); Ph2As(CH2)2AsPh2 (3); 1,3-(NH2CH2)2C6H4 (4); Ph2P(CH2)2AsPh2 (5); Ph2P(CH2)2NH2 (6)), with the
bidentate ligands bridging the two cyclometallated fragments.
The reaction with the homobidentate ligands in a 1:2 molar ratio in the presence of NaClO4 afforded the
mononuclear compounds [[Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{L-P,P}][ClO4] (L = Ph2PC4H6(NH)CH2PPh2
(7); (o-Tol)2P(CH2)2P(o-Tol)2 (8)), [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2As(CH2)2AsPh2-As,A-
s}][ClO4] (9) and [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{L-N,N}][ClO4] (L = NH2(CH2)3NH2 (10);
NH2(C6H8)CH2(C6H8)NH2 (11); 1,3-(NH2CH2)2C6H4 (12); 1,3-(NH2)2C5H3N (13); NH2(C6H4)O(C6H4)NH2
(14); NMe2(CH2)2NMe2 (15)), in which the chloro ligands are absent and the bidentate ligands are che-
lated to the palladium atom.
Keywords:
Palladium
Metallation
Diphosphines
[P,As] ligands
[P,O] ligands
Reaction of 1 with Ph2P(CH2)2AsPh2 in 1:2 molar ratio in acetone in the presence of NH4PF6 afforded the
analogous mononuclear compound [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2P(CH2)2AsPh2-P,As}][PF6]
(16); whereas reaction with Ph2P(CH2)3NH2 gave [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2P(CH2)3N-
(C@Me2)-P,N}][PF6] (17), derived from intermolecular condensation between the aminophosphine and
acetone. Condensation of the NH2 group was precluded by change of solvent, using dichloromethane.
Iminophoshines also reacted with 1 in 1:2 molar ratio in acetone to give a new series of mononuclear
cyclometallated complexes: [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{L-P,N}][ClO4] (L = Ph2PC6H4C(H)
@NCy (20); Ph2PC6H4C(H)@NC(CH3)3 (21); Ph2PC6H4C(H)@NNMe2 (22); Ph2PC6H4C(H)@NNHMe (23);
Ph2PC6H4C(H)@NNHPh (24)). Analogous complexes with a stable P,O-chelate were obtained using biden-
tate [P,O] donor ligands: [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{L-P,O}][Cl] (L = 2-(Ph2P)C6H4CHO (25);
Ph2PN(Me)C(@O)Me (26)).
The crystal structures of compounds 1, 5, 15, 16, 18, 20 have been determined by X-ray crystallography.
Ó 2008 Elsevier B.V. All rights reserved.
1. Introduction
have prepared a series of related complexes with diarsines [10].
We were now interested in looking further into the chemistry of
Cyclometallated compounds have been widely studied over the
last decades especially due to their numerous applications in cata-
lytic and synthetic processes [1], in medicine and biology [2], and
to their interesting mesogenic [3], luminiscent and electronic prop-
erties [4].
In the past we have researched the reactivity of cyclometallated
compounds with diphosphines, due to the versality of the elec-
tronic and steric properties of the latter [5–9]; more recently we
cyclopalladated complexes when they react with other bidentate
group 15 donor atom ligands such as diamines. Furthermore, there
has been recent interest in the chemistry of polydentate ligands,
especially those which combine ‘‘soft” and ‘‘hard” donor atoms
[11–18]. These ligands show a characteristic behaviour when bind-
ing to soft metal centers giving complexes that are good catalysts
in numerous processes [19–23]. Thus, in the present paper we also
describe the synthesis and characterization of new cyclometallated
compounds derived from heterobidentate [P,N], [P,As] and [P,O] li-
gands, amongst which are the widely studied iminophosphines
[24–27]. Accordingly, we have prepared a series of iminophosphine
* Corresponding authors.
E-mail address: qideport@usc.es (J.M. Vila).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.08.023

3656
R. Ares et al. / Journal of Organometallic Chemistry 693 (2008) 3655–3667
ligands via condensation between amines or hydrazines and o-
(diphenylphosphino)benzaldehyde; the latter being one of the
simplest bidentate P,O-chelating agents [28–33], for which we
have also explored its coordination chemistry, as well as that of
the related N-methyl acetamido phosphine: Ph2PN(Me)C(O)Me
[34,35].
2. Results and discussion
For the convenience of the reader the compounds and reactions
are shown in Schemes 1–3. The compounds described in this paper
were characterized by elemental analysis (C, H, N), by mass spec-
trometry, and by IR and 1H, 31P-{1H} and (in part) 13C-{1H} NMR
spectroscopy (data in Section 3).
These homo- and heterofunctional ligands have been reacted
with the chloro-bridged dinuclear complex [Pd{3,4-(MeO)2C6H2C-
Treatment of the chloro-bridged dinuclear complex [Pd{3,4-
(H)@N(Cy)-C6,N}(l-Cl)]2 (1) previously synthetized by us [36],
(MeO)2C6H2C(H)@N(Cy)-C6,N}(
l-Cl)]2 (1) with Ph2PC4H6(NH)CH2-
and herein we report the synthesis and characterization of the
resulting species, inclusive of the crystal structures of 1 and of
some of its derivatives.
PPh2 in a complex/phosphine 1:1 molar ratio gave the dinuclear
complex [{Pd[3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N](Cl)}2{
(NH)CH2PPh2}] (2) which was fully characterized.
l-Ph2PC4H6
Cy
N
Cl
Pd
OMe
P
Ph2
MeO
OMe
Ph2
P
Cy
N
OMe
NH
Pd
Cl
OMe
Pd
As
Ph2
Cl
N
MeO
2
Ph2
As
Cy
OMe
Pd
OMe
Cl
N
3
Cy
i
Cy
N
ii
Cl
Pd
OMe
OMe
NH2
4
MeO
3
5
6
MeO
OM
e
iii
2
Cl
H2N
Pd
OMe
1
Pd
2
Cl
N
Hi
N
4
Cy
Cy
1
iv
v
Cy
N
Cy
Hi'
N
Cl
OMe
4
Cl
P
OMe
Pd
1'
Pd
MeO
6'
5
2'
3'
OMe
MeO
As
3
Ph2
P
Ph2
6
Ph2
2
5'
H2N
Pd
1
4'
OMe
OMe
Pd
Cl
OMe
N
Hi
Cl
N
Cy
Cy
5
6
Scheme 1. (i) Ph2PC4H6(NH)CH2PPh2 (1:1), dichloromethane; (ii) Ph2As(CH2)2AsPh2 (1:1), dichloromethane; (iii) 1,3-(CH2NH2)C6H4 (1:1), dichloromethane; (iv)
Ph2As(CH2)2PPh2 (1:1), dichloromethane; (v) H2N(CH2)2PPh2 (1:1), dichloromethane.

R. Ares et al. / Journal of Organometallic Chemistry 693 (2008) 3655–3667
3657
OMe
MeO
R2
Pα
ClO4
Pd
R1
Pβ
N
R2
Cy
7
8
, R1 = C4H6(NH)CH2, R2 = (Ph2)2
, R1 = (CH2)2, R2 = (o -Tol)2
i
OMe
4
OMe
MeO
MeO
3
5
Ph2
As
Pd
ClO4
ii
6
2
Cl
2
1
Pd
As
N
N
Hi
Ph2
Cy
Cy
1
9
iii
OMe
MeO
R2
N
ClO4
Pd
R1
N
N
R2
Cy
10, R1 = (CH2)3, R2 = (H)2
11, R1 = (C6H8)CH2(C6H8), R2 = (H)2
12, R1 = 1,3-(CH2)2C6H4, R2 = (H)2
13, R1 =1,3-C5H3N, R2 = (H)2
14 , R1 = (C6H4)O(C6H4), R2 = (H)2
15, R1 = (CH2)2, R2 = Me2
Scheme 2. (i) R2PR1PR2 (1:2), NaClO4, dichloromethane; (ii) Ph2As(CH2)2AsPh2 (1:2), NaClO4, dichloromethane; (iii) R2NR1NR2 (1:2), NaClO4, dichloromethane.
The IR spectrum showed the shift of the C@N stretch towards
lower wavenumbers, as compared to the free Schiff base ligand
(ca. 1614 vs. 1644 cmꢀ1), indicating nitrogen coordination of the
C@N group.[37] The MS-FAB spectrum showed peaks assigned to
[MꢀCl]+ and [LPd(PP)]+ (L = cyclometallated ligand), which were
characteristic clusters of isotopic peaks covering about 10 m/z units,
due to the presence of the numerous palladium isotopes [38,39].
The 31P-{1H} NMR spectrum showed two singlets at d39.26 and
d41.02 assigned to the two non-equivalent phosphorus atoms, con-
sequent on the asymmetric structure of the diphosphine. The sing-
lets were shifted to higher frequency from the free phosphine,
suggesting coordination of both phosphorus atoms to the metal
center [40].
The 1H NMR spectrum showed two doublets at d5.78 and d5.96,
assigned to the H5/H50 protons, coupled to the 31P nucleus, and
two singlets at d2.83 and d2.99 assigned to the two 4-MeO groups,
thus putting forward the asymmetry of the diphosphine. These res-
onances were shifted to lower frequency from the starting product
due to the shielding effect of the phosphine phenyl rings, in agree-
ment with a P trans to N arrangement, typical of these reactions
and within the terms of the ‘‘transphobic effect” as coined by
Vicente et al. [41].
Reaction of 1 with the diarsine Ph2As(CH2)2AsPh2 or with the
diamine 1,3-(NH2CH2)C6H4 in 1:1 molar ratio afforded the dinucle-
ar complexes [{Pd[3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N](Cl)}2{
l-
Ph2As(CH2)2AsPh2}] (3) and [{Pd[3,4-(MeO)2C6H2C(H)@N(Cy)-

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R. Ares et al. / Journal of Organometallic Chemistry 693 (2008) 3655–3667
OMe
MeO
N
P
Ph2
P
PF6
Pd
Ph2P
NH2
18
19
22
As
N
Ph2
Ph2P
CH
Cy
OMe
NH2
Ph2P
N
MeO
16
NMe2
Ph2
P
PF6
Pd
N
Ph2P
CH
N
20
21
23
24
i
N
Cy
Ph2P
CH
N
Me
Me
Cy
NHMe
17
ii
OMe
4
Ph2P
CH
MeO
3
5
Ph2P
CH
N
N
tBu
6
2
Cl
1
Pd
NHPh
2
N
E
Hi
O
P
Cy
OMe
1
MeO
iii
ClO4
P
N
Pd
PF6
Ph2P
CH
25
26
iv
N
O
Cy
18-24
Me
N
Me
Cl
Ph2P
OMe
O
MeO
E
P
Pd
O
N
Cy
25, 26
Scheme 3. (i) Ph2P(CH2)2AsPh2 (1:2), NH4PF6, acetone/water; (ii) Ph2P(CH2)3NH2 (1:2), NH4PF6, acetone/water; (iii) [P,N] (1:2), NaClO4, toluene, 18, 19; dichloromethane, 20–
24; (iv) Ph2P(C6H4)CHO (1:2), NH4PF6, acetone/water (25), Ph2PN(CH3)C(@O)CH3 (1:2), dichloromethane (26).
C6,N](Cl)}2{
l
-1,3-(NH2CH2)2C6H4}] (4), respectively. The IR and the
the starting material by 1 ppm upon arsenic coordination to the
metal.
Reaction of 1 with the heterobidentate [P,As] and [P,N] ligands
Ph2P(CH2)2AsPh2 and Ph2P(CH2)2NH2 in 1:1 molar ratio gave the
dinuclear complexes [{Pd[3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N](Cl)}2
FAB-mass spectra were similar to those for complex 2. In the 1H
NMR spectra of 3 and 4, the multiplicity of some of the signals
was simplified due to the absence of the phosphorus atoms. Thus,
the HC@N resonance appeared as a singlet at ca. d8.00. A singlet ca.
d6.02 (3) d6.27 (4) was assigned to the H5 resonance, putting for-
ward the centrosymmetric nature of the complexes. In the spec-
trum of 3 these resonances were shifted to higher field due to
the shielding effect of the diarsine phenyl rings, in agreement with
a As trans to N arrangement. This shielding also influenced the 4-
MeO signal at d2.76 (3), which was also shifted to higher field from
{l-Ph2P(CH2)2AsPh2}] (5) and [{Pd[3,4-(MeO)2C6H2C(H)@N(Cy)-
C6,N](Cl)}2{l-Ph2P(CH2)2NH2}] (6). A singlet at d39.50 (5) d52.58
(6) in the 31P-{1H} NMR spectrum confirmed phosphorus coordina-
tion of the heterobidentate ligand to the metal center. Thus, in the
1H NMR spectrum of 5 the H5 and H50 protons gave rase to a dou-
blet at d5.91, by coupling to the phosphorus nucleus, and a singlet

R. Ares et al. / Journal of Organometallic Chemistry 693 (2008) 3655–3667
3659
at d6.00, respectively. In the 1H NMR spectrum of 6 two singlets at
d7.97 and d6.78 were assigned to the H0C@N and the H50 protons,
respectively, and two doublets at d8.03 and d6.10 were assigned
to the HC@N and the H5 protons, also, respectively. The H5 reso-
nance was upfield shifted with respect to H50 in agreement with
the shielding effect of the phosphine phenyl rings, absent in the
case of the amino group.
absorptions of the PFꢀ6 anion ca. 840 and 558 cmꢀ1. The IR spec-
trum of 17 showed two bands at 1616 and 1648 cmꢀ1 consistent
with the presence of two different imino groups: the HC@N group
in the cyclometallated ring and the Me2C@N group in the chelating
[P,N] ligand after condensation. Furthermore, the 1H NMR spec-
trum showed the presence of two singlets at d2.28 and d2.04
assignable to the non-equivalent N@CMe2 methyl groups.
In the 13C-{1H} NMR spectrum of 6 a doublet and a singlet ca.
d170 and a doublet and a singlet ca. d150 were assigned to the
C@N/C0@N and C6/C60 carbon atoms, respectively, downfield
shifted from the spectrum of the free ligand (d158, C@N; d122.7,
C6) thereby confirming metallation. The C4 and the C5 resonances
appeared as two doublets at d149.7 and d121.2, respectively, by
coupling to the phosphorus nucleus. However, the C40 and C50 res-
onances appeared as singlets at d149.8 and d125.0. These findings
reflected the asymmetry of the bidentate ligands.
Treatment of the chloro-bridged complex 1 with diphosphines
or with the diarsine Ph2As(CH2)2AsPh2 in a 1:2 molar ratio in the
presence of NaClO4 gave the mononuclear compounds [[Pd{3,4-
(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2PC4H6(NH)CH2PPh2-P,P}][ClO4]
Condensation of the NH2 group was precluded by change of sol-
vent. Thus, reaction of 1 with Ph2P(CH2)nNH2, in dichloromethane,
in the presence of NaClO4, afforded compounds [Pd{3,4-
(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2P(CH2)3NH2-P,N}][ClO4]
(18)
and [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2P(CH2)2NH2-P,N}]
[ClO4] (19). The analytical and mass data were in agreement with
the proposed structures. The conductivity measurements, (130–
165
X
ꢀ1 cm2 molꢀ1 in 10ꢀ3 mol dmꢀ3 solutions in dry acetonitrile)
showed them to be 1:1 electrolytes, confirming the presence of the
aminophosphine ligand in its neutral form. The IR and NMR data
were similar to that observed for compound 17. In the 13C-{1H}
NMR spectrum of 18, the C4, C5, C6 and the C@N, resonances ap-
peared as four doublets at d149.4, d121.2, d149.6 and d172.0,
respectively, by coupling to the phosphorus nucleus.
Treatment of 1 with different iminophoshines in 1:2 molar ratio
in dichloromethane in the presence of NaClO4 gave [Pd{3,4-
(MeO)2C6H2C(H)@N(Cy)-C6,N}{L-P,N}][ClO4] (L = Ph2PC6H4C(H)@
NCy (20); Ph2PC6H4C(H)@NC(Me)3 (21); Ph2PC6H4C(H)@NNMe2
(22); Ph2PC6H4C(H)@NNHMe (23); Ph2PC6H4C(H)@NNHPh (24)).
A strong band at 1628–1648 cmꢀ1 was assigned to the C@N
stretch, at lower frequency than in the free ligand, in accordance
with coordination of the iminophosphine ligand. The 1H NMR spec-
tra showed the corresponding aromatic signals of the neutral li-
gands, with a typical imine doublet resonance (Hi0) at 7.9–8.8
ppm [4J(PHi0) = 2.0–3.5 Hz].
(7),
[Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{(o-Tol)2P(CH2)2P(o-
(8) and [Pd{3,4-(OMe)2C6H2C(H)@N(Cy)-
Tol)2-P,P}][ClO4]
C6,N}{Ph2As(CH2)2AsPh2-As,As}][ClO4] (9). An analogous reaction
with different diamines gave [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-
C6,N}{L-N,N}][ClO4] [L = NH2(CH2)3NH2 (10); NH2(C6H8)CH2(C6H8)
NH2 (11); 1,3-(NH2CH2)2C6H4 (12); 1,3-(NH2)2C5H3N (13);
NH2(C6H4)O(C6H4)NH2 (14); NMe2(CH2)2NMe2 (15)].
The MS-FAB spectra showed the corresponding peaks assigned to
[M]+ (see Section 3). The IR spectra exhibited the characteristic
absorptions of the ClO4ꢀ anion ca. 1100 and 600 cmꢀ1 and the
molar conductivity measurements (125–150
X
ꢀ1 cm2 molꢀ1 in
10ꢀ3 mol dmꢀ3 solutionsin dryacetonitrile)were in agreementwith
1:1 electrolytes [42].
The 13C-{1H} NMR spectrum of 21 showed two singlets at d29.7
and d30.9 for the methyl groups of the ter-butyl fragment, suggest-
ing the hindered rotation of the CMe3 substituent around the C@N
bond.
Finally, treatment of 1 with Ph2P(C6H4)CHO or Ph2PN(Me)
C(@O)Me in a 1:2 molar ratio gave the mononuclear compounds
[Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{2-(Ph2P) C6H4-CHO-P,O}]
[PF6] (25) and [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N} {Ph2PN(Me)-
C(@O)Me-P,O}][Cl] (26) as 1:1 electrolytes with the ligand chelated
to the metal center.
The 31P-{1H} NMR spectra of 7 and 8 showed two doublets for
the two non-equivalent phosphorus. The resonance at lower fre-
quency was assigned to the phosphorus nucleus trans to the phenyl
carbon atom in accordance with the higher trans influence of the
latter with respect to the C@N nitrogen atom [40].
The 31P chemical shifts were clearly influence by ring size [43].
Thus, compared to an analogous compound where the P phospho-
a
rous of the chelated diphosphine is a triphenylphosphine ligand
[36], the five-membered ring compound, 8, gave a positive Dring
(11.64), whereas the four-membered ring compound 7 gave a neg-
ative Dring (ꢀ3.65).
Bonding of the P,O-chelate to the Pd centre resulted in
m
m
(C@O)
(C@O)
bands at 1647 (25) and 1584 cmꢀ1 (26) (cf. free ligand
In the 1H NMR spectra of the diphosphine compounds a doublet
of doublets ca. d6.00 was assigned to H5, coupled to both phospho-
1700 and 1669 cmꢀ1, respectively), and low-field shifted 31P-{1H}
NMR resonances at d35.90 (25) and d94.81 (26) (cf. free ligand d
ꢀ11.2 and d55.1, respectively). The 1H NMR data was in agreement
with P-trans-N and O-trans-C(phenyl ring) coordination.
rus nuclei [4J(P H5) ca. 5 Hz, 4J(PbH5) ca.8 Hz]. However, the HC@N
a
resonance appeared ca. d8.00 as a doublet by coupling to only the
31P nucleus trans to nitrogen; this was confirmed by selective irra-
diation experiments. In the 1H NMR spectra of the remaining the
compounds, 9–15, absence of the phosphorus nuclei was reflected
in the simplification of signal multiplicity and in the position of the
H5 and 4-OMe resonances (see Section 3).
In the 1H NMR spectra of compound 25, a doublet at d10.15 was
assigned to the CHO group of the [P,O] ligand [4J(PH) = 1.5 Hz], up-
field shifted ca. 0.35 ppm from the spectrum of the free ligand con-
firming oxygen coordination to the metal center [44].
Along with 25 an additional compound was obtained prior to
the addition of NaClO4, which was separated by filtration. The
spectroscopic data was in agreement with a species bearing a
monocoordinated phosphine-P. The IR spectrum exhibited an
absorption band at 1696 cmꢀ1, characteristic of a non coordinated
formyl group. The 1H NMR spectrum showed a doublet at d10.44
(d, PCHO, 4J(PH) = 2.4 Hz) close to the free ligand value of
10.5 ppm. A singlet resonance at d38.86, in the 31P-{1H} NMR spec-
trum, was in accordance with phosphorus coordination to the me-
tal center (see Section 3).
The 13C-{1H} NMR spectrum of 15 was very similar to that for 1;
two singlets at d51.5 and d48.5 were ascribed to the diamine
methyl groups of the non-equivalent nitrogen atoms.
Reaction of 1 with Ph2P(CH2)2AsPh2 or Ph2P(CH2)3NH2 in 1:2
molar ratio in acetone in the presence of NH4PF6 afforded
[Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2P(CH2)2AsPh2-P,As}][PF6]
(16) and [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2P (CH2)3N(C@
Me2)-P,N}][PF6] (17), after intermolecular condensation between
the aminophosphine and the acetone.
The 31P-{1H} NMR spectra showed a singlet at d28.61 in agree-
ment with phosphorus coordination. In the 1H NMR spectra the 4-
MeO and H5 resonances were high-field shifted with respect to
those of 1 (vide supra). The IR spectra showed the characteristic
For the mononuclear compounds with chelated heterobidentate
ligands the 31P chemical shifts were influenced by ring size; the
data for (16–26) are summarized in Table 1. With respect to a
non-chelated complex [36], 6-membered rings are shielded

3660
R. Ares et al. / Journal of Organometallic Chemistry 693 (2008) 3655–3667
Table 1
Table 3
31P parameters
Crystal and structure refinement data for complexes 18, 20
a
P
Dring
18 ꢁ 0.5H2O
20 ꢁ 2CH2Cl2
a
16
17
18
19
20
21
22
23
24
25
26
60.67
29.69
29.22
51.83
39.81
40.08
39.50
40.40
36.55
35.90
94.81
17.17
ꢀ13.81
ꢀ14.28
8.33
ꢀ3.69
ꢀ3.42
ꢀ4.00
ꢀ3.10
ꢀ6.95
ꢀ7.60
51.31
Fórmula
Mr
Temperature (K)
Wavelength (Å)
Crystal system
Space Group
C30H39ClN2O6.5PPd
704.45
293(2)
C42H50Cl5N2O6PPd
993.46
100(2)
0.71073
0.71073
Triclinic
Triclinic
ꢀ
ꢀ
P1
P1
Cell dimensions
a (Å)
b (Å)
13.695(3)
14.508(3)
17.253(3)
98.405(3)
94.019(4)
100.332(4)
3319.8(12)
4
13.0763(7)
13.4561(7)
15.1561(8)
102.497(10)
106.676(10)
113.146(10)
2178.8(2)
2
c (Å)
a
(°)
a
b (°)
Difference respect to an equivalent phosphorus in a non-chelated analogue
c
(°)
[Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}(Cl)(PPh3)] (P trans to nitrogen d 43.50) [36].
V (Å3)
Z
Dcalc. (mg/m3)
1.409
0.731
1.514
0.818
l
(mmꢀ1
)
whereas 5-membered rings (16, 19 and 26) are deshielded. The
presence of the more electronegative nitrogen heteroatom in the
phosphine backbone gives an unusually large value of Dring for
compound 26, similar to that described in related complexes [45].
Crystal size (mm)
2hmax (°)
Independent reflections [R(int)
S
0.31 ꢂ 0.25 ꢂ 0.12
0.43 ꢂ 0.35 ꢂ 0.12
57.78
56.64
]
1498 (0.0503)
0.910
0.0626
0.1858
0.998
10386 (0.0166)
1.044
0.0210
0.0525
0.436
R [F, I > 2
wR [F2, all data]
max
(e Å3)
r
(I)]
2.1. X-ray diffraction analysis
q
Suitable crystals were grown by slowly evaporating chloroform/
n-hexane (1, 5, 15, 16) or dichloromethane/n-hexane (18, 20) solu-
tions of the complexes.
The labeling schemes for all the compounds are shown in Figs.
1–6.
All crystals consist of discrete molecules, separated by normal
van der Waals distances. Crystallographic data and selected inter-
atomic distances and angles are listed in Tables 2–5.
For both complexes the four-coordinated palladium(II) is
bonded to an adjacent ortho-carbon atom (C1) of the deprotonated
Schiff base ligand, to the nitrogen atom of the imine group and to a
chlorine atom (trans to C1), with the fourth coordination position
occupied by another chlorine atom, 1 (Fig. 1), or by a P/As atom,
5 (Fig. 2) thus completing the metal coordination sphere. Note that
in 5, even though the bridging ligand is asymmetric, the dinuclear
molecule is crystallographically centrosymmetric; this is caused by
the disordered distribution of the P and As atoms (population
parameters 50%) and the quasi centrosymmetric nature of the com-
pound, which gives similar environments for both P and As atoms.
This behaviour has been observed in other complexes derived from
the arsino-phosphine ligand [17,46]; however, in compound 16
2.1.1. Molecular structures of [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-
C6,N}(l-Cl)]2 (1) and [{Pd[3,4-(MeO)2C6H2C(H)@N(Cy)-
C6,N](Cl)}2{
l-Ph2P(CH2)2AsPh2}] (5)
The crystal structure comprises a centrosymmetric dinuclear
molecule (half molecule per asymmetric unit) and two, 1, or four,
5, CHCl3 solvent molecules.
Table 2
Crystal and structure refinement data for complexes 1, 5, 15 and 16
1 ꢁ 2CHCl3
5 ꢁ 4CHCl3
15 ꢁ 2CHCl3
16 ꢁ 0.5CHCl3
Fórmula
Mr
Temperature (K)
Wavelength (A)
Crystal system
Space group
C32H42Cl8N2O4Pd2
1015.08
293(2)
C60H68AsCl14N2O4PPd2
1696.15
293(2)
0.71073
Monoclinic
P21/c
C23H38Cl7N3O6Pd
807.11
100(2)
C41.5H44.5Cl1.5F6NO2P2Pd
999.72
293(2)
0.71073
Triclinic
P21/c
0.71073
0.71073
Triclinic
Triclinic
ꢀ
ꢀ
P1
P1
Cell dimensions
a (Å)
b (Å)
7.789(10)
9.103(10)
14.780(10)
96.487(10)
91.392(10)
102.430(10)
1015.6(18)
1
13.669(5)
12.817(5)
20.175(5)
90
90.122(5)
90
3535(2)
2
1.594
10.185(2)
13.779(2)
13.828(2)
60.130(2)
77.721(3)
82.864(3)
1643.9(5)
2
12.787(9)
12.653(9)
28.61(2)
90
100.592(13)
90
4550(6)
4
1.459
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dcalc. (mg/m3)
1.660
1.448
1.631
1.174
l
(mmꢀ1
)
1.570
1.346
Crystal size (mm)
2hmax (°)
0.55 ꢂ 0.50 ꢂ 0.45
0.24 ꢂ 0.18 ꢂ 0.03
0.39 ꢂ 0.34 ꢂ 0.10
0.50 ꢂ 0.39 ꢂ 0.30
56.58
56.64
56.61
57.32
Independent reflections [R(int)
S
]
4792 (0.0143)
1.063
8458 (0.0889)
0.991
7481 (0.0121)
1.055
10806 (0.0427)
1.016
R [F, I > 2
wR [F2, all data]
max
(e Å3)
r
(I)]
0.0333
0.0943
0.881
0.0646
0.1621
0.987
0.0209
0.0561
0.702
0.0525
0.1704
1.356
q

R. Ares et al. / Journal of Organometallic Chemistry 693 (2008) 3655–3667
3661
Table 4
Selected bond distances (A) and angles (°) for complexes 1, 5, 15 and 16
Table 5
Selected bond distances (A) and angles (°) for complexes 18, 20
1
5
15
16
18
20
Pd(1)–C(1)
Pd(1)–N(1)
Pd(1)–N(2)
Pd(1)–N(3)
1.973(3)
2.038(2)
2.031(6)
2.111(4)
2.032(1)
2.078(1)
2.105(1)
2.209(1)
2.055(4)
2.108(4)
Pd(1)–C(1)
Pd(1)–N(1)
Pd(1)–P(1)
Pd(1)–N(2)
2.013(6)
2.117(5)
2.246(2)
2.176(5)
2.022(1)
2.120(1)
2.218(4)
2.131(1)
Pd(1)–Cl(1)
Pd(1)–Cl(1A)
2.329(1)
2.463(1)
2.403(2)
Pd(1)–As(1)
Pd(1)–As(2)
Pd(1)–P(1)
Pd(1)–As(1)
C(1)–C(6)
C(6)–C(7)
2.262(2)
2.425(1)
1.400(6)
1.442(6)
1.290(6)
80.89(16)
Pd(1)–Cl(1)
Pd(1)–Cl(2)
C(1)–C(6)
C(6)–C(7)
2.313(1)
1.406(8)
1.429(8)
1.289(7)
81.3(2)
1.392(3)
1.445(4)
1.281(4)
81.33(10)
94.31(8)
85.81(3)
98.71(6)
1.405(2)
1.442(2)
1.287(2)
81.17(5)
1.401(9)
1.444(9)
1.268(8)
80.9(2)
95.0(2)
91.47(17)
92.4(2)
112.3(4)
118.4(6)
116.7(6)
111.4(5)
1.408(2)
1.453(2)
1.284(2)
81.16(5)
99.19(4)
85.41(3)
96.51(4)
112.28(9)
117.93(12)
116.70(12)
111.39(9)
N(1)–C(7)
N(1)–C(7)
C(1)–Pd(1)–N(1)
C(1)–Pd(1)–Cl(1)
Cl(1)–Pd(1)–Cl(1A)
N(1)–Pd(1)–Cl(1A)
C(1)–Pd(1)–P(1)
C(1)–Pd(1)–As(1)
C(1)–Pd(1)–N(2)
N(2)–Pd(1)–N(3)
P(1)–Pd(1)–As(1)
As(1)–Pd(1)–Cl(1)
N(1)–Pd(1)–Cl(1)
N(1)–Pd(1)–P(1)
N(1)–Pd(1)–N(3)
N(1)–Pd(1)–As(1)
C(7)–N(1)–Pd(1)
N(1)–C(7)–C(6)
C(1)–C(6)–C(7)
C(6)–C(1)–Pd(1)
C(1)–Pd(1)–N(1)
C(1)–Pd(1)–P(1)
P(1)–Pd(1)–N(2)
N(1)–Pd(1)–N(2)
C(7)–N(1)–Pd(1)
N(1)–C(7)–C(6)
C(1)–C(6)–C(7)
C(6)–C(1)–Pd(1)
As(1)–Pd(1)–As(2)
As(2)–Pd(1)–Cl(2)
Cl(2)–Pd(1)–Cl(1)
Cl(1)–Pd(1)–As(1)
98.12(13)
83.42(5)
93.31(17)
97.81(5)
83.71(5)
91.27(5)
93.92(14)
98.00(5)
97.64(10)
112.4(3)
118.7(4)
117.1(4)
110.8(3)
113.83(18)
117.1(2)
114.7(2)
111.9(4)
118.4(6)
117.7(6)
110.5(4)
112.97(10)
118.44(13)
115.94(13)
111.35(10)
5 reflect the higher trans influence of the aryl carbon as compared
to the imine nitrogen atom of the organic ligand [50].
112.91(18)
For complex 1 the mean deviation from the least-squares planes
of the Pd1 C1 N1 Cl1 Cl1A plane (plane 1), the cyclometallated ring
(plane 2) and the metallated phenyl ring (plane 3) are 0.0153,
0.0124 and 0.0026 Å. The angles between planes are as follows:
1/2: 0.5°, 1/3: 1.5 y 2/3: 1.6°. Thus, apart from the MeO groups
and the cyclohexyl rings, the other five rings in the complex are
near coplanar, as observed in other halide-bridged cyclometallated
complexes [47–49], and in contrast with the situation in similar
non-planar Pd2X2 bridging units [51,52].
(vide infra) where the P and the As atoms are in different chemical
surroundings, the technique clearly distinguishes both atoms.
The Pd–C and Pd–N bond lengths for both palladium complexes
are similar to those reported for related compounds [16,47–49].
The differing Pd–Cl(1)trans-N [2.329(1)] and PdCl(1A)trans-C [2.463
(1)] bond lengths in compound 1 and PdCl(1)trans-C [2.403(2)] for
O(1)
O(2)
C(3)
C(2)
C(4)
Cl(1)
C(1)
C(5)
Pd(1)
C(6)
C(7)
N(1)
C(8)
Fig. 1. Molecular structure of [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}(l-Cl)]2 (1), with labelling scheme. Hydrogen atoms have been omitted for clarity.

3662
R. Ares et al. / Journal of Organometallic Chemistry 693 (2008) 3655–3667
O(1)
O(2)
C(4)
C(3)
C(5)
C(6)
C(7)
C(2)
C(1)
P/As(1)
C(16)
Pd(1)
N(1)
C(8)
Cl(1)
Fig. 2. Molecular structure of [{Pd[3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N](Cl)}2 {l-Ph2P(CH2)2AsPh2}] (5), with labelling scheme. Hydrogen atoms have been omitted for clarity.
2.1.2. Molecular structures of [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-
C6,N}{NMe2(CH2)2NMe2-N,N}][ClO4] (15), [Pd{3,4-(MeO)2C6H2
C(H)@N(Cy)-C6,N}{Ph2P(CH2)2AsPh2-P,As}][PF6] (16), [Pd{3,4-
(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2P(CH2)3NH2-P,N}][ClO4] (18),
[Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2PC6H4C(H)@NCy-
P,N}][ClO4] (20)
orate or a hexafluorophosphate (16) anion and two CHCl3 (15),
one half CHCl3 (16) or two CH2Cl2 (20) solvent molecules.
The crystal structure of 18 consists of a mononuclear cation, a
perclorate anion and half molecule of H2O; in this case, the asym-
metric unit comprises two cations with similar structures, of which
only one will be discussed.
The crystal structures of compounds 15, 16 and 20 comprise a
mononuclear cation (one molecule per asymmetric unit), a percl-
For the mononuclear complex 15 the palladium(II) atom is
bonded to the C1 atom and to three nitrogen atoms, one from
the Schiff base ligand and two from the diamine chelating ligand
(see Fig. 3). In compounds 16, 18 and 20 the palladium(II) atom
O(1)
O(1)
C(3)
O(2)
O(2)
C(3)
C(2)
C(1)
C(2)
C(1)
C(4)
C(4)
C(5)
N(2)
N(3)
C(16)
P(1)
Pd(1)
C(5)
C(6)
C(7)
Pd(1)
C(6)
C(16)
C(17)
C(17)
N(1)
C(7)
As(1)
N(1)
C(8)
C(8)
Fig. 3. Molecular structure of the cation for [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-
C6,N}{NMe2(CH2)2NMe2-N,N}][ClO4] (15), with labelling scheme. Hydrogen atoms
have been omitted for clarity.
Fig. 4. Molecular structure of the cation for [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-
C6,N}{Ph2P(CH2)2AsPh2-P,As}][PF6] (16), with labelling scheme. Hydrogen atoms
have been omitted for clarity.

R. Ares et al. / Journal of Organometallic Chemistry 693 (2008) 3655–3667
3663
is bonded to an ortho-carbon of the phenyl ring, to a nitrogen atom
of the benzylidene ligand, and to the phosphorus and arsenic (16)
or nitrogen (18, 20) atoms of the chelating arsino-phosphine or
phosphinoamine ligand, giving a five- or a six-membered chetale
ring, respectively (see Figs. 4–6).
The sum of angles about palladium is approximately 360° as ex-
pected for a square-planar geometry. The angles between adjacent
atoms in the coordination sphere are close to 90°; the most notice-
able distortion corresponds to the C(1)–Pd(1)–N(1) angle in the
cyclometallated ring, of 81.17(5)° (15), 80.89(16)° (16), 80.9(2)°
(18), 81.16(5)° (20), consequent upon chelation. The geometry
around the palladium atom is slightly distorted square-planar,
the mean deviations from the least-squares plane (plane 1: Pd1,
C1, N1, N2, N3, 15; Pd1, C1, N1, P1, As1, 16; Pd1, C1, N1, P1, N2,
18, 20) are 0.0925, 0.0320, 0.0541 and 0.1622 Å, respectively.
The mean deviations from the least-squares planes determined
for the metallacycle (plane 2: Pd1, C1, C6, C7, N1) and the metallat-
ed phenyl ring (plane 3: C1, C2, C3, C4, C5, C6) are 0.134 and
0.0083 Å (15), 0.0188 and 0.0062 Å (16), 0.0230 and 0.0078 Å
(18), 0.0253 and 0.0094 Å (20), respectively. The angle between
these planes are as follows: 3.7°, 2.9°, 4.8° and 10.5°, also respec-
tively. The angles between plane 1 and the previous planes are:
plane 1/plane 2: 5.5°(15), 2.1°(16), 5.9°(18), 10.5°(20) and plane
1/plane 3: 9.0°(15), 3.1°(16), 10.6°(18), 20.2°(20), with the most
noticeable distortion in compound 20 with the P1 and N2 of the
iminophosphine ligand lying in a different side in relation to the
Pd1 C1 N1 plane (+0.38 and ꢀ0.49 Å, respectively). The torsion an-
gles of 1.0° for C14 C15 C16 P1 and 42.2° for the Pd1 P1 C16 C15
units points to a perturbed envelop conformation of the six-mem-
bered ring of the iminophosphine, similar to that described in
other related complexes [53,54].
O(2)
C(3)
C(2)
C(4)
C(1)
C(5)
P(1)
Pd(1)
C(6)
C(7)
C(16)
C(17)
The palladium–carbon bond lengths, (2.032(1) Å (15),
2.055(4) Å (16), 2.013(6) Å (18), 2.022(1) Å (20)), are somewhat
shorter than the expected value of 2.081 Å (based on the sum of
the covalent radii for carbon(sp2) and palladium, 0.771 and
1.31 Å, respectively) [55].
N(1)
C(8)
C(18)
N(2)
The palladium-nitrogen bond lengths in the cyclometallated
ring (Pd–N1), (2.078(1) Å (15), 2.108(4) Å (16), 2.117(5) Å (18),
2.120(1) Å (20)), are longer than the predicted single bond value
of 2.011 Å (based on the sum of covalent radii for nitrogen(sp2)
and palladium, 0.701 and 1.31 Å, respectively), and reflect the
influence of the atom in trans position. In 15 the distinct palla-
dium–nitrogen bond lengths with the diamine chelating ligand
(Pd–N2 = 2.105(1) Å and Pd–N3 = 2.209(1) Å) reflect the differing
trans influence of the metallated carbon and the nitrogen atoms
of the Schiff base ligand.
Fig. 5. Molecular structure of the cation for [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-
C6,N}{Ph2P(CH2)3NH2-P,N}][ClO4] (18), with labelling scheme. Hydrogen atoms
have been omitted for clarity.
The Pd–P (2.262(2) Å (16), 2.246(2) Å (18), 2.218(4) Å (20), and
Pd–As (2.425(1) (16)) bond distances, similar those found in re-
lated palladium complexes [17,56,57], are shorter than the sum
of the single bond radii for palladium and the corresponding atoms
(2.41 Å for Pd–P and 2.55 Å for Pd–As), suggesting partial double
bond character between the palladium and the donor atom.
O(1)
O(2)
C(3)
C(2)
C(4)
3. Experimental
P(1)
C(1)
C(5)
CAUTION (safety note): perchlorate salts of metal complexes
with organic ligands are potentially explosive. Only small amounts
of these materials should be prepared and handled with great
caution.
C(6)
Pd(1)
C(16)
C(15)
C(7)
3.1. General remarks
N(1)
N(2)
All solvents were distilled prior to use from appropriate drying
agents [58]. Chemicals were used as supplied from commercial
sources. Elemental analyses (C, H, N) were carried out in a Carlo-
Erba 1108 elemental analyser. IR spectra were recorded as KBr pel-
lets or Nujol mulls on a Perkin–Elmer 1330 spectrophotometer.
Mass spectra were obtained in a QUATRO mass spectrometer with
Cs ion-gun and 3-NBA matrix. NMR spectra were obtained as CDCl3
solutions and referenced to SiMe4 (1H, 13C-{1H}) or 85% H3PO4 (31P-
{1H}); and were recorded on a Bruker AC-200F spectrometer
(200.0 MHz for 1H, 50.3 MHz for 13C-{1H}, 81.0 MHz for 31P-{1H}).
Conductivity measurements were made on a Crison GLP 32 con-
C(14)
C(8)
Fig. 6. Molecular structure of the cation for [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-
C6,N}{Ph2PC6H4C(H)@N(Cy)-P,N}][ClO4] (20), with labelling scheme. Hydrogen
atoms have been omitted for clarity.

3664
R. Ares et al. / Journal of Organometallic Chemistry 693 (2008) 3655–3667
ductivimeter using 10ꢀ3 M solutions in dry acetonitrile at room
temperature (298 K). The ligand Ph2PN(Me)C(@O)Me was prepared
as described previously in the literature [34]. The syntheses of the
heteroligands Ph2PC6H4C(H)@NCy, Ph2PC6H4C(H)@NCMe3, Ph2-
Yield: 75%. Anal. Calc. for C44H56Cl2N3O4PPd2: C, 52.5; H, 5.6; N,
4.1. Found: C, 52.2; H, 5.6; N, 3.9%. IR: (C@N): 1608m. FAB-Mass:
m
581 [LPd(PN)]+, 352 [LPd]+ 581, 246 [L]+. 1H NMR: d = 3.10 (s, 4-
OMe), 3.80, 3.81 (s, OMe), 6.10 (d, H5, 4J(PH5) = 5.4 Hz), 6.78 (s,
H50), 6.80 (s, H2), 7.97 (s, Hi0), 8.03 (d, Hi, 4J(PHi) = 6.8 Hz). 13C-
{1H} NMR: d = 25.3 (s, C9, C11), 25.7 (s, C10), 29.6 (s, CH2CH2P),
33.7 (s, C8, C12), 41.0 (d, CH2P, 1J(PC) 8 3.9 Hz), 65.0 (s, C7), 55.4,
(s, 4-OMe), 55.9, 56.0, 56.1 (s, OMe), 111.6 (s, C2), 121.2 (d, C5,
3J(PC5) 8 11.4 Hz), 125.0 (s, C50), 127.2 (d, Ci, 1J(PCi) = 49.7 Hz),
129.3 (d, Cm, 3J(PCm) = 10.6 Hz), 132.0 (d, Cp, 4J(PCp) = 2.8 Hz),
134.2 (d, Co, 2J(PCo) = 12.8 Hz), 140.5 (s, C1), 146.0 (s, C3),
149.7(d, C4, 4J(PC4) = 5.6 Hz), 149.8 (s, C40), 151.1(d, C6,
2J(PC6) = 2.8 Hz), 151.2 (s, C60), 171.3 (s, C@N0), 171.3 (d, C@N,
3J(PC@N) = 3.6 Hz). 31P-{1H} NMR: d 8 52.58 (s).
PC6H4C(H)@NNMe2,
Ph2PC6H4C(H)@NNHMe,
Ph2PC6H4C(H)@
NNHPh were performed by heating chloroform solutions of the
appropriate quantities of o-(diphenylphosphino)benzaldehyde
and the corresponding amine or hydrazine in a Dean–Stark appara-
tus under reflux.
3.2. Syntheses
3.2.1. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}(
l-Cl)]2 (1)
The synthesis of 1 has been reported previously from this labo-
ratory [36].
13C-{1H} NMR: d = 24.8 (s, C9, C11), 25.4 (s, C10), 32.9 (s, C8,
C12), 55.9, 56.2 (s, OMe), 63.5 (s, C7), 109.9 (s, C5), 115.8 (s, C2),
138.0 (s, C1), 146.5 (s, C3), 147.7 (s, C6), 148.0 (s, C4), 169.4 (s,
C@N).
3.2.7. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2PC4H6(NH)CH2PPh2-
P,P}]-[ClO4] (7)
To a suspension of 1 (20.00 mg, 0.026 mmol) in dichlorometh-
ane (ca. 15 mL), Ph2PC4H6(NH)CH2PPh2 (23.57 mg, 0.052 mmol)
was added. The mixture was stirred for 2 h at room temperature,
after which an estequiometric amount of sodium perclorate was
added and the resultant solution stirred for a further 1 h. Then
the solvent was removed under reduced pressure, and the residue
triturated with hexane to yield a solid, which was filtered off and
dried in vacuo. The desired complex was recrystallized from chlo-
roform/n-hexane as yellow microcrystals.
3.2.2. [{Pd[3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N](Cl)}2{
CH2PPh2}] (2)
l-Ph2PC4H6(NH)
To a suspension of 1 (40.00 mg, 0.052 mmol) in dichlorometh-
ane (ca. 10 mL), Ph2PC4H6(NH)CH2PPh2 (21.22 mg, 0.047 mmol)
was added. The mixture was stirred for 12 h at room temperature,
after which the precipitate formed was filtered off, dried in vacuo,
and recrystallized from chloroform/n-hexane to yield the desired
product as a yellow solid.
Yield: 66%. Anal. Calc. for C44H49ClN2O6P2Pd: C, 58.3; H, 5.4; N,
3.1. Found: C, 58.3; H, 5.1; N, 3.3%. IR: m(C@N): 1612m. FAB-Mass:
Yield: 67%. Anal. Calc. for C59H65Cl2N3O4P2Pd2: C, 57.8; H, 5.3; N
805 [M]+, 291 [(L-2MeO)Pd]+. 1H NMR: d = 2.99 (s, 4-OMe), 3.79 (s,
3.4. Found: C, 57.5; H, 5.3; N, 3.1%. IR:
m
(C@N): 1614m. FAB-Mass:
3-OMe), 5.94 (dd, H5, 4J(PbH5) = 8.4 Hz, 4J(P H5) = 5.4 Hz), 6.89 (s,
a
1190 [M-Cl]+, 801 [LPd(PP)]+. 1H NMR: d = 2.83, 2.99 (s, 4-OMe),
3.76 (s, 3-OMe), 5.78, 5.96 (d, H5, 4J(PH5) = 6.4, 5.9 Hz), 6.83,
6.84 (s, H2). 31P-{1H} NMR: d = 39.26 (s), 41.02 (s).
H2), 8.11 (d, Hi, 4J(PHi) = 6.4 Hz). 31P-{1H} NMR: d = 1.59 (d, Pb,
5J(PP) = 115.1 Hz), 39.85 (d, P ).
a
3.2.8. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{(o-Tol)2P(CH2)2P
(o-Tol)2-P,P}] [ClO4] (8)
Complex 8 was synthesized with a procedure similar to that de-
scribed for complex 7, using (o-Tol)2P(CH2)2P(o-Tol)2.
Yield: 51%. Anal. Calc. for C45H52ClNO6P2Pd: C, 59.6; H, 5.8; N,
3.2.3. [{Pd[3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N](Cl)}2{
AsPh2}] (3)
Complex 3 was synthesized with a procedure similar to that de-
scribed for complex 2, but using Ph2As(CH2)2AsPh2.
l-Ph2As(CH2)2
Yield: 51%. Anal. Calc. for C56H64Cl2N2O4As2Pd2: C, 53.3; H, 5.1;
1.5. Found: C, 59.9; H, 5.7; N, 1.8%. IR: m(C@N): 1618m. FAB-Mass:
N, 2.2. Found: C, 53.6; H, 5.0; N, 2.1%. IR:
m
(C@N): 1616m. FAB-
806 [M]+. 1H NMR: d = 2.97 (s, 4-OMe), 3.82 (s, 3-OMe), 6.17 (dd,
Mass: 838 [LPd(AsAs)]+, 352 [LPd]+, 246 [L]+. 1H NMR: d = 2.76 (s,
H5, 4J(PbH5) = 8.3 Hz, 4J(P H5) = 5.9 Hz), 7.13 (s, H2), 8.31 (d, Hi,
a
4-OMe), 3.75 (s, 3-OMe), 6.02 (s, H5), 6.82 (s, H2), 7.95 (s, Hi).
4J(PHi) = 8.3 Hz). 31P-{1H} NMR: d = 41.91 (d, Pb, 3J(PP) = 17.2 Hz),
55.14 (d, P ).
a
3.2.4. [{Pd[3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N](Cl)}2{
C6H4}] (4)
Complex 4 was synthesized with a procedure similar to that de-
scribed for complex 2, but using 1,3-(NH2CH2)C6H4.
l-1,3-(NH2CH2)2
3.2.9. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2As(CH2)2AsPh2-
As,As}][ClO4] (9)
Complex 9 was synthesized using a procedure similar to that
described for complex 7, but using Ph2As(CH2)2AsPh2.
Yield: 78%. Anal. Calc. for C41H44ClNO6As2Pd: C, 52.5; H, 4.7; N,
Yield: 67%. Anal. Calc. for C38H52Cl2N4O4Pd2: C, 50.0; H, 5.7; N,
6.1. Found: C, 49.9; H, 5.6; N, 6.1%. IR: m(C@N): 1607m. FAB-Mass:
488 [LPd(NN)]+, 352 [LPd]+, 246 [L]+. 1H NMR: d = 3.89, 3.90 (s,
1.5. Found: C, 53.1; H, 5.0; N, 1.4%. IR: m(C@N): 1626m. FAB-Mass:
OMe), 6.27 (s, H5), 6.84 (s, H2), 8.03 (s, Hi).
838 [M]+. 1H NMR: d = 2.96 (s, 4-OMe), 3.84 (s, 3-OMe), 6.32 (s, H5),
7.19 (s, H2), 8.29 (s, Hi).
3.2.5. [{Pd[3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N](Cl)}2{
AsPh2}] (5)
Complex 5 was synthesized with a procedure similar to that de-
scribed for complex 2, but using Ph2P(CH2)2AsPh2.
l-Ph2P(CH2)2
3.2.10. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{NH2(CH2)3NH2-
N,N}][ClO4] (10)
Complex 10 was synthesized with a procedure similar to that
described for complex 7, but using NH2(CH2)3NH2.
Yield: 45%. Anal. Calc. for C18H30ClN3O6Pd: C, 41.1; H, 5.7; N, 8.0.
Yield: 30%. Anal. Calc. for C56H64Cl2N2O4AsPPd2: C, 55.1; H, 5.3;
N, 2.3. Found: C, 55.1; H, 5.1; N, 2.2%. IR: m(C@N): 1619m. FAB-
Mass: 795 [LPd(PAs)]+. 1H NMR: d = 2.73, 2.84 (s, 4-OMe), 3.75 (s,
Found: C, 41.0; H, 5.9; N, 7.7%. IR: m(C@N): 1611m. FAB-Mass: 426
4
3-OMe), 5.91 (d, H5, J(PH5) = 6.4 Hz), 6.00 (s, H50), 6.81 (s, H2).
[M]+, 352 [LPd]+, 248 [L+H]+. 1H NMR: d = 3.66, 3.80 (s, OMe), 6.53
31P-{1H} NMR: d = 39.50 (s).
(s, H5), 7.11 (s, H2), 8.12 (s, Hi).
3.2.6. [{Pd[3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N](Cl)}2{
NH2}] (6)
l-Ph2P(CH2)2
3.2.11. 3.2.11.[Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-
C6,N}{NH2(C6H8)CH2(C6H8)NH2-N,N}][ClO4] (11)
Complex 6 was synthesized with a procedure similar to that de-
scribed for complex 2, but using Ph2P(CH2)2NH2.
Complex 11 was synthesized with a procedure similar to that
described for complex 7, but using NH2(C6H8)CH2(C6H8)NH2.

R. Ares et al. / Journal of Organometallic Chemistry 693 (2008) 3655–3667
3665
Yield: 49%. Anal. Calc. for C28H46ClN3O6Pd: C, 50.8; H, 7.0; N, 6.3.
Yield: 40%. Anal. Calc. for C33H42F6N2O2P2Pd: C, 50.7; H, 5.4; N,
Found: C, 50.3; H, 7.4; N, 6.5%. IR:
m
(C@N): 1609m. FAB-Mass: 352
3.6. Found: C, 51.2; H, 5.7; N, 3.9%. IR: m(C@N): 1616m, 1648m.
[LPd]+, 291 [(Lꢀ2OMe)Pd]+, 248 [L+H]+. 1H NMR: d = 3.83, 3.92 (s,
FAB-Mass: 635 [M]+, 352 [LPd]+, 291 [(L-2OMe)Pd]+. 1H NMR:
d = 2.04, 2.28 (s, N(C@Me2)), 2.91 (s, 4-OMe), 3.81 (s, 3-OMe),
5.92 (d, H5, 4J(PH5) = 5.9 Hz), 6.95 (s, H2), 8.11 (d, Hi,
4J(PHi) = 7.3 Hz). 31P-{1H} NMR: d = 29.69 (s).
OMe), 6.36 (s, H5), 6.88 (s, H2), 7.76 (s, Hi).
3.2.12. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{1,3-(NH2CH2)2C6H4-
N,N}][ClO4] (12)
Complex 12 was synthesized with a procedure similar to that
described for complex 7, but using 1,3-(NH2CH2)2C6H4.
Yield: 34%. Anal. Calc. for C23H32ClN3O6Pd: C, 47.0; H, 5.5; N, 7.1.
3.2.18. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2P(CH2)3NH2-
P,N}][ClO4] (18)
Complex 18 was synthesized with a procedure similar to that
described for complex 7, using PPh2(CH2)3NH2 in dichloromethane.
Yield: 52%. Anal. Calc. for C30H38ClN2O6PPd: C, 51.8; H, 5.5; N,
Found: C, 46.9; H, 5.4; N, 7.3%. IR: m(C@N): 1617m. FAB-Mass: 488
[M]+, 352 [LPd]+, 248 [L+H]+. 1H NMR: d = 3.85, 3.94 (s, OMe), 6.53
(s, H5), 6.92 (s, H2), 7.89 (s, Hi).
4.0. Found: C, 51.5; H, 5.6; N, 4.0%. IR: m(C@N): 1618m. FAB-Mass:
595 [M]+, 352 [LPd]+, 291 [(Lꢀ2OMe)Pd]+, 248 [L+H]+. 1H NMR:
d = 2.89 (s, 4-OMe), 3.79 (s, 3-OMe), 5.91 (d, H5, 4J(PH5) = 6.4 Hz),
6.92 (s, H2), 8.09 (d, Hi, 4J(PHi) = 7.8 Hz).
3.2.13. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{1,3-(NH2)2C5H3N-
N,N}][ClO4] (13)
Complex 13 was synthesized with a procedure similar to that
described for complex 7, using 1,3-(NH2)2C5H3N.
Yield: 31%. Anal. Calc. for C20H27ClN4O6Pd: C, 42.8; H, 4.9; N,
13C-{1H} NMR: d = 29.7 (s, CH2CH2P), 23.5 (s, NCH2), 25.7 (s,
C10), 25.1 (s, C9, C11), 33.6 (s, C8, C12), 42.2 (d, CH2P,
1J(PC) = 5.0 Hz), 55.2, (s, 4-OMe) 55.9 (s, 3-OMe), 62.0 (s, C7),
111.8 (s, C2), 121.2 (d, C5, 3J(PC5) = 12.8 Hz), 127.2 (d, Ci,
1J(PCi) = 49.7 Hz), 129.3 (d, Cm, 3J(PCm) = 10.6 Hz), 132.0 (d, Cp,
4J(PCp) = 2.8 Hz), 134.2 (d, Co, 2J(PCo) = 12.8 Hz), 140.3 (s, C1),
146.2 (s, C3), 149.4 (d, C4, 4J(PC4) = 6.3 Hz), 149.6 (d, C6,
2J(PC6) = 2.1 Hz), 172.0 (d, C@N, 3J(PC@N) = 3.5 Hz). 31P-{1H}
NMR: d = 29.22 (s).
10.0. Found: C, 42.7; H, 4.9; N, 10.2%. IR: m(C@N): 1607m. FAB-
Mass: 461 [M]+, 352 [LPd]+, 248 [L+H]+. 1H NMR: d = 3.57, 3.80 (s,
OMe), 5.64 (s, H5), 6.86 (s, H2), 7.85 (s, Hi).
3.2.14. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{NH2(C6H4)O(C6H4)
NH2-N,N}] [ClO4] (14)
Complex 14 was synthesized with a procedure similar to that
described for complex 7, but using NH2(C6H4)O(C6H4)NH2.
Yield: 38%. Anal. Calc. for C27H32ClN3O7Pd: C, 49.7; H, 5.0; N, 6.4.
3.2.19. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2P(CH2)2NH2-
P,N}][ClO4] (19)
Found: C, 49.4; H, 5.0; N, 6.6%. IR:
m
(C@N): 1615m. FAB-Mass: 552
Complex 19 was synthesized with a procedure similar to that
described for complex 7, using PPh2(CH2)2NH2 in dichloromethane.
Yield: 62%. Anal. Calc. for C29H36ClN2O6PPd: C, 51.1; H, 5.3; N,
[M]+, 352 [LPd]+, 248 [L+H]+. 1H NMR: d = 3.81, 3.91 (s, OMe), 6.67
(s, H5), 6.80 (s, H2), 7.72 (s, Hi).
4.1. Found: C, 50.9; H, 5.3; N, 4.0%. IR: m(C@N): 1615m. FAB-Mass:
3.2.15. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{NMe2(CH2)2NMe2-
N,N}][ClO4] (15)
Complex 15 was synthesized with a procedure similar to that
described for complex 7, but using NMe2(CH2)2NMe2.
Yield: 50%. Anal. Calc. for C21H36ClN3O6Pd: C, 44.4; H, 6.4; N, 7.4.
581 [M]+, 291 [(Lꢀ2OMe)Pd]+. 1H NMR: d = 3.05 (s, 4-OMe), 3.80 (s,
3-OMe), 6.07 (d, H5, 4J(PH5) = 5.4 Hz), 6.92 (s, H2), 8.06 (d, Hi,
4J(PHi) = 8.8 Hz). 31P-{1H} NMR: d = 51.83 (s).
3.2.20. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2PC6H4C(H)@
NC6H11-P,N}] [ClO4] (20)
Complex 20 was synthesized with a procedure similar to that
described for complex 7, using Ph2PC6H4C(H)@NCy.
Yield: 21%. Anal. Calc. for C40H46ClN2O6PPd: C, 58.3; H, 5.6; N,
Found: C, 44.6; H, 6.4; N, 7.2%. IR: m(C@N): 1618m. FAB-Mass: 468
[M]+, 352 [LPd]+. 1H NMR: d = 3.82, 3.96 (s, OMe), 6.68 (s, H5), 6.94
(s, H2), 7.91 (s, Hi).
13C-{1H} NMR: d = 25.2 (s, C9, C11), 25.8 (s, C10), 34.0 (s, C8,
C12), 48.5, 51.5 (s, NCH3), 56.2, 56.4 (s, OMe), 60.7, 64.6 (s,
CH2CH2N), 63.5 (s, C7), 111.6 (s, C2), 115.0 (s, C5), 139.2 (s, C1),
147.4, 147.9 (s, C3, C6), 149.8 (s, C4), 174.9 (s, C@N).
3.4. Found: C, 58.1; H, 5.4; N, 3.1%. IR: m(C@N): 1617m, 1648m.
FAB-Mass: 723 [M]+, 352 [LPd]+, 291 [(L-2OMe)Pd]+. 1H NMR:
d = 3.05 (s, 4-OMe), 3.83 (s, 3-OMe), 6.03 (d, H5, 4J(PH5) = 6.3 Hz),
6.96 (s, H2), 8.27 (d, Hi, 4J(PHi) = 7.8 Hz), 8.68 (d, Hi0,
4J(PHi0) = 2.4 Hz). 31P-{1H} NMR: d = 39.81 (s).
3.2.16. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2P(CH2)2AsPh2-
P,As}][PF6] (16)
To a suspension of 1 (20.00 mg, 0.026 mmol) in acetone (ca.
15 mL), Ph2P(CH2)2AsPh2 (23.00 mg, 0.052 mmol) was added. The
mixture was stirred for 2 h at room temperature, after which
ammonium hexafluorophosphate in estequiometric amount was
added and the resulting solution stirred for a further 1 h. Then,
water (ca. 40 cm3) was added dropwise and the resulting mixture
stirred for 2 h. The precipitate formed was filtered off, washed with
water (2 ꢂ 5 mL) and dried in vacuo. The desired complex was
recrystallized from chloroform/n-hexane.
3.2.21. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2PC6H4C(H)@
NC(CH3)3-P,N}] [ClO4] (21)
Complex 21 was synthesized with a procedure similar to that
described for complex 7, using Ph2PC6H4C(H)@NCMe3.
Yield: 35%. Anal. Calc. for C38H44ClN2O6PPd: C, 57.2; H, 5.6; N,
3.5. Found: C, 57.3; H, 5.8; N, 3.6%. IR: m(C@N): 1615m, 1628m.
FAB-Mass: 697 [M]+, 291 [(L-2OMe)Pd]+. 1H NMR: d = 1.26, 1.33
(s, C(CH3)3), 3.08 (s, 4-OMe), 3.82 (s, 3-OMe), 5.99 (d, H5,
4J(PH5) = 6.0 Hz), 6.97 (s, H2), 8.14 (d, Hi, 4J(PHi) = 7.8 Hz) 8.82
Yield: 46%. Anal. Calc. for C41H44F6NO2AsP2Pd: C, 52.4; H, 4.7; N,
4
(d, Hi0, J(PHi0) = 3.5 Hz). 13C-{1H} NMR: d = 25.4 (s, C9, C11), 25.6
1.5. Found: C, 52.5; H, 4.5; N, 1.4%. IR: m(C@N): 1611m. FAB-Mass:
794 [M]+, 291 [(Lꢀ2OMe)Pd]+, 248 [L+H]+. 1H NMR: d = 2.97 (s, 4-
OMe), 3.83 (s, 3-OMe), 6.11 (d, H5, 4J(PH5) = 5.8 Hz), 7.07 (s, H2),
8.25 (d, Hi, 4J(PHi) = 8.8 Hz). 31P-{1H} NMR: d = 60.67 (s).
(s, C10), 29.7, 30.9 (s, NC(CH3)3), 55.0, (s, 4-OMe) 56.0 (s, 3-OMe),
64.2 (s, C7), 64.2, 64.6 (s, NC(CH3)3), 111.2 (s, C2), 121.5 (d, C5,
3J(PC5) = 12.8 Hz), 123.0 (d, Ci, 1J(PCi) = 49.1 Hz), 130.1 (d, Cm,
3J(PCm) = 11.4 Hz), 132.6 (d, Cp, 4J(PCp) = 2.3 Hz), 133.1 (d, Co,
2J(PCo) = 12.7 Hz), 140.1 (d, C1, 3J(PC1) = 1.4 Hz), 146.6 (s, C3),
149.8 (d, C4, 4J(PC4) = 7.1 Hz), 153.1 (d, C6, 2J(PC6) = 2.7 Hz),
3.2.17. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2P(CH2)3N(C@Me2)-
P,N}][PF6] (17)
Complex 17 was synthesized with a procedure similar to that
described for complex 7, albeit in acetone, using PPh2(CH2)3NH2.
167.9
(d,
C@N0,
3J(PC@N) = 4.8 Hz),
171.4
(d,
C@N,
3J(PC@N) = 4.0 Hz). 31P-{1H} NMR: d = 40.08 (s).

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R. Ares et al. / Journal of Organometallic Chemistry 693 (2008) 3655–3667
3.2.22. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2PC6H4C(H)@
NNMe2-P,N}] [ClO4] (22)
OMe), 5.97 (d, H5, 4J(PH5) = 7.3 Hz), 6.89 (s, H2). 31P-{1H} NMR:
d = 94.81 (s).
Complex 22 was synthesized with a procedure similar to that
described for complex 7, using Ph2PC6H4C(H)@NNMe2.
Yield: 59%. Anal. Calc. for C36H41ClN3O6PPd: C, 55.1; H, 5.3; N,
3.2.27. X-ray crystallographic study
Three-dimensional X-ray data were collected on a Bruker Smart
1K and Bruker AXS CCD diffractometers using graphite-monochro-
5.4. Found: C, 55.0; H, 5.1; N, 5.2%. IR: m(C@N): 1617m, 1642m.
FAB-Mass: 684 [M]+, 291 [(L-2OMe)Pd]+. 1H NMR: d = 3.02 (s,
N(CH3)2), 3.08 (s, 4-OMe), 3.82 (s, 3-OMe), 5.96 (d, H5,
mated Mo Ka radiation. All the measured reflections were cor-
rected for Lorentz and polarisation effects and for absorption by
semi-empirical methods based on symmetry-equivalent and re-
peated reflections. The structures were solved by direct methods
and refined by full matrix least-squares on F2.
4
4J(PH5) = 6.3 Hz), 6.95 (s, H2), 7.90 (d, Hi0, J(PHi0) = 2.4 Hz), 8.08
(d, Hi, 4J(PHi) = 7.3 Hz). 31P-{1H} NMR: d = 39.50 (s).
3.2.23. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2PC6H4
C(H)@NNHMe-P,N}] [ClO4] (23)
Complex 23 was synthesized with a procedure similar to that
described for complex 7, using Ph2PC6H4C(H)@NNHMe.
Yield: 36%. Anal. Calc. for C35H39ClN3O6PPd: C, 54.6; H, 5.1; N,
Of the two CH2Cl2 solvent molecules in compound 20 one was
found to be disordered over two positions (76% and 24% occu-
pancy) while in the other one only one of the chloride atoms,
Cl4, was disordered occupying two positions, with each component
having approximately 50% occupancy (0.58% and 0.42%).
Hydrogen atoms were included in calculated positions and re-
fined in riding mode. All non-hydrogen atoms were refined aniso-
tropically. The structure solution and refinement were carried out
using the program package SHELX-97 [59].
5.5. Found: C, 54.2; H, 4.9; N, 5.6%. IR: m(C@N): 1620m, 1640m.
FAB-Mass: 670 [M]+, 291 [(L-2OMe)Pd]+. 1H NMR: d = 2.90 (d,
NHCH3, 3J(HCH3) = 4.3 Hz), 2.98 (s, 4-OMe), 3.90 (s, 3-OMe), 5.85
(d, H5, 4J(PH5) = 6.3 Hz), 6.79 (s, H2), 8.07 (d, Hi, 4J(PHi) = 7.8 Hz).
31P-{1H} NMR: d = 40.40 (s).
Supplementary material
3.2.24. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{Ph2PC6H4
C(H)@NNHPh-P,N}] [ClO4] (24)
CCDC 655186, 655187, 655188, 655189, 655190 and 655191
contains the supplementary crystallographic data for 1, 5, 15, 16,
18 and 20. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Complex 24 was synthesized with a procedure similar to that
described for complex 7, using Ph2PC6H4C(H)@NNHPh.
Yield: 35%. Anal. Calc. for C40H41ClN3O6PPd: C, 57.7; H, 5.0; N,
5.0. Found: C, 57.5; H, 4.8; N, 4.9%. IR: m(C@N): 1610m, 1639m.
FAB-Mass: 732 [M]+, 291 [(Lꢀ2OMe)Pd]+. 1H NMR: d = 3.06 (s, 4-
OMe), 3.78 (s, 3-OMe), 6.05 (d, H5, 4J(PH5) = 6.8 Hz), 6.74 (s, H2),
4
8.70 (d, Hi0, J(PHi0) = 2.0 Hz), 9.82 (s, NH). 31P-{1H} NMR:
Acknowledgements
d = 36.55 (s).
We thank the Ministerio de Educación y Ciencia (Projects
CTQ2006-15621-C02-02/BQU, UDC, and CTQ2006-15621-C02-01/
BQU, USC) and the Xunta de Galicia (Ref. PGIDIT04PXI10301IF)
for financial support.
3.2.25. [Pd{3,4-(MeO)2C6H2C(H)@N(Cy)-C6,N}{2-(Ph2P)C6H4CHO-
P,O}][PF6] (25)
Complex 25 was synthesized with a procedure similar to that
described for complex 16, using Ph2P(C6H4)CHO.
Yield: 32%. Anal. Calc. for C34H35F6NO3P2Pd: C, 51.8; H, 4.5; N,
References
1.8. Found: C, 52.0; H, 4.8; N, 1.6%. IR: m(C@O): 1647s, m(C@N):
1620m. FAB-Mass: 642 [M]+, 291 [(Lꢀ2OMe)Pd]+, 248 [L+H]+. 1H
NMR: d = 2.95 (s, 4-OMe), 3.82 (s, 3-OMe), 5.93 (d, H5,
4J(PH5) = 5.8 Hz), 6.95 (s, H2), 8.08 (d, Hi, 4J(PHi) = 8.8 Hz), 10.15
(d, PCHO, 4J(PH) = 1.5 Hz). 31P-{1H} NMR: d = 35.90 (s).
During the synthesis of compound 25, an additional compound
was obtained previously to the addition of the NaClO4 which was
separated by filtration:
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R. Ares et al. / Journal of Organometallic Chemistry 693 (2008) 3655–3667
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