Cyclometallated complexes of Pd(II) with heterobidentate P, As and P, N coordinating ligands

Article abstract of DOI:10.1016/S0022-328X(02)02066-1

Treatment of the choride-bridged dimer with Ph₂PCH₂CH₂AsPh₂ (arphos) in 1:1 molar ratio in acetone gave the dinuclear complex [{Pd[4-(COH)C₆H₃C(H)=N(Cy)-C2,N](Cl)}₂ (μ-Ph₂

Full text of DOI:10.1016/S0022-328X(02)02066-1

Journal of Organometallic Chemistry 665 (2003) 87ꢀ94
/
www.elsevier.com/locate/jorganchem
Cyclometallated complexes of Pd(II) with heterobidentate P, As and
P, N coordinating ligands
Raquel Ares a, Margarita Lo´pez-Torres a, Alberto Ferna´ndez a, M. Teresa Pereira b,
Antonio Sua´rez a, Roberto Mosteiro a, Jesu´s J. Ferna´ndez a,*, Jose´ M. Vila b,*
a Departamento de Qu´ımica Fundamental, Universidad de A Coruna, 15071 A Coruna, Spain
˜
˜
b Departamento de Qu´ımica Inorga´nica, Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spain
Received 11 August 2002; received in revised form 24 October 2002; accepted 24 October 2002
Abstract
Treatment of the choride-bridged dimer [Pd{4-(COH)C6H3C(H)Ä
in 1:1 molar ratio in acetone gave the dinuclear complex [{Pd[4-(COH)C6H3C(H)Ä
with the arsinophosphine as a bridging ligand, and in 1:2 molar ratio in the presence of NH4PF6 gave the mononuclear compound
[Pd{4-(COH)C6H3C(H)ÄN(Cy)ÃC2,N}(Ph2PCH2CH2AsPh2ÃP,As)][PF6], (3), with the arsinophosphine chelated to the metal
center. Reaction of 1 with Ph2PCH2CH2CH2NH2 in 1:2 molar ratio in acetone and NH4PF6 afforded [Pd{4-(COH)C6H3C(H)Ä
P,N}][PF6] (4), after intermolecular condensation between the aminophosphine and
/
N(Cy)Ã
/
C2,N}(m-Cl)]2 (1), with Ph2PCH2CH2AsPh2 (arphos)
/
N(Cy)ÃC2,N](Cl)}2(m-Ph2PCH2CH2AsPh2)] (2),
/
/
/
/
/
N(Cy)Ã
/
C2,N}{Ph2PCH2CH2CH2N(Ä
/
CMe2)Ã
/
the solvent. Condensation was precluded by treatment in toluene to give the mononuclear compound [Pd{4-(COH)C6H3C(H)Ä
/
N(Cy)Ã
/
C2,N}(Ph2PCH2CH2CH2NH2Ã
/
P,N)][PF6], (5). 1H, 31P{1H} and 13C{1H}-NMR, IR and mass spectral data are given. The
4 have been determined by X-Ray crystallography.
crystal structures of compounds 2ꢀ
/
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Palladium; Metallation; Phosphines; As ligands; P,N ligands
1. Introduction
the key to these reactions. Unfortunately, the metallic
species involved have not been fully characterized in
most of the published work in this field.
A large number of transition metal phosphine com-
plexes have been used in catalysis due to the character-
istic steric and electronic properties of the tertiary
phosphine ligands [1]. The past decade has seen a
growing interest in reactions that include these type of
ligands and complexes, which have proved to be active
catalysts in processes such as the hydrogenation of
aldehydes [2] and aromatic ketones [3] or the carbonyla-
The cyclometallation reaction, i.e. the intramolecular
H bonds of coordinated
activation of aromatic CÃ
/
ligands by transition metals, has been widely investi-
gated in view of their growing chemistry [7] and of the
novel and outstanding applications they present. To
name but a few, the synthesis of new organometallic and
organic compounds, many of which are obtained via
tion of metalꢀmethyl bonds [4], as therapeutic agents in
/
insertion reactions of unsaturated species to the metalꢀ
/
anticancer drugs [5] or as structural fragments on
polystyrene-immobilized catalysts [6]. The pronounced
difference in electronic as well as in steric properties
between the coordinating atoms (i.e. N/P/As, in terms or
the soft and hard base concept) has been shown to be
carbon bond [8]; the design of complexes with interest-
ing photochemical and electrochemical properties [9],
the remarkable and specific antitumor activity toward
some forms of cancer [10] or promising properties as
liquid crystals [11]; and their use in the isolation of
enantiomerically pure chiral compounds [12] or as
efficient catalytic materials [13].
We have been interested in cyclopalladation reactions
in which the metallated carbon atom, bearing sp2
hybridization, is part of an aromatic ring belonging to
* Corresponding authors. Tel.: ꢁ
/
34-981-167000; fax: ꢁ
/
34-981-
167065 (J.J.F.); Tel.: ꢁ34-981-563100; fax: ꢁ
/
/
34-981-595012 (J.M.V.)
E-mail addresses: lujjfs@udc.es (J.J. Ferna´ndez), qideport@usc.es
(J.M. Vila).
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 2 0 6 6 - 1

88
R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 87ꢀ94
/
differently substituted [C, N] Schiff bases derived from
mono- or diamines [14], and dialdehydes [15], as well as
(H)Ä
/
N(Cy)ÃC2,N](Cl)}2(m-Ph2PCH2CH2AsPh2)] (2).
/
The FAB mass spectrum only showed a maximum
peak at m/z 762 assigned to the [LPd(arphos)]ꢁ ion;
nevertheless, the new compound gave a satisfactory
elemental analysis. The 31P{1H}-NMR spectrum
showed a singlet at d 37.78, shifted to higher frequency
from the free phosphine, in agreement with phosphorus
coordination to metal center [24]. The IR spectrum
[C, N, X] (XꢂN, [16] O, [17] S [18]) terdentate ligands.
/
We have also reported five-membered metallacycles
derived from substituted imidazoles [19] and ferroceny-
limines [20]. The corresponding derivatives of these
complexes with nucleophiles such as acetylacetonate,
cyclopentadienyl or mono-, di- and triphospines have
been described. Also, compounds derived from [C, N,
N] terdentate ligands with Pt(II) [21] and [C, P]
bidentate ligands with Pd(II) [22] have been reported.
In the present paper we describe the synthesis and
characterization of new cyclopalladated compounds
derived from heterobidentate P, N and P, As ligands.
showed the shift of the CÄ
wavenumbers, as compared with the free Schiff base
ligand (1638 vs. 1621 cmꢃ1), indicating N-coordination
/N stretch towards lower
O) band at 1687 cmꢃ1
˚
of the CÄ
/
N group [25]. A n(CÄ
/
was assigned to the free formyl group [26].
In the 1H-NMR spectrum the COH and COH? groups
gave rise to two singlets ca. d 9.15 which could not be
unambiguously assigned. The signals were shifted to
lower field from the starting product ca. 0.8 ppm due to
the shielding effect of the arphos phenyl rings, in
agreement with a P, As cis to carbon disposition. The
resonances of the H5/H5? and H6/H6? protons were
overlapped and could not be adequately assigned.
Nevertheless, the corresponding Hi/Hi? and H3/H3?
resonances were clearly distinguished (see Section 3).
Thus, two doublets of doublets at d 8.15 and d 6.80
were assigned Hi and H3, and two doublets at d 8.11
and d 6.86 were assigned to Hi?and H3?; the former two
2. Results and discussion
For the convenience of the reader the compounds and
reactions are shown in Scheme 1. The compounds
described in this paper were characterized by elemental
analysis (C, H, N), by mass spectrometry, and by IR and
1H, 31P{1H} and (in part) 13C{1H}-NMR spectroscopy
(data in Section 3).
Reaction
of
[Pd{4-(COH)C6H3C(H)Ä
/
N(Cy)Ã
/
C2,N}(m-Cl)]2 (1) [23] with Ph2PCH2CH2AsPh2 (ar-
phos) in 1:1 molar ratio, in acetone at room temperature
afforded the dinuclear complex [{Pd[4-(COH)C6H3C-
resonances coupled to the phosphorus nucleus
5.9 Hz]. Similar chloro-
[4J(PHi)ꢂ
bridge splitting reactions of dinuclear compounds de-
/
8.3 Hz, J(PH3)ꢂ
/
4
rived from trisꢀt-butylphosphine with arphos yielded,
/
irrespective of the molar ratio used, complexes in which
the arsinophosphine was acting as a monodentate ligand
via P-coordination, whilst the arsenic atom remained
uncoordinated [22]. The 13C{1H}-NMR spectrum of
compound 2 also showed that some resonances were
well diferentiated for each cyclometallated fragment and
for the arphos phenyl rings (see Section 3). The signals
at d 170.3 and d 170.2 [d, 4J(PC)ꢂ
to C?ÄN and CÄN carbons, respectively, and the signals
/
5.7 Hz] were asigned
/
/
at d 154.4 and d 154.3 to the C2/C2?carbons. These
values were shifted downfield compared with the
spectrum of the free ligand (ca. 12, CÄ
/
N, and 26, C2,
ppm) thereby confirming cyclometallation [23,27]. The
1
ethylene resonances appeared at d 30.7 [d, J(PC)ꢂ5.7
/
Hz] and d 24.4, and were assigned to the PCH2 and
CH2As carbon atoms, respectively. These findings were
confirmed by the X-ray crystal structure determination
of compound 2 (see below).
Treatment of the chloro-bridged complex 1 with
Ph2PCH2CH2AsPh2 and NH4PF6 in 1:2 molar ratio in
acetoneꢀ
nuclear compound [Pd{4-(COH)C6H3C(H)Ä
C2,N}(Ph2PCH2CH2AsPh2ÃP,As)][PF6] (3). The IR
spectrum showed, as the main difference from the
starting material, a broad and strong band at 850
cmꢃ1 arising from the PF6ꢃ counterion [26]. The
/
water at room temperature yielded the mono-
/
N(Cy)Ã
/
/
Scheme 1. (i) Ph2PCH2CH2AsPh2 (1:1), acetone; (ii) Ph2PCH2-
CH2AsPh2, NH4PF6 (1:2), acetoneꢀ
CH2NH2, NH4PF6 (1:2), acetoneꢀwater; (iv) Ph2PCH2CH2CH2NH2,
NH4PF6 (1:2), toluene.
/water; (iii) Ph2PCH2CH2-
/

R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 87ꢀ
/
94
89
MSFAB spectrum showed the corresponding peaks at
m/z 762 and 735 assigned to [M]ꢁ and [MꢃCOH]ꢁ,
NCMe2 resonances in the 1H-NMR spectrum (see
Section 3).
/
respectively, after consideration of the palladium iso-
topes [28]. The 31P{1H}-NMR spectrum showed a
singlet at d 60.27, downfield shifted due to the ring
2.1. Molecular structures of complexes 2, 3 and 4
Suitable crystals were grown by slowly evaporating
size effect in five-membered chelates [29]. The HCÄ
/
N
and H3 resonances in the H-NMR spectrum at d 8.48
1
chloroformꢀ
(3) or acetonitrileꢀ
complexes. The labeling schemes for the compounds
are shown in Figs. 1ꢀ3. All crystals consist of discrete
/
n-hexane (2), dichloromethaneꢀ/n-hexane
and d 6.98 were split by coupling to the 31P nucleus
/ethyl ether (4) solutions of the
4
trans to nitrogen [4J(PHi)ꢂ
/
7.8 Hz, J(PH3)ꢂ
/5.6 Hz],
as we found in related systems with monophosphine
ligands linked to a palladium atom [23,30]. The 13C{1H}
data were consistent with the proposed structure. A
broad signal at d 176.8 and two doublets at d 161.0
/
molecules, separated by normal van der Waals dis-
tances. Crystallographic data and selected interatomic
distances and angles are listed in Tables 1 and 2.
In compound 2, the dinuclear molecule comprises two
palladium centers each of which is bonded to an
adjacent ortho-carbon atom and to the nitrogen atom
of the imine group of the deprotonated Schiff base
ligand and to a chlorine atom (trans to C2). The ligand
[2J(PC)ꢂ
assigned to the HCÄ
/
5.7 Hz] and d 137.2 [3J(PC)ꢂ
N, C2 and C3 carbon atoms,
/
10.6 Hz] were
/
respectively. The crystal structure of 3 has been deter-
mined by X-ray diffraction analysis (see below) and
confirms the spectroscopic data.
The reaction of 1 with Ph2PCH2CH2CH2NH2, under
a similar experimental procedure as above, afforded
1-diphenylphosphino-2-diphenylarsinoethane
which
bridges the two metal centers, completes the metal
coordination sphere. Although the bridging ligand,
Ph2PCH2CH2AsPh2, is asymmetric, the dinuclear mo-
lecule is crystallographically centrosymmetric; this is
caused by the disordered distribution of the P and As
atoms (population parameter 50%) and by the quasi
centrosymmetric nature of the compound, which gives
similar environments for both P and As. However, in
compound 3 (vide supra) where the P and As atoms are
in different chemical surroundings, the technique clearly
distinguishes both atoms. This behavior has been
observed in other complexes derived from the arsino-
phosphine ligand [32,33].
For mononuclear complexes 3 and 4 the palladium(II)
atom is bonded to four atoms: an ortho carbon of the
phenyl ring and a nitrogen atom of the benzylidene
ligand, and a phosphorus atom and an arsenic (3) or a
nitrogen (4) atom of the chelating arsinophosphine or
phosphinoamine ligands, respectively.
[Pd{4-(COH)C6H3C(H)Ä
/
N(Cy)Ã
/
C2,N}{Ph2PCH2CH2-
CH2N(ÄCMe2)ÃP,N}][PF6] (4), after intermolecular
/
/
condensation between the aminophosphine and the
solvent. The elemental analysis was in agreement with
the proposed structure (see Section 3). The mass
spectrum showed very well defined peaks at m/z 603,
576, 522 and 497 assigned to [M]ꢁ, [Mꢃ
/
COH]ꢁ, [Mꢃ
/
Cy]ꢁ and [Mꢃ
/
COHꢃ
Cy]ꢁ, respectively. The IR
/
stretches for compound 4 at 1644 and 1620 cmꢃ1 were
consistent with the presence of two different imino
groups, Me2CÄ
/
NÃ
/
and HCÄ
/
NÃ
/
, respectively. The
chemical shift in the 31P{1H}-NMR spectrum at d
27.97 was indicative of P-coordination to the palladium
atom. The displacement of the HCÄ
/
N, HCÄ
/
O and H3
resonances in the 1H-NMR spectrum with respect to the
corresponding ones in the spectrum of the starting
compound, as well as the observed splittings (see Section
3) were in accordance with a P trans to N arrangement
1
in the palladium environment. The H-NMR spectrum
also showed two singlets at d 2.30 and d 2.02 assignable
to the NMe2 methyl groups, which were non-equivalent.
X-ray diffraction analysis of compound 4 confirmed
these findings (see below).
Following a similar procedure to that for 4, reaction
of 1 with Ph2PCH2CH2CH2NH2 in toluene, where
condensation of the solvent to the NH2 group is
precluded, gave the expected mononuclear com-
pound
PCH2CH2Ã
[Pd{4-(COH)C6H3C(H)Ä
/
N(Cy)Ã
/
C2,N}(Ph2-
/
CH2NH2ÃP,N)][PF6] (5). The elemental
/
analysis and the mass spectrum ([M]ꢁ at m/z 563)
gave satisfactory results. The conductivity data (164.6
Vꢃ1 cm2 molꢃ1 in 10ꢃ3 mol dm3 solution in dry
acetonitrile) showed it to be a 1:1 electrolyte [31],
confirming the presence of the aminophosphine ligand
in its neutral form. The spectroscopic data was similar
to that observed for compound 4, with absence of the
Fig. 1. Molecular structure of [{Pd[4-(COH)C6H3C(H)Ä
/
N(Cy)Ã
/
C2,N](Cl)}2(m-Ph2PCH2CH2AsPh2)] (2), with labeling scheme. Hy-
drogen atoms have been omitted for clarity.

90
R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 87ꢀ94
/
˚
than the predicted single bond value of 2.011 A, based
on the sum of covalent radii for nitrogen(sp2) and
˚
palladium, 0.701 and 1.31 A, respectively [34], and
reflects the trans influence of the phosphorusꢀ
atom [5,35].
The palladiumÃ
/
arsenic
˚
/
carbon bond length (2.003(5) A, 2;
2.066(5) A, 3; 2.010(3) A, 4) is within the expected value
˚
˚
˚
of 2.081 A (based on the sum of covalent radii for
2
carbon(sp ) and palladium, 0.771 and 1.31 A, respec-
˚
tively), but longer than those found in related complexes
where partial multiple-bond character of the PdÃ
was proposed [19,30].
The PdÃP and PdÃ
/
C bond
˚
/
/
As bond distances (2.311(1) A, 2;
2.263(1) A and 2.452(1) A, 3; 2.250(1) A, 4) are shorter
˚
˚
˚
than the sum of the single bond radii for palladium and
˚
˚
the corresponding atom (2.41 A for PdÃ
PdÃAs), suggesting partial double bond character
similar to others reported earlier [36]. In compound 2,
/
P, 2.55 A for
/
Fig. 2. Molecular structure of the cation for [Pd{4-(COH)C6H3C(H)Ä
N(Cy)ÃC2,N}(Ph2PCH2CH2AsPh2ÃP,As)][PF6] (3), with labeling
scheme. Hydrogen atoms have been omitted for clarity.
/
˚
Cl bond length, 2.384(5) A, is consistent with
/
/
the PdÃ
/
PdÃCl distances found in related species [37] but longer
/
˚
than the sum of the covalent radii (2.30 A) as a
consecuence of the trans influence of the C(phenyl)
carbon.
3. Experimental
3.1. General remarks
All solvents were distilled prior to use from appro-
priate drying agents [38]. All chemicals were used as
supplied from commercial sources. Elemental analyses
(C, H, N) were carried out in a Carloꢀ
elemental analyzer. IR spectra were recorded as KBr
pellets or Nujol mulls on a PerkinꢀElmer 1330 spectro-
/Erba 1108
/
photometer. 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-
1
200F spectrometer (200.0 MHz for H, 50.3 MHz for
13C{1H}, 81.0 MHz for 31P{1H}). Mass spectra were
obtained in a QUATRO mass spectrometer with Cs ion-
gun and 3-NBA matrix. Conductivity measurements
were made on a Crison GLP 32 conductivimeter using
10ꢃ3 M solutions in dry acetonitrile at room tempera-
ture (r.t.) (298 K). The synthesis of [Pd{4-
Fig. 3. Molecular structure of the cation for [Pd{4-(COH)C6H3C(H)Ä
/
N(Cy)Ã
/
C2,N}{Ph2PCH2CH2CH2N(ꢂ P,N}][PF6] (4), with
/
CMe2)Ã
/
labeling scheme. Hydrogen atoms have been omitted for clarity.
The sum of angles about palladium is 360.56 (2),
360.23 (3) and 361.278 (4); with the distortions most
noticeable in the somewhat reduced ‘bite’ angles of the
cyclometallated moiety consequent upon chelation. The
requirements of the five-membered ring forces the bond
(COH)C6H3C(H)Ä
/
N(Cy)ÃC2,N}(m-Cl)]2 (1) was re-
/
ported in a recent paper from this laboratory [23].
angle N(1)Ã
/
Pd(1)Ã
/
C(1) to 80.57(19) (2), 81.37(19) (3)
and 81.00(12)8 (4). The geometry around the palladium
atom is slightly distorted square-planar, the mean
deviations from the least squares planes (plane 1: Pd1,
3.2. Synthesis of [{Pd[4-(COH)C6H3C(H)Ä
/
N(Cy)Ã
/
C2,N](Cl)}2(m-Ph2PCH2CH2AsPh2)] (2)
C1, N1, P1Ã
/
As1, Cl1, 2; Pd1, C1, N1, P1, As1, 3; Pd1,
˚
To a solution of 1 (50 mg, 0.070 mmol) in acetone (ca.
10 ml), Ph2PCH2CH2AsPh2 (28 mg, 0.064 mmol) was
added. The mixture was stirred for 12 h at r.t., after
which the precipitate formed was filtered off, dried in
C1, N1, P1, N2, 4) are 0.1084, 0.0796 and 0.1296 A,
respectively.
The palladiumÃ
/nitrogen bond length in the metalla-
˚
cycle (2.104(4) A, 2; 2.107(4) A, 3; 2.114(3), 4) is longer
˚
vacuo, and recrystallized from chloroformꢀn-hexane to
/

R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 87ꢀ
/
94
91
Table 1
Crystal and structure refinement data for complexes 2ꢀ
/
4
2
3
4
Formula
Mr
C
54H56AsCl2N2O2PPd2
C40H40AsF6NOP2Pd
907.99
293(2)
C32H38F6N2OP2Pd
748.98
293(2)
1154.60
293(2)
0.71073
Temperature (K)
˚
Wavelenght (A)
0.71073
Triclinic
0.71073
Triclinic
Crystal system
Space group
Cell dimensions
Triclinic
¯
¯
¯
P
/
1/
P/
1
/
P/ /
1
˚
a (A)
9.838(1)
11.311(1)
13.132(1)
76.65(1)
73.00(1)
88.626(2)
1358.2(2)
1
12.613(1)
13.767(1)
14.049(2)
99.45(1)
116.43(1)
101.25(1)
2052.9(2)
2
10.642(1)
11.639(1)
13.810(2)
79.59(1)
81.62(1)
80.04(1)
1645.4(1)
2
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
3
˚
V (A )
Z
Dcalc. (Mg mꢃ3
m (mmꢃ1
)
1.412
1.433
1.469
1.388
1.512
0.724
)
Crystal size (mm)
2umax (8)
Reflections collected
0.20ꢄ
56.58
9771
/0.15ꢄ/0.15
0.35ꢄ
56.62
14 644
/0.25ꢄ/0.20
0.30ꢄ
56.58
11 795
/
0.20ꢄ0.20
/
Reflections independent
6595 (Rint
0.0525
0.1937
0.665
ꢂ/
0.0560)
9961 (Rint
0.0528
0.2230
0.916
ꢂ/0.0475)
7971 (Rint
0.0480
0.1235
0.623
ꢂ/0.0396)
R [F, I ꢀ2s(I)]
/
wR [F2 , all data]
ꢃ3
˚
max r (e A
)
1
yield the desired product as pale yellow microcrystals.
Yield: 68% (49.9 mg). Anal. Found: C, 56.6; H, 4.9; N,
2.2%. C54H56AsCl2N2O2PPd2 requires: C, 56.2; H, 4.9;
762 [LPd(arphos)]ꢁ. H-NMR: 9.20, 9.13 (s, Ha, Ha?),
8.15 (dd, Hi, 4J(PHi)ꢂ8.3 Hz, 5J(HiH7)ꢂ
1.0 Hz), 8.11
(d, Hi?, 5J(Hi?H7?)ꢂ
1.0 Hz), 6.86 (d, H3?,
3J(H3?H5?)ꢂ
1.0 Hz), 6.80 (dd, H3, J(PH3)ꢂ
/
/
/
4
N, 2.4. IR: n(CÄ
/
N): 1621m, n(CÄ/O): 1687s. FAB-Mass:
/
/5.9 Hz,
Table 2
Selected bond distances (A) and angles (8) for complexes 2ꢀ
˚
/
4
2
3
4
Bond lengths
Pd(1)Ã
Pd(1)Ã
Pd(1)Ã
Pd(1)Ã
/
C(1)
2.003(5)
2.104(4)
2.384(5)
2.311(1)
1.403(7)
1.465(8)
1.276(7)
1.181(9)
2.311(1)
Pd(1)Ã
Pd(1)Ã
Pd(1)Ã
Pd(1)Ã
/
C(1)
N(1)
P(1)
2.066(5)
2.107(4)
2.263(1)
2.452(1)
1.396(8)
1.446(9)
1.284(8)
1.205(8)
1.847(7)
Pd(1)Ã
Pd(1)Ã
Pd(1)Ã
Pd(1)Ã
/
C(1)
N(1)
P(1)
N(2)
2.010(3)
/
N(1)
Cl(1)
As(1)
/
/
2.114(3)
2.250(1)
2.144(3)
1.413(5)
1.448(5)
1.283(4)
1.113(7)
1.127(10)
/
/
/
/
/As(1)
/
C(1)Ã
C(6)Ã
N(1)Ã
O(1)Ã
/
C(6)
C(1)Ã
C(6)Ã
N(1)Ã
O(1)Ã
P(1)Ã
As(1)Ã
/
C(6)
C(1)Ã
C(6)Ã
N(1)Ã
O(1A)Ã
O(1B)ÃC(14)
N(2)ÃC(30)
/
C(6)
/
C(7)
/C(7)
/C(7)
/
C(7)
C(14)
/
C(7)
/
C(7)
C(14)
/
/C(14)
/
Pd(2)Ã
/
P(1)
/C(15)
/
/
C(16)
/
Bond angles
C(1)ÃPd(1)Ã
C(1)ÃPd(1)Ã
As(1)Ã
N(1)ÃPd(1)Ã
C(7)ÃN(1)Ã
N(1)ÃC(7)Ã
C(1)ÃC(6)Ã
C(6)ÃC(1)Ã
/
/
N(1)
80.57(19)
94.05(15)
91.12(4)
94.82(13)
113.7(4)
116.6(5)
116.1(5)
112.4(4)
1.956(6)
1.285(5)
81.00(12)
96.31(10)
88.21(8)
95.75(11)
112.7(2)
117.8(3)
116.5(3)
111.7(2)
107.75(12)
120.6(2)
/
/As(1)
C(1)Ã
C(1)Ã
P(1)ÃPd(1)Ã
N(1)ÃPd(1)Ã
C(7)ÃN(1)Ã
N(1)ÃC(7)Ã
C(1)ÃC(6)Ã
C(6)ÃC(1)Ã
C(15)Ã
C(16)Ã
/
Pd(1)Ã
/
N(1)
81.37(19)
98.38(15)
82.27(4)
C(1)Ã
C(1)Ã
N(2)Ã
N(1)Ã
C(7)ÃN(1)Ã
N(1)ÃC(7)Ã
C(1)ÃC(6)Ã
C(6)ÃC(1)Ã
C(27)Ã
C(29)Ã
/
Pd(1)Ã
Pd(1)Ã
Pd(1)Ã
Pd(1)Ã
/
N(1)
/
Pd(1)Ã
/
Cl(1)
Cl(1)
/
Pd(1)Ã
/P(1)
/
/P(1)
/
/
/
/As(1)
/
/
P(1)
/
/
Pd(1)
/
/
As(1)
98.21(13)
111.1(4)
/
/
N(2)
/
/
C(6)
/
/
Pd(1)
C(6)
/
/
Pd(1)
/
/
C(7)
/
/
120.6(5)
/
/C(6)
/
/
Pd(1)
/
/C(7)
116.2(5)
/
/C(7)
/
/Pd(1)
110.6(4)
/
/Pd(1)
/
Pd(1)Ã
/P(1)
107.45(18)
106.69(18)
/
P(1)Ã
/
Pd(1)
Pd(1)
/
Pd(1)Ã
/As(1)
/
N(2)Ã
/

92
R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 87ꢀ94
/
3J(H3H5)ꢂ
/
1.9 Hz), 4.5 (m, Ha). 31P{1H}-NMR: 37.78
4J(H3H5)ꢂ
NMR: 27.97 (s)
/
1.2 Hz), 2.30 (s, Me), 2.02 (s, Me). 31P{1H}-
(s). 13C-NMR: 192.2 (s, COH), 192.1 (s, C?OH), 170.3
4
(s, C?Ä
/
N), 170.2 (d, CÄ
/
N, J(PC)ꢂ
/5.7 Hz), 155.7 (s,
C1, C1?), 154.4, 154.3 (C2, C2?), 139.4 (d, C3,
3J(PC3)ꢂ
4J(PC4)ꢂ
/
10.6 Hz), 139.8 (s, C3?), 135.6 (d, C4,
3.5. Synthesis of [Pd{4-(COH)C6H3C(H)Ä
C2,N}(Ph2PCH2CH2CH2NH2ÃP,N)][PF6] (5)
/
N(Cy)Ã
/
/
4.3 Hz), 135.5 (s, C4?), 127.4 (C5, C5?),
/
2
?
11.4 Hz), 134.0 (s, Co), 131.1
134.2 (d, Co, J(PCo)ꢂ
/
4
?
?
(d, Cp, J(PCp)ꢂ
128.6 (d, Cm, 3J(PCm)ꢂ
C6?), 63.0 (s, C7, C7?), 33.4 (s, C8, C8?, C12, C12?), 30.7
(d, Ca,1J(PCa)ꢂ
5.7Hz), 25, 8 (C10, C10?), 25.4 (s, C9,
C9?, C11, C11?), 24.4 (s, Cb).
/
2.1 Hz) 130.5 (s, Cp), 129.0 (s, Cm),
To a solution of 1 (20 mg, 0.028 mmol) in toluene (ca.
15 ml), Ph2PCH2CH2CH2NH2 (13.67 mg, 0.056 mmol)
was added. The mixture was stirred for 2 h at r.t., after
which ammonium hexafluorophosphate (4.6 mg, 0.028
mmol) was added and the resultant solution stirred for a
further 1 h. A precipitate formed was filtered off, dried
in vacuo over anhidrous CaCl2, and the desired complex
/10.6 Hz), 124.3, 124.0 (C6,
/
3.3. Synthesis of [Pd{4-(COH)C6H3C(H)Ä
C2,N}(Ph2PCH2CH2AsPh2ÃP,As)][PF6] (3)
/
N(Cy)Ã
/
/
recrystallized from chloroformꢀn-hexane as yellow
/
crystals. Yield: 50% (20.2 mg). Anal. Found: C, 49.0;
H, 4.4; N, 4.1%. C29H34F6N2OP2Pd requires: C, 49.2; H,
To a solution of 1 (20 mg, 0.028 mmol) in acetone (ca.
15 ml), Ph2PCH2CH2AsPh2 (24.84 mg, 0.056 mmol) was
added. The mixture was stirred for 2 h at r.t., after which
ammonium hexafluorophosphate (4.6 mg, 0.028 mmol)
was added, the resultant solution stirred for a further 1
h, water (ca. 40 ml) was added dropwise and the
resulting mixture stirred for 2 h. A precipitate formed
4.7; N, 4.0. IR: n(CÄ
FAB-Mass: 563 [M]ꢁ, 534 [Mꢃ
Cy]ꢁ, 291 [(LꢃCOH)Pd]ꢁ. 1H-NMR: 9.25 (s, Ha),
8.30 (dd, Hi, 4J(PHi)ꢂ7.3 Hz, 5J(HiH7)ꢂ
1.0 Hz), 6.74
5.9 Hz, 4J(H3H5)ꢂ
1.2 Hz).
/
N): 1622sh, m, n(CÄ
/
O): 1698s.
/
COH]ꢁ, 480 [Mꢃ
/
/
/
/
(d, H3, 4J(PH3)ꢂ
/
/
31P{1H}-NMR: 28.29 (s).
was filtered off, washed with water (2ꢄ
in vacuo over anhidrous CaCl2. The desired complex
was recrystallized from dichloromethaneꢀn-hexane as
/5 ml) and dried
/
pale yellow microcrystals. Yield: 88% (22.4 mg). Anal.
Found: C, 53.1; H, 4.5; N, 1.5%. C40H40AsF6NOP2Pd
4. X-ray crystallographic study
requires: C, 52.9; H, 4.4; N, 1.5. IR: n(CÄ
n(CÄ
O): 1691s. FAB-Mass: 762 [M]ꢁ, 735 [Mꢃ
COH]ꢁ. 1H-NMR: 9.37 (s, Ha), 8.48 (d, Hi,
4J(PHi)ꢂ7.8 Hz), 6.98 (dd, H3, 4J(PH3)ꢂ
5.6 Hz,
4J(H3H5)ꢂ1.2 Hz). 31P{1H}-NMR: 60.27 (s). 13C-
NMR: 191.6 (s, COH), 176.8 (b, CÄN), 161.0 (d, C2,
2J(PC2)ꢂ
5.7 Hz), 154.8 (s, C1), 137.2 (d, C3,
3J(PC3)ꢂ10.6 Hz), 137.0 (d, C4, 3J(PC4)ꢂ
4.2 Hz),
134.0 (d, Co, 2J(PCo)ꢂ
/N): 1619m,
/
/
Three-dimensional, room temperature X-ray data
were collected on a Siemens Smart CCD diffractometer
by the v scan method using graphite-monochromated
/
/
/
MoꢀKa radiation. All the measured reflections were
/
/
corrected for Lorentz and polarization effects and for
absorption by semi-empirical methods based on sym-
metry-equivalent and repeated reflections. The struc-
tures were solved by direct methods and refined by full
matrix least squares on F2. As the molecule of 2, which
is not centrosymmetric, lies on a symmetry center, it was
necessary to postulate a disordered distribution of As
and P assuming an occupancy factor which turned out
to be 0.5 for both atoms, from the refinement. For
complex 4 the O(1) oxygen atom was found to be
disordered over two positions. The occupancies of these
were tied to give an overall value of 1.0 and then refined
taking into account the minor components (final
occupancies: 0.5). Hydrogen atoms were included in
calculated positions and refined in riding mode. Refine-
/
/
/
?
/
11.1 Hz), 132.9 (s, Co), 130.1 (d,
Cm, 3J(PCm)ꢂ
/
14.8 Hz, 129.7 (s, Cm), 127.8 (s, C6),
?
1
?
87.2 Hz), 125.0 (s, Ci ), 131.8 (s,
126.9 (d, Ci, J(PCi)ꢂ
/
?
Cp, Cp), 70.5 (s, C7), 33.6 (s, C8, C12), 31.4 (d, Ca,
1J(PCa)ꢂ
36.7 Hz), 24.6 (s, C9, C11), 24.9 (s, C10), 24.3
(d, Cb, J(PCb)ꢂ7.1 Hz)
/
1
/
3.4. Synthesis of [Pd{4-(COH)C6H3C(H)Ä
C2,N}{Ph2PCH2CH2CH2N(ÄCMe2)ÃP,N}][PF6]
(4)
/
N(Cy)Ã
/
/
/
The desired compound was prepared similarly and
isolated as pale yellow solid, but using
a
ment converged at a final Rꢂ
(for complexes 2, 3 and 4, respectively, observed data,
0.1937, 0.2230 and 0.1235 (for complexes
2, 3 and 4, respectively, unique data, F2), with allowance
for thermal anisotropy of all non-hydrogen atoms. The
structure solution and refinement were carried out using
the program package SHELX-97 [39].
/
0.0525, 0.0528 and 0.0480
Ph2PCH2CH2CH2NH2 as appropiate. Yield: 62% (26
mg). Anal. Found: C, 51.1; H, 5.0; N, 3.6%.
C32H38F6N2OP2Pd requires: C, 51.3; H, 5.1; N, 3.7.
F) and wR2ꢂ
/
IR: n(CÄ
/
N): 1644m, 1620m, n(CÄ
/
O): 1697s. FAB-
Mass: 603 [M]ꢁ, 576 [Mꢃ
/
COH]ꢁ, 522 [MꢃCy]ꢁ,
/
1
497 [MꢃCOHꢃ
/
/
Cy]ꢁ. H-NMR: 9.21 (s, Ha), 8.33 (d,
4
4
Hi, J(PHi)ꢂ
/
7.8 Hz), 6.58 (d, H3, J(PH3)ꢂ
/5.9 Hz,

R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 87ꢀ
/
94
93
[11] M. Marcos, in: J.L. Serrano (Ed.), Metallomesogens. Synthesis,
Properties and Applications, VCH, Weinheim, 1996.
[12] (a) S.B. Wild, Coord. Chem. Rev. 166 (1997) 291;
5. Supporting information available
Crystallographic data for structural analysis have
been deposited with the Cambridge Crystallographic
Data Center, CCDC no. 190994, 190995 and 190996 for
compounds 4, 3 and 2, respectively. Copies of the
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2
¨
(b) W.A. Herrmann, C. Brossmer, K. .Okefe, C.P. Reisinger, T.
Priermeier, M. Beller, H. Fischer, Angew. Chem. Int. Ed. Engl.
107 (1995) 1844.
[13] (a) J. Dupont, M. Pfeffer, J. Spencer, Eur. J. Inorg. Chem. (2001)
1917;
(b) L. Botella, C. Najera, Angew. Chem. Int. Ed. 41 (2002) 179.
[14] (a) J.M. Vila, M. Gayoso, M. Lo´pez Torres, J.J. Ferna´ndez, A.
Ferna´ndez, J.M. Ortigueira, N.A. Bailey, H. Adams, J. Organo-
met. Chem. 511 (1996) 129;
1EZ, UK (Fax: ꢁ44-1223-336033; e-mail: deposit@
/
ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk).
(b) B. Teijido, A. Ferna´ndez, M. Lo´pez-Torres, A. Sua´rez, J.M.
Vila, R. Mosteiro, J.J. Ferna´ndez, Organometallics 21 (2002)
1304.
Acknowledgements
[15] (a) A. Ferna´ndez, J.J. Ferna´ndez, M. Lo´pez-Torres, A. Sua´rez,
J.M. Ortigueira, J.M. Vila, H. Adams, J. Organomet. Chem. 612
(2000) 85;
We thank the DGES (Proyecto PB98-0638-C02-01/
02) for financial support. R.M. acknowledges a fellow-
ship from the Ministerio de Ciencia y Tecnolog´ıa
(Spain).
(b) M. Lo´pez-Torres, A. Ferna´ndez, J.J. Ferna´ndez, A. Sua´rez,
M.T. Pereira, S. Castro-Juiz, J.M. Vila, Organometallics 20 (2001)
1350.
[16] A. Ferna´ndez, P. Ur´ıa, J.J. Ferna´ndez, M. Lo´pez-Torres, A.
Sua´rez, D. Va´zquez-Garc´ıa, M.T. Pereira, J.M. Vila, J. Organo-
met. Chem. 620 (2001) 8.
[17] A. Ferna´ndez, M. Lo´pez-Torres, A. Sua´rez, J.M. Ortigueira,
M.T. Pereira, J.J. Ferna´ndez, J.M. Vila, H. Adams, J. Organomet.
Chem. 598 (2000) 1.
References
[1] (a) C.A. McAuliffe, W. Levason, Phosphine, Arsine and Stibine
Complexes of the Transition Elements, Elsevier, Amsterdam,
1979;
[18] A. Ferna´ndez, D. Vazquez-Garcia, J.J. Ferna´ndez, M. Lopez-
Torres, A. Suarez, S. Castro-Juiz, J.M. Ortigueira, J.M. Vila, New
J. Chem. 26 (2002) 105.
(b) D.W. Meek, in: L.H. Pignolet (Ed.), Homogeneus Catalysis
with Metal Phosphine Complexes, Plenum Press, New York,
1983;
[19] M. Lousame, A. Ferna´ndez, M. Lo´pez-Torres, D. Va´zquez-
Garc´ıa, J.M. Vila, A. Sua´rez, J.M. Ortigueira, J.J. Ferna´ndez,
Eur. J. Inorg. Chem. (2000) 2055.
(c) O. Stelzer, K.P. Langhans, in: F.R. Hartley (Ed.), The
Chemistry of Organophosphorus Compounds, Wiley, New
York, 1990;
[20] J.M. Vila, E. Gayoso, M.T. Pereira, M. Marino, J. Mart´ınez, J.J.
˜
Ferna´ndez, A. Ferna´ndez, M. Lo´pez-Torres, J. Organomet.
Chem. 637ꢀ639 (2001) 577.
/
(d) F.A. Cotton, B. Hong, Prog. Inorg. Chem. 40 (1992) 179.
[2] (a) K.-I. Na, S. Huh, K.M. Sung, M.-J. Jun, Polyhedron 15 (1996)
1841;
[21] G. Minghetti, M.A. Cinellu, S. Stoccoro, A. Zucca, M. Mana-
ssero, J. Chem. Soc. Dalton Trans. (1995) 777.
[22] A.B. Goel, S. Goel, Inorg. Chim. Acta 98 (1985) 67.
[23] J.M. Vila, M. Gayoso, M.T. Pereira, M. Lo´pez, G. Alonso, J.J.
Ferna´ndez, J. Organomet. Chem. 445 (1993) 287.
[24] P.S. Pregosin, R.W. Kuntz, 31P and 13C-NMR of transition metal
phosphine complexes, in: P. Diehl, E. Fluck, R. Kosfeld (Eds.),
NMR Basic Principles and Progress, vol. 16, Springer, Berlin,
1979.
(b) J.-Y. Kim, M.-J. Jun, W.-Y. Lee, Polyhedron 15 (1996) 3787.
[3] M. Ito, M. Hirakawa, K. Murata, T. Ikariya, Organometallics 20
(2001) 379.
[4] G.P.C.M. Dekker, A. Buijs, C.J. Elsevier, K. Vrieze, P.W.N.M.
van Leeuwen, W.J.J. Smeets, A.L. Spek, Y.F. Wang, C.H. Stam,
Organometallics 11 (1992) 1937.
[5] A. Habtemariam, B. Watchman, B.S. Potter, R. Palmer, S.
Parsons, A. Parkin, P.J. Sadler, J. Chem. Soc. Dalton Trans.
(2001) 1306.
[25] H. Onoue, I. Moritani, J. Organomet. Chem. 43 (1972) 431.
[26] K. Nakamoto, Infrared and Raman Spectra of Inorganic and
Coordination Compounds, 5th ed, Wiley, New York, 1997.
[27] J. Granell, D. Sa´inz, J. Sales, X. Sola´ns, M. Font-Altaba, J.
Chem. Soc. Dalton Trans. (1986) 1785.
[6] A. Mansour, M. Portnoy, J. Chem. Soc. Perkin Trans. 1 (2001)
952.
[7] (a) E.C. Constable, Polyhedron 3 (1984) 1037;
(b) I. Omae, Organometallic intramolecular-coordination com-
pounds, in: Journal of Organometallic Chemistry Library, Else-
vier, Amterdam, 1986;
[28] L. Tusek-Bozic, M. Curic, P. Traldi, Inorg. Chim. Acta 254 (1997)
49.
[29] P.E. Garrou, Chem. Rev. 81 (1981) 229.
[30] J.M. Vila, M.T. Pereira, J.M. Ortigueira, M. Lo´pez-Torres, A.
(c) O.A. Dunina, V.M. Zalevskaya, V.M. Potapov, Russ. Chem.
Rev. 57 (1988) 434.
[8] (a) A.D. Ryabov, Synthesis 3 (1985) 233;
Castineiras, D. Lata, J.J. Ferna´ndez, A. Ferna´ndez, J. Organo-
˜
met. Chem. 556 (1998) 31.
[31] W.J. Geary, Coord. Chem. Rev. 7 (1971) 81.
[32] L.P. Battaglia, A.B. Corradi, M. Nardelli, Inorg. Chim. Acta 50
(1981) 125.
(b) J. Spencer, M. Pfeffer, Adv. Met. Org. Chem. 6 (1998) 103;
(c) J. Spencer, M. Pfeffer, Adv. Met. Org. Chem. 3 (1994) 103.
[9] A. von Zelewski, P. Belser, P. Hayos, R. Dux, X. Hua, A.
Suckling, H. Stoeckli-Evans, Coord. Chem. Rev. 132 (1994) 75.
[10] (a) C. Navarro-Ranninger, I. Lopez-Solera, V.M. Gonzalez, J.M.
Perez, J.H. Rodriguez, J.L. Garcia-Ruano, P. Raithby, J.R.
Masaguer, C. Alonso, J. Med. Chem. 36 (1993) 3795;
(b) C. Navarro-Ranninger, I. Lopez-Solera, V.M. Gonzalez, J.M.
Perez, A. Alvarez-Valdes, A. Martin, P. Raithby, J.R. Masaguer,
C. Alonso, Inorg. Chem. 35 (1996) 5181.
[33] B.F. Abrahams, R. Colton, B.F. Hoskins, K. McGregor, Aust. J.
Chem. 45 (1992) 941.
[34] L. Pauling, The Nature of Chemical Bond, 3rd ed, Cornell
University Press, New York, 1960.
[35] (a) J.M. Vila, M. Gayoso, M. Lo´pez Torres, J.J. Ferna´ndez, A.
Ferna´ndez, J.M. Ortigueira, N.A. Bailey, H. Adams, J. Organo-
met. Chem. 511 (1996) 129;

94
R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 87ꢀ94
/
(b) T. Suzuki, A. Morikawa, K. Kashiwabara, Bull. Chem. Soc.
Jpn. 69 (1996) 2539.
[37] J.M. Vila, M. Gayoso, A. Ferna´ndez, H. Adams, N.A. Bailey, J.
Organomet. Chem. 448 (1993) 233.
[36] (a) A. Suarez, J.M. Vila, E. Gayoso, M. Gayoso, W. Hiller, A.
Castineiras, J. Strahle, Z. Inorg. Allg. Chem. 535 (1986) 213;
[38] W.L.F. Armarego, D.D. Perrin, Purification of Laboratory
Chemicals, 4th ed, Butterworth-Heinemann, Oxford, 1997.
[39] G.M. Sheldrick, SHELX-97, University of Gottingen, Germany,
˜
¨
(b) R. Bosque, C. Lo´pez, X. Solans, M. Font-Bardia´, Organo-
metallics 18 (1999) 1267.
¨
1997.