Functionalized cyclopalladated compounds with bidentate group 15 donor atom ligands (see abstract)

Article abstract of DOI:10.1016/S0022-328X(02)02065-X

The chloro-bridged dinuclear compound [{Pd[5-(COH)C₆H₃C(H)=N(Cy)-C2,N]}(μ-Cl)] ₂(1), reacts with tertiary diphosphines in 1:1 molar ratio to give [{Pd[5-(COH)C₆H₃C(H)=NCy-C2,N](Cl)} ₂(μ-Ph<

Full text of DOI:10.1016/S0022-328X(02)02065-X

Journal of Organometallic Chemistry 665 (2003) 76ꢁ86
/
www.elsevier.com/locate/jorganchem
Functionalized cyclopalladated compounds with bidentate Group 15
donor atom ligands: the crystal and molecular structures of [{Pd[5-
(COH)C6H3C(H)Ä
/
NCy-C2,N](Cl)}2(m-Ph2PRPPh2)] (Rꢀ
NCy-C2,N}(Ph2PCH2PPh2-
N(Cy)-
/
CH2CH2,
Fe(C5H4)2], [Pd{5-(COH)C6H3C(H)Ä
/
P,P)][PF6] and [Pd{5-(COH)C6H3C(H)Ä
/
C2,N}(Ph2PCH2CH2AsPh2-P,As)][PF6]
Raquel Ares a, Margarita Lo´pez-Torres a, Alberto Ferna´ndez a, Ma Teresa Pereira b,
Gemma Alberdi b, Digna Va´zquez-Garc´ıa a, Jesus J. Ferna´ndez b,*, Jose´ M. Vila b,*
´
a Departamento de Qu´ımica Fundamental, Universidad de A Coruna, La Zapateira, s/n, 15071 A Coruna, Spain
˜
˜
b Departamento de Qu´ımica Inorga´nica, Universidad de Santiago de Compostela, Av. de las Ciencias, s/n, 15782 Santiago de Compostela, Spain
Received 30 July 2002; received in revised form 23 October 2002; accepted 23 October 2002
Abstract
The chloro-bridged dinuclear compound [{Pd[5-(COH)C6H3C(H)Ä
1:1 molar ratio to give [{Pd[5-(COH)C6H3C(H)ÄNCy-C2,N](Cl)}2(m-Ph2PRPPh2)] (R: CH2, 2; CH2CH2, 3; (CH2)4, 4; (CH2)6, 5;
Fe(C5H4)2, 6; trans-CHÄCH, 7; CꢀC, 8). Treatment of 1 with Ph2PCH2CH2AsPh2 (arphos) gives the dinuclear complex [{Pd[5-
(COH)C6H3C(H)ÄN(Cy)-C2,N](Cl)}2(m-Ph2PCH2CH2AsPh2)] (9). The reaction of 1 with tertiary diphosphines or arphos in 1:2
molar ratio in the presence of NH4PF6 yields the mononuclear compounds [Pd{5-(COH)C6H3C(H)ÄNCy-C2,N}(Ph2PRPPh2-
N(Cy)-
/
N(Cy)-C2,N]}(m-Cl)]2 (1), reacts with tertiary diphosphines in
/
/
/
/
/
P,P)][PF6] (R: (CH2)4, 10; (CH2)6, 11; Fe(C5H4)2, 12; 1,2-C6H4, 13; cis-CHÄ
/
CH, 14; NH, 15) and [Pd{5-(COH)C6H3C(H)Ä
/
C2,N}(Ph2PCH2CH2AsPh2-P,As)][PF6] (16). H-, 31P-{1H}- and 13C-{1H}-NMR, IR and mass spectroscopic data are given. The
crystal structures of compounds 3, 6, 9 and 16 have been determined by X-ray crystallography.
# 2002 Elsevier Science B.V. All rights reserved.
1
Keywords: Palladium; Metallation; Phosphines; As ligands; X-ray diffraction
1. Introduction
active components [8,9], in the design of complexes with
promising photochemical and electrochemical proper-
ties [10,11] and specific antitumor activity toward
various forms of cancer [12,13].
Our interest in cyclometallated systems has been
related, in the majority of cases, with palladium(II)
compounds which involved the coordination of one
metal atom per organic ligand, i.e. derivatives of
The synthesis of cyclometallated compounds [1,2] is
an ever expanding area of chemical research and
numerous articles and reviews have recorded their
ongoing developments as well as their applications
over the years, such as the use as active catalysts [3,4],
as intermediates in the synthesis of new organometallic
and organic compounds [5ꢁ
racemic mixtures into the corresponding pure optically
/
7] in the resolution of
differently substituted [C,N] Schiff bases [14ꢁ
cenylimines [17] or substituted imidazoles [18], as well as
derivatives of [C,N,X] (XꢀN, O, S) terdentate ligands
[19ꢁ21]. Furthermore, we have also reported com-
pounds with two metal atoms bonded to the same
organic moiety derived from diamines [22] or dialde-
hydes [23,24].
/
16], ferro-
/
/
* Corresponding authors. Fax: ꢂ
/
34-981-16-7065 (J.J.F.); fax: ꢂ34-
/
981-59-5012 (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 5 - X

R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 76ꢁ
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86
77
In the former case the reaction conditions influence
the cyclometallation process, and we have found that
potentially tetradentate Schiff bases derived from 1,4-
(COH)2C6H4 (terephthalaldehyde) and 1,3-(COH)2-
C6H4 (isophthaladehyde) give rise to different products.
as well as their numerous applications [28ꢁ
/
32]. Never-
theless, the corresponding derivatives of functionalized
and/or heterobidentate ligands containing phosphorus
atoms are scarce, probably due to their complicated
synthetic procedures. The past years have seen a
growing interest in reactions that include these type of
ligands and complexes, which have proved to be active
Thus, reaction of 1,4-(CyNÄ/CH)2C6H4 with palladiu-
m(II) acetate in glacial acetic acid afforded the mono-
cyclometallated compound I (as depicted in Fig. 1) in
which the acidic nature of the solvent caused hydrolysis
catalysts in numerous processes [33ꢁ36]. In the present
/
paper we describe the synthesis and characterization of
new cyclopalladated compounds derived from com-
pound III with homo- P,P, and heterobidentate,
P,As, ligands.
of one of the CÄ/N double bonds and palladium
coordination stabilizes the second imine group [25].
The dicyclometallated compound II can only be
achieved via oxidative addition reaction of [Pd2(dba)3]
with the dichloro derivative 1,4-(CyNÄ
C6H2 in benzene [26]. Nevertheless treatment of 1,3-
(CyNÄCH)2C6H4 with Pd(OAc)2 in AcOH gives a
/
CH)2-2,5-Cl2-
2. Results and discussion
/
mixture of the mono- and the dicyclometallated com-
pounds III and IV, respectively, the formation of the
former suggests that the meta disposition of the imine
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
1
analysis (C, H, N), mass spectrometry, by IR, H-, 31P-
groups and ulterior coordination of the CÄ/N group to
{1H} and (in part) 13C-{1H}-NMR spectroscopy data in
Section 4.
the palladium atom impedes hydrolysis [27]. Mono- (V,
VII) and dicyclomanganated (VI, VIII) compounds (see
Fig. 1) derived from terephthalaldehyde and isophtha-
ladehyde could also be achieved by the reaction of the
Schiff base ligands with [MeMn(CO)5] in n-octane
depending on the molar ratio [25,27]. The existence of
a free formyl group in the monocyclometallated com-
pounds represents a novel an interesting functionaliza-
tion of these complexes.
Reaction of [Pd{5-(COH)C6H3C(H)Ä/N(Cy)-C2,N}-
(m-Cl)]2 (1) [27] with bis(diphenylphosphine)methane
(dppm), in a 1:1 molar ratio, in acetone at room
temperature afforded the dinuclear complex [{Pd[5-
(COH)C6H3C(H)Ä
/
NCy-C2,N](Cl)}2(m-Ph2PCH2PPh2)]
/
(2). The IR spectrum showed the shift of the CÄ
N
stretch towards lower wavenumbers, as compared with
the free Schiff base ligand (1630 vs. 1623 cmꢃ1),
A large number metal complexes containing one or
more phosphorus donor atoms have been reported due
to the versatility of their electronic and steric properties
indicating N-coordination of the CÄ
/
N group [37]. A
O) band at 1693 cmꢃ1 was assigned to the free
n(CÄ
/
Fig. 1.

78
R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 76ꢁ
/
86
Scheme 1.
formyl group [38]. The MS-FAB spectrum showed
peaks at m/z 1061, 704 and 676, assigned to [Mꢃ
dance with a P trans to N arrangement, typical of these
reactions and within the terms of the ‘transphobic effect’
coined by Vicente et al. [42]. The reaction of 1 with the
short-bite diphosphine bis(diphenyphosphino)amine,
(dppa), under similar reaction conditions did not give
the analogous dinuclear compound, and yielded a
mixture of the starting complex and the chloride salt
of compound 15 (vide infra), indicating a low tendency
of this diphosphine to coordinate in a bridging mode.
Other diphosphines such as cis-bis(diphenylphosphine)
ethene (cis-dppe) and 1,2-bis(diphenylphosphino)ben-
zene (1,2-dppb) failed to give dinuclear compounds, due
to the cis-geometry of these ligands.
/
Cl]ꢂ, [LPd(PP)]ꢂ and [LPdCl]ꢂ, respectively, which
were characteristic clusters of isotopic peaks covering
ca. 10 m/z units, due to the presence of the numerous
palladium isotopes [39,40], thereby confirming the di-
nuclear nature of this complex. The 31P-{1H}-NMR
spectrum showed a singlet at d30.45, shifted to higher
frequency from the spectrum of the free phosphine, in
agreement with phosphorus coordination to metal
center [41] and indicated that the two phosphorus nuclei
were equivalent, with the diphosphine acting as a
bridging ligand.
In the 1H-NMR spectrum a singlet at d9.73 was
Treatment of 1 with 1,2-bis(diphenylphosphine)-
assigend to the HCÄ
at d8.07 appeared as a doublet of doublets due to
coupling with the 31P nucleus [4J(PHi)ꢀ
7.8 Hz] and
with the a proton of the cyclohexyl ring [5J(HiH7)ꢀ
1.0
Hz]. The signals corresponding to the metallated phenyl
ring protons were clearly distinguished. Thus, a doublet
at d7.64 and a doublet of doublets at d6.94 were
/
O resonance. The HCN resonance
ethane
(dppb), 1,6-bis(diphenylphosphine)hexane (dpph) and
(dppe),
1,4-bis(diphenylphosphine)butane
/
1,1?-bis(diphenylphosphine)ferrocene (dppf), long-bite
/
diphosphines, gave the dinuclear complexes 3ꢁ
the trimetallic complex 6, respectively, [{Pd[5-(COH)-
C6H3C(H)ÄNCy-C2,N](Cl)}2(m-Ph2PRPPh2)] (R: CH2,
/5 and
/
2; CH2CH2, 3; (CH2)4, 4; (CH2)6, 5; Fe(C5H4)2, 6),
which were fully characterized (see Section 4). The X-ray
crystal structure determination of compounds 3 and 6
(see below) confirmed the spectroscopic data.
assigned to H6 and H4, respectively [4J(H4H6)ꢀ
Hz, 3J(H3H4)ꢀ
was assigned to H3, coupled to the phosphorus atom
[4J(PH3)ꢀ
5.8 Hz]. The former two resonances were
/1.5
/
8.1 Hz]. A doublet of doublets at d6.25
/
Reaction of
ne)ethene (trans-dppe) and bis(diphenylphosphine)ace-
1
with trans-bis(diphenylphosphi-
shifted to lower field from the starting product ca. 0.5
and 1.3 ppm, respectively, due to the shielding effect of
the phosphine phenyl rings. These data are in accor-
tylene (dppac) afforded the dinuclear complexes [{Pd[5-
(COH)C6H3C(H)ÄNCy-C2,N](Cl)}2(m-Ph2PRPPh2)]
/

R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 76ꢁ
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86
79
(trans-CHÄ
/
CH, 7; CÅ
/
C, 8), irrespective of the molar
treatment of 1 with silver trifluorosulfonate was needed
to obtain the desired product (see Section 4). The new
compounds were air-stable and soluble in the more
ratio used, probably due to the trans-geometry of these
ligands. The compounds gave satisfactory elemental
analysis, as well as IR, FAB-Mass and NMR spectra
(see Section 4). The 13C-{1H}-NMR spectrum of
compound 7 showed a broad signal at d170.5 and a
common solvents. The conductivity data (125ꢁ
150 Vꢃ1
/
cm2 molꢃ1 in 10ꢃ3 mol dmꢃ3 solutions in dry
acetonitrile) showed them to be 1:1 electrolytes [44].
The IR spectrum showed a broad and strong band at
850 cmꢃ1 arising from the PF6ꢃ counterion [38]. The
MS-FAB spectra showed the corresponding peaks
multiplet at d149.8 assignable to HCÄ
/
N and C2,
respectively, downfield shifted from the spectrum of
the free ligand (ca. 22 and 20 ppm, also respectively)
[27], thereby confirming that cyclometallation was
maintained [25,43]. The C3 and C4 resonances appeared
as multiplet at d138.0 and d131.0, respectively, by
coupling with the phosphorus nucleus. An apparent
assigned to [M]ꢂ, [Mꢃ
/
COH]ꢂ and/or [MꢃCy]ꢂ, after
/
consideration of the palladium isotopes. The 31P-{1H}-
NMR spectra showed two doublets, suggesting the two
phosphorus atoms to be non-equivalent (Pa, Pb), as well
triplet at d126.8 was assigned to the HC Ä
atoms. In the 1H-NMR, the AA?XX? spin sustem of the
PCH ÄCHP group gave rise to an apparent triplet at
d6.80 [Nꢀ43.0 Hz].
/CH carbon
as an heptuplet ca. ꢁ
146 ppm assignable to PF6ꢃ
/
[1J(PF) ca. 712 Hz]. The assignment of the doublets
was made on the assumption that a ligand of greater
trans influence shifts the resonance of the phosphorus
atoms trans to it to lower frequency [41], and was
confirmed by selective decoupling experiments. The 31P
chemical shifts were clearly influenced by ring size [45],
and consequently were shifted downfield.
/
/
Reaction of [Pd{5-(COH)C6H3C(H)Ä
(m-Cl)]2 (1) with Ph2PCH2CH2AsPh2 (arphos) in 1:1
molar ratio, in acetone at room temperature afforded
/N(Cy)-C2,N}-
the dinuclear complex [{Pd[5-(COH)C6H3C(H)Ä
/N(Cy)-
C2,N](Cl)}2(m-Ph2PCH2CH2AsPh2)] (9), which was
fully characterized (see Section 4). A singlet at d38.85
in the 31P-{1H}-NMR spectrum confirmed phosphorus
The HCÄ
/
N resonance in the 1H-NMR spectra ca.
d8.50 appeared as a doublet due to coupling with the
31P nucleus trans to nitrogen. The H6 resonance was
overlapped by the phosphine phenyl protons or ap-
peared as a broad signal, but in compound 13 it could be
clearly distinguished as a triplet at d7.99 by coupling to
H4 and long-range coupling to the phosphorus nucleus
1
coordination to metal center. In the H-NMR spectrum
the COH and COH? groups gave rise to two singlets at
d9.74 and d9.73 which could not be unambiguously
assigned, as well as the H4/H4? resonances, which
appeared as two doublets of doublets ca. d7.00. Never-
theless, the corresponding Hi/Hi? and H3/H3? reso-
nances were clearly distinguished. Thus, two doublets
of doublets at d8.21 and d6.60 were assigned to Hi and
H3, respectively, and two doublets at d8.16 and d6.66
were assigned to Hi?and H3?, also respectively; the
former two resonances were coupled to the phosphorus
nucleus.
trans
[4J(H4H6):5
was assigned to the H3 resonance, shifted to lower
frequency by 0.4ꢁ0.9 ppm due to the shielding effect of
to
the
metallated
carbon
atom
/
J(PH6):/2.0 Hz]. A multiplet ca. d7.00
/
the phosphine phenyl rings. This signal was split by
coupling to both phosphorus atoms. In the case of
compound 12, selective decoupling experiments allowed
the correct assignment of the corresponding coupling
In the 13C-{1H}-NMR spectrum of compound 9 some
resonances were well differentiated for each cyclometal-
lated fragment and for the arphos phenyl rings (see
Section 4). Thus, a singlet and a broad signal at d170.5
constants [trans-4J(PH3)ꢀ
/
7.3, cis-4J(PH3)ꢀ
4.9 Hz].
/
For complexes 12 and 14 the 13C-{1H} data were
consistent with the proposed structure (see Section 4).
Two doublets of doublets at d185.5 (12) and d178.4 (14)
and d170.3 were assigned to C?Ä
/
N and CÄ
/
N carbons,
were assigned to the CÄ
/
N carbon atom, coupled to both
3
respectively; two singlets at d138.1 and d135.4 to the
C3? and C4?, respectively; and two doublets at d137.8
phosphorus atoms [3J(PaC)ꢀ
/
7.8 Hz, J(PbC) ca. 4.0
Hz). The C2 resonance was downfield shifted from the
spectrum of the free ligand by ca. 45 ppm, and showed
strong coupling to the phosphorus atom trans to carbon
(3J(PbC) ca. 120 Hz). The diphosphine carbon atoms
showed well defined resonances and most of them could
be unambiguously assigned (see Section 4).
(3J(PC)ꢀ
/
10.6 Hz) and d135.2 (4J(PC)ꢀ
/
3.6 Hz) to the
C3 and C4 resonances, also respectively. The ethylene
resonances appeared at d30.5 [d, 1J(PC)ꢀ
5.4 Hz,
/
PCH2] and d24.7 [s, CH2As]. These findings were
confirmed by the X-ray crystal structure determination
of compound 9 (see below).
Treatment of complex 1 with Ph2PCH2CH2AsPh2
Treatment of the chloride-bridged complex 1 with
dppb, dpph, dppf, cis-dppe, 1,2-dppb, and dppa in 1:2
molar ratio in the presence of NH4PF6 yielded the
and NH4PF6 in a 1:2 molar ratio in acetoneꢁ
room temperature yielded the mononuclear compound
N(Cy)-C2,N}(Ph2PCH2CH2-
/
water at
[Pd{5-(COH)C6H3C(H)Ä
/
cyclometallated compounds [Pd{5-(COH)C6H3C(H)Ä
NCy-C2,N}(Ph2PRPPh2-P,P)][PF6] (R: (CH2)4, 10;
(CH2)6, 11; Fe(C5H4)2, 12; 1,2-C6H4, 13; cis-CHÄCH,
14; NH, 15). In the case of compound 14, previous
/
AsPh2-P,As)][PF6] (16). The MS-FAB spectrum showed
the corresponding peaks at m/z 762, 735 and 679
/
assigned to [M]ꢂ, [Mꢃ
/
COH]ꢂ and [MꢃCy]ꢂ, respec-
/
tively. The NMR data were consistent with the pro-

80
R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 76ꢁ86
/
posed structure. The 31P-{1H}-NMR spectrum showed
a singlet at d61.44, downfield shifted due to the ring size
effect in five-membered chelates. In the 1H-NMR
spectra a doublet of doublets at d6.89 was assigned to
the H3 resonance, split by coupling to the 31P nucleus
trans to nitrogen [4J(PH3)ꢀ
7.8 Hz], as appeared in
/
related systems with monophosphine ligands linked to a
palladium atom, [46,47] and upfield shifted due to the
shielding effect of the phenyl rings linked to the
phosphorus atom. The crystal structure of 16 has been
determined by X-ray diffraction analysis (see below) and
confirms the spectroscopic data.
2.1. Molecular structures of complexes 3, 6, 9 and 16
Suitable crystals were grown by slowly evaporating
chloroformꢁ
hexane (6, 9) solutions of the complexes. The labeling
schemes for the compounds are shown in Figs. 2ꢁ5. All
/
n-hexane (3, 16) or dichloromethaneꢁn-
/
/
crystals consist of discrete molecules, separated by
normal van der Waals distances. Crystallographic data
and selected interatomic distances and angles are listed
in Tables 1 and 2.
Fig. 3. Molecular structure of [{Pd[5-(COH)C6H3C(H)ÄNCy-
C2,N](Cl)}2{m-(Ph2PC5H4)2Fe}] (6), with labelling scheme. Hydrogen
atoms have been omitted for clarity.
/
For compounds 3 and 9, the crystal structure
comprises a centrosymmetric dinuclear molecule (half
molecule per asymmetric unit). In the case of complex 9,
even though the bridging ligand, 1-diphenylphosphino-
2-diphenylarsinoethane, is asymmetric, the dinuclear
molecule 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. This behavior
has been observed in other complexes derived from the
arsinophosphine ligand [48,49]. The crystal structures of
6 and 16 comprise one molecule per asymmetric unit. In
the case of complex 16, the bridging ligand 1,1?-
bis(diphenylphosphino)ferrocene is not totally sym-
metric, though both cyclometallated moieties have
Fig. 2. Molecular structure of [{Pd[5-(COH)C6H3C(H)Ä
/
NCy-C2,N](Cl)}2(m-Ph2PCH2CH2PPh2)] (3), with labelling scheme. Hydrogen atoms have
been omitted for clarity.

R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 76ꢁ
/
86
81
Fig. 4. Molecular structure of [{Pd[5-(COH)C6H3C(H)Ä
/
NCy-C2,N](Cl)}2(m-Ph2PCH2CH2AsPh2)] (9), with labelling scheme. Hydrogen atoms have
been omitted for clarity.
a nitrogen atom of the benzylidene ligand, and phos-
phorus and arsenic atoms of the chelating arsinopho-
sphine ligand.
The sum of angles about palladium is 359.088 (3),
362.548 (6), 360.148 (9) and 360.508 (16); 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 angle N(1)Ã
/
Pd(1)ÃC(1) to 81.1(2)8
/
(3), 81.3(3)8 (6), 80.6(2)8 (9) and 81.3(2)8 (16). In the case
of compounds 3, 9 and 16, the geometry around the
palladium atom is slightly distorted square-planar, the
mean deviations from the least squares planes (plane 1:
Pd1, C1, N1, P1, Cl1, 3; Pd1, C1, N1, P1/As1, Cl1, 9;
Pd1, C1, N1, P1, As1, 16) are 0.0330, 0.0381 and 0.1018
A, respectively. However, for compound 6, coordination
about palladium is slightly twisted toward tetrahedral
˚
(rms deviation of the mean plane 1:0.1920 A), C1 and
Cl1 are above the plane (deviations 0.2157 and 0.2644
˚
A, respectively), and N1 and P1 are below the plane
˚
(deviations 0.2463 and 0.1969 A, also respectively).
The palladiumꢁnitrogen bond length in the metalla-
/
˚
˚
cycle (2.122(5) A, 3; 2.094(6) A, 6; 2.110(5) A, 9; 2.091(5)
˚
Fig. 5. Molecular structure of the cation for [Pd{5-(COH)C6H3C(H)Ä
NCy-C2,N}(Ph2PCH2CH2AsPh2-P,As)][PF6] (16), with labelling
scheme. Hydrogen atoms have been omitted for clarity.
/
˚
A, 16) is longer than the predicted single bond value of
˚
2.011 A, based on the sum of covalent radii for
2
nitrogen(sp ) and palladium, 0.701 and 1.31 A, respec-
˚
very similar bond distances and angles; therefore,
discussion will be limited to only one of them.
tively [50,51], and reflects the trans influence of the
phosphorusꢁ
/
arsenic atom [22,52,53]. The palladiumꢁ
/
In compounds 3, 6 and 9 each four-coordinated
palladium(II) 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 diphosphine (dppe, 3; dppf, 6) or the
arsinophosphine ligand (9) which bridges the two metal
centers, completes the metal coordination sphere. In
compound 16 the palladium(II) atom is bonded to four
different atoms: an ortho carbon of the phenyl ring and
˚
carbon bond length (2.020(6) A, 3; 2.021(8) A, 6;
˚
˚
2.015(6) A, 9; 2.060(6) A, 16) 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) [18,54,55].
˚
As bond distances (2.263(1) A, 3;
The PdÃ
/
P and PdÃ
/
˚
2.258(2) A, 6; 2.312(1) A, 9; 2.2598(16) and 2.4540(8) A,
˚
˚
16) are shorter than the sum of the single bond radii for
˚
palladium and the corresponding atom (2.41 A for PdÃ
/

82
R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 76ꢁ86
/
Table 1
Crystal and structure refinement data for complexes 3, 6, 9 and 16
3
6×
/
2CH2Cl2
9
16×H2O
/
Formula
Mr
Temperature (K)
C
54H56Cl2N2O2Pd2P2
C64H62Cl8FeN2O2Pd2P2
1505.35
293(2)
C54H56AsCl2N2O2Pd2P
1154.60
293(2)
C40H42AsF6NO2PdP
926.01
0(2)
1110.65
293(2)
0.71073
˚
Wavelenght (A)
0.71073
Triclinic
0.71073
Triclinic
0.71073
Triclinic
Crystal system
Space group
Cell dimensions
Triclinic
¯
¯
¯
¯
P
/
1/
P/
1
/
P/
1
/
P/ /
1
˚
a (A)
10.071(2)
11.520(1)
11.532(1)
89.128(10)
81.108(2)
65.788(10)
1203.90(14)
1
12.4733(19)
16.020(2)
17.750(3)
111.141(3)
105.159(3)
92.585(3)
3190.1(8)
2
10.130(5)
11.539(8)
11.568(1)
88.857(10)
81.805(10)
65.863(10)
1220.26(15)
1
12.6211(13)
14.0036(14)
14.1417(14)
97.830(2)
116.288(2)
105.001(2)
2071.7(4)
2
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
3
˚
V (A )
Z
Dcalc. (mg mꢃ3
m (mmꢃ1
)
1.532
0.968
1.567
1.212
1.571
1.595
1.484
1.379
)
Crystal size (mm)
2umax (8)
Independent reflections
0.15ꢄ
/
0.25ꢄ
/
0.15
0.20ꢄ
/
0.18ꢄ
/
0.13
0.25ꢄ
/
0.15ꢄ
/
0.15
0.29ꢄ
/
0.23ꢄ
/
0.13
0.0484)
56.62
5853 (Rint
1.005
52.82
13022 (Rint
0.924
56.64
5546 (Rint
1.058
56.60
10054 (Rint
0.945
ꢀ
/
0.0612)
ꢀ/
0.0000)
ꢀ
/
0.0399)
ꢀ/
S
R[F,I ꢁ
/
2s(I)]
wR [F2, all data]
0.0617
0.1766
0.741
0.0593
0.1847
1.059
0.0490
0.2049
1.015
0.0545
0.1727
1.645
ꢃ3
˚
max r (e A
)
˚
P, 2.55 A for PdÃ
/
As), suggesting partial double bond
Table 2
character similar to others reported earlier [56,57]. In
˚
Selected bond distances (A) and angles (8) for complexes 3, 6, 9 and 16
compounds 3, 6 and 9, the PdÃ
/Cl bond lengths, ca. 2.37
˚
3
6
9
16
A, are consistent with PdÃ
/
Cl distances found in related
species [57,58] but longer than the sum of the covalent
Bond distances
Pd(1)ÃC(1)
Pd(l)ÃN(1)
Pd(1)Ã
Pd(1)Ã
Pd(1)Ã
˚
radii (2.30 A) as a consequence of the trans influence of
the C(phenyl) carbon.
The mean deviations from the least squares planes
determined for the metallacycle (plane 2: Pd1, C1, C6,
C7, N1) and the metallated phenyl ring (plane 3: C1, C2,
˚
C3, C4, C5, C6) are 0.0169 and 0.0031 A (3); 0.0114 and
˚
0.0173 A (6); 0.0082 and 0.0057 A (9); 0.0032 and 0.0064
˚
A (16), respectively. The angles between these planes are
as follows: 2.8, 4.8, 1.3 and 1.48, also respectively. The
angles between plane 1 and the previous planes are:
plane 1/plane 2: 2.98 (3), 1.58 (6), 2.58 (9) and 5.98 (16);
and plane 1/plane 3: 5.38 (3), 6.38 (6), 3.68 (9) and 7.28
(16).
/
2.020(6)
2.122(5)
2.263(1)
2.367(1)
2.021(8)
2.094(6)
2.258(2)
2.386(2)
2.015(6)
2.110(5)
2.312(1)
2.375(2)
2.060(6)
2.091(5)
2.2598(16)
/
/P(1)
/Cl(1)
/As(1)
2.4540(8)
1.402(9)
1.436(9)
1.273(8)
C(1)Ã
C(6)Ã
N(1)Ã
O(1)Ã
P(1)Ã
P(1)Ã
/
C(6)
1.401(9)
1.414(10) 1.418(9)
/C(7)
1.432(10) 1.435(11) 1.454(9)
1.268(8) 1.275(9) 1.255(8)
˚
/
C(7)
/
C(14)
1.267(11) 1.216(11) 1.210(10) 1.290(14)
/C(15)
1.853(6)
1.894(5)
/C(27)
1.806(7)
As(1)Ã
/C(15)
1.953(6)
1.826(6)
P(1)ÃC(16)
/
Bond angles
C(1)ÃPd(1)Ã
C(1)ÃPd(1)Ã
P(1)ÃPd(1)Ã
N(1)ÃPd(1)Ã
N(1)ÃPd(1)Ã
P(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(27)Ã
C(16)Ã
C(15)Ã
/
/
N(1)
81.1(2)
81.3(3)
80.6(2)
81.3(2)
/
/P(1)
94.86(19) 99.0(2)
91.73(6) 89.50(8)
95.32(17) 97.34(18)
90.40(5)
/
/Cl(1)
/
/
Cl(1)
As(1)
92.39(15) 92.74(17) 93.82(15)
3. Conclusion
/
/
99.50(13)
82.36(5)
111.6(4)
120.7(6)
116.0(5)
110.4(4)
/
/As(1)
New cyclopalladated compounds, functionalized
through a free formyl group have been synthesized.
The mono-, di- or trimetallic nature of these compounds
/
/
Pd(1)
110.4(5)
121.2(6)
115.1(6)
111.9(5)
118.7(2)
112.7(5)
118.4(7)
116.7(7)
110.7(6)
113.5(4)
118.5(6)
115.5(5)
112.0(4)
120.20(18)
/
/
C(6)
/
/
C(7)
/
/
Pd(1)
depends on the chloro-bridged dimerꢁphosphine ligand
/
/
P(1)Ã
P(1)Ã
P(1)Ã
/
Pd(1)
Pd(1)
Pd(1)
molar ratio used, as well as on the characteristics of the
phosphines. The reactions carried out with diohosphines
in a 1:1 molar ratio give compounds with the dipho-
sphine acting as a bridging ligand. In the case of the
/
/
116.9(2)
/
/
107.7(2)
/
As(1)Ã
/Pd(1)
106.36(19)

R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 76ꢁ
/
86
83
arphos ligand, the resulting asymmetry in the final
compound makes both metallated units non-equivalent.
However, in the X-ray difraction analysis the P and As
atoms are not distinguishable due to a disordered
distribution of both atoms. The reactions performed in
a 1:2 molar ratio gave compounds with the diphosphine
acting as a chelating ligand. In the corresponding
mononuclear compound with arphos, the X-ray difrac-
tion analysis discerns the P and As atoms, which are
now in different chemical surroundings.
4.1.2. [{Pd[5-(COH)C6H3C(H)Ä
/
NCy-
C2,N](Cl)}2(m-Ph2PCH2CH2PPh2)] (3)
Yield: 72%. Anal. Found: C, 58.2; H, 5.0; N, 2.3.
C54H56Cl2N2O2P2Pd2 requires: C, 58.4; H, 5.1; N, 2.5.
IR: n(CÄ
[Mꢃ2Clꢃ
COH)Pd(PP)]ꢂ. H-NMR: 9.74 (s, Ha), 7.69 (d, H6,
4J(H4H6)ꢀ1.5 Hz), 6.99 (dd, H4, 3J(H3H4)ꢀ
7.8 Hz),
4.51(t, CH2P, 2J(PH) ꢀ10.5 Hz). 31P-{1H}-NMR:
38.00 (s).
/
O): 1689s, n(CÄ
/
N): 1621m. FAB-Mass: 826
/
/
L]ꢂ,
718
[LPd(PP)]ꢂ,
690 [(Lꢃ
/
1
/
/
/
4.1.3. [{Pd[5-(COH)C6H3C(H)Ä
/
NCy-
C2,N](Cl)}2{m-Ph2P(CH2)4PPh2}] (4)
Yield: 58%. Anal. Found: C, 59.7; H, 5.5; N, 2.3.
C56H60Cl2N2O2P2Pd2 requires: C, 59.1; H, 5.3; N, 2.5%.
4. Experimental
IR: n(CÄ
[Mꢃ
Cl]ꢂ, 853 [Mꢃ
NMR: 9.71 (s, Ha), 8.17 (dd, Hi, 4J(PHi)ꢀ
/
O): 1692s, n(CÄ
/
N): 1624m. FAB-Mass: 1103
4.1. General remarks
/
/
2Clꢃ
/
L]ꢂ, 746 [LPd(PP)]ꢂ. 1H-
/
8.3 Hz,
All solvents were distilled prior to use from appro-
priate drying agents [59]. All chemicals were used as
supplied from commercial sources. Elemental analyzes
(C, H, N) were carried out in a Carloꢁ
elemental analyzer. IR spectra were recorded as KBr
pellets or Nujol mulls on a PerkinꢁElmer 1330 spectro-
5J(HiH7)ꢀ
7.03 (dd, H4, 3J(H3H4)ꢀ
4J(PH3)ꢀ5.9 Hz). 31P-{1H}-NMR: 34.16 (s).
/
1.0 Hz), 7.68 (d, H6, J(H4H6)ꢀ
/
1.9 Hz),
4
/8.0 Hz), 6.66 (dd, H3,
/
/
Erba 1108
4.1.4. [{Pd[5-(COH)C6H3C(H)Ä
/
NCy-
C2,N](Cl)}2{m-Ph2P(CH2)6PPh2}] (5)
/
photometer. 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
Yield: 78%. Anal. Found: C, 59.6; H, 5.4; N, 2.3.
C58H64Cl2N2O2P2Pd2 requires: C, 59.7; H, 5.5; N, 2.4%.
IR: n(CÄ
[Mꢃ
Cl]ꢂ, 774 [LPd(PP)]ꢂ.1H-NMR: 9.76 (s, Ha), 8.18
(dd, Hi, J(PHi)ꢀ
/
O): 1693s, n(CÄ/N): 1624m. FAB-Mass: 1131
/
4
5
spectrometer (200.0 MHz for H, 50.3 MHz for 13C-
1
/
8.8 Hz, J(HiH7)ꢀ1.0 Hz), 7.70 (d,
/
4
3
{1H}, 81.0 MHz for 31P-{1H}). Conductivity measure-
ments were made on a Crison GLP 32 conductivimeter
using 10ꢃ3 M solutions in dry acetonitrile at room
temperature (298K). The synthesis of [Pd{5-
H6, J(H4H6)ꢀ
Hz), 6.63 (dd, H3, J(PH3)ꢀ
34.08 (s).
/
1.7 Hz), 7.04 (dd, H4, J(H3H4)ꢀ
/
8.1
5.9 Hz). 31P-{1H}-NMR:
4
/
4.1.5. [{Pd[5-(COH)C6H3C(H)Ä
/
NCy-
C2,N](Cl)}2{m-(Ph2PC5H4)2Fe}] (6)
(COH)C6H3C(H)Ä
/
NCy-C2,N}(m-Cl)]2 (1) was reported
in a recent paper from this laboratory [27].
Yield: 57%. Anal. Found: C, 58.6; H, 4.4; N, 2.1.
C62H58Cl2FeN2O2P2Pd2 requires: C, 58.9; H, 4.6; N,
4.1.1. Preparation of [{Pd[5-(COH)C6H3C(H)Ä
/
NCy-
2.2%. IR: n(CÄ
1229 [Mꢃ
845 [(Lꢃ
/
O): 1695s, n(CÄ
/
N): 1623m. FAB-Mass:
C2,N](Cl)}2(m-Ph2PCH2PPh2)] (2)
/
Cl]ꢂ, 982 [Mꢃ
/
2Clꢃ
L]ꢂ, 874 [LPd(PP)]ꢂ,
/
To a solution of 1 (25.00 mg, 0.035 mmol) in acetone
(ca. 10 ml), Ph2PCH2PPh2 (dppm, 12.13 mg, 0.032
mmol) was added. The mixture was stirred for 12 h at
r.t., after which the precipitate formed was filtered off,
/
COH)Pd(PP)]ꢂ.1H-NMR: 9.97 (s, Ha), 8.19
4
5
(dd, Hi, J(PHi)ꢀ
/
9.3 Hz, J(HiH7)ꢀ
/
1.0 Hz), 7.73 (d,
3
4
H6, J(H4H6)ꢀ
Hz), 6.47 (dd, H3, 4J(PH3)ꢀ
H
ferrocene). 31P-{1H}-NMR: 31.58 (s).
/
1.9 Hz), 7.00 (dd, H4, J(H3H4)ꢀ
/7.8
/
5.8 Hz), 5.00, 4.62, m,
dried in vacuo, and recrystallized from chloroformꢁ
/n-
hexane to yield the desired product as pale yellow
microcrystals.Yield: 36% (26.45 mg). Anal. Found: C,
58.2; H, 5.0; N, 2.4. C53H54Cl2N2O2P2Pd2 requires: C,
4.1.6. [{Pd[5-(COH)C6H3C(H)Ä
/
NCy-
C2,N](Cl)}2{m-trans(Ph2PCHÄCHPPh2)}] (7)
/
58.0; H, 5.0; N, 2.5%. IR: n(CÄ
1623m. FAB-Mass: 1061 [Mꢃ
Cl]ꢂ, 704 [LPd(PP)]ꢂ,
676 [LPdCl]ꢂ. 1H-NMR: 9.73 (s, Ha), 8.07 (dd, Hi,
4J(PHi)ꢀ7.8 Hz, 5J(HiH7)ꢀ
1.0 Hz), 7.64 (d, H6,
4J(H4H6)ꢀ
Hz), 6.25 (dd, H3, J(PH3)ꢀ
30.45 (s).
Compounds 3ꢁ
/
O): 1693s, n(CÄ
/N):
To a solution of 1 (50.00 mg, 0.070 mmol) in acetone
(ca. 10 ml), trans-dppe (25.04 mg, 0.063 mmol) was
added. The mixture was stirred for 12 h at r.t., after
which solvent was removed under reduced pressure, and
the residue triturated with diethylether to yield a brown
solid, which was filtered off and dried in vacuo.
/
/
/
/
1.5 Hz), 6.94 (dd, H4, 3J(H3H4)ꢀ
/
8.1
4
/
5.8 Hz). 31P-{1H}-NMR:
Yield: 54% (37.50 mg). Anal. Found: C, 58.5; H, 4.7;
N, 2.6. C54H54Cl2N2O2P2Pd2 requires: C, 58.5; H, 4.9;
/6 were prepared similarly, but using
dppe, dppb, dpph and dppf as appropriate, respectively.
N, 2.5%. IR: n(CÄ
/
O): 1694s, n(CÄ/N): 1625m. FAB-

84
R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 76ꢁ86
/
Mass: 1073 [Mꢃ
[LPd(PP)]ꢂ. 1H-NMR: 9.75 (s, Ha), 7.73 (d, H6,
4J(H4H6)ꢀ1.9 Hz), 7.00 (dd, H4, 3J(H3H4)ꢀ
8.3
Hz), 6.80 (at, HCÄCH, N(PH)ꢀ43.0 Hz), 6.62 (m,
H3). 31P-{1H}-NMR: 35.54 (s). 13C-NMR: 191.3 (s,
COH), 170.5 (b, CÄN), 167.7 (s, C1), 149.8 (m, C2),
138.0 (m, C3), 135.5 (at, Co), 132.7 (s, C5), 132.3 (s, Cp),
CH), 126.7
/
Cl]ꢂ, 1008 [Mꢃ
/
Clꢃ
/
COH]ꢂ, 716
and dried in vacuo over anhydrous CaCl2. The desired
complex was recrystallized from chloroformꢁn-hexane
as pale yellow microcrystals.
Yield: 24% (12.20 mg). Anal. Found: C, 56.5; H, 4.7;
N, 1.4. C42H44F6NOP3Pd requires: C, 56.5; H, 5.0; N,
/
/
/
/
/
/
1.6%. IR: n(CÄ
/
O): 1687s, n(CÄ
/
N): 1616m. FAB-Mass:
1
664 [Mꢃ
/
Cy]ꢂ. H-NMR: 9.78 (s, Ha), 6.74 (m, H3).
2
131.0 (m, C4), 128.7 (at, Cm), 126.8 (at, HC Ä
/
31P-{1H}-NMR: 32.43 (d, Pa, J(PP)ꢀ
/
42.8 Hz), 20.62
(s, C6), 62.4 (s, C7), 33.5 (s, C8, C12), 25.7 (s, C9, C11),
25.4 (s, C10).
(d, Pb).
Compounds 11ꢁ/13 were prepared similarly, but using
Compounds 8 and 9 were obtained in a similar
fashion to 7, but using dppac and arphos, respectively,
as appropiate.
dpph, dppf, and 1,2-dppb, respectively, as appropriate.
4.1.10. [Pd{5-(COH)C6H3C(H)Ä
/
NCy-
C2,N}{Ph2P(CH2)6PPh2-P,P}][PF6] (11)
4.1.7. [{Pd[5-(COH)C6H3C(H)Ä
/NCy-
Yield: 83%. Anal. Found: C, 53.2; H, 5.1; N, 1.7.
C44H48F6NOP3Pd requires: C, 53.4; H, 5.3; N, 1.5%. IR:
C2,N](Cl)}2(m-Ph2PCCPPh2)] (8)
Yield: 28%. Anal. Found: C, 58.4; H, 4.6; N, 2.6
C54H52Cl2N2O2P2Pd2 requires: C, 58.6; H, 4.7; N, 2.5%.
n(CÄ
COHꢃ
Ha), 8.66 (b, Hi), 7.01 (dd, H4, 3J(H3H4)ꢀ
4J(H4H6)ꢀ1.9 Hz), 6.90 (m, H3). 31P-{1H}-NMR:
/
O): 1690s, n(CÄ
/
N): 1627m. FAB-Mass: 663 [Mꢃ
/
1
/
Cy]ꢂ, 291 [(Lꢃ
/
COH)Pd]ꢂ. H-NMR: 9.69 (s,
IR: n(CÄ
[M]ꢂ, 714 [LPd(PP)]ꢂ. 1H-NMR: 9.71 (s, Ha), 8.17 (dd,
Hi, 4J(PHi)ꢀ8.8 Hz, 5J(HiH7)ꢀ
1.0 Hz)), 6.93 (dd,
H4, 3J(H3H4)ꢀ8.0 Hz, 4J(H4H6)ꢀ1.7 Hz). 31P-{1H}-
NMR: 15.59 (s).
/
O): 1698s, n(CÄ/N): 1626m. FAB-Mass: 1106
/
7.7 Hz,
/
2
/
/
33.35 (d, Pa, J(PP)ꢀ43.7 Hz), 16.05 (d, Pb).
/
/
/
4.1.11. [Pd{5-(COH)C6H3C(H)Ä
/
NCy-
C2,N}{(Ph2PC5H4)2Fe-P,P}][PF6] (12)
4.1.8. [{Pd[5-(COH)C6H3C(H)Ä
/NCy-
Yield: 77%. Anal. Found: C, 56.3; H, 4.0; N, 1.2.
C48H42F6FeNOP3Pd requires: C, 56.6; H, 4.2; N, 1.4%.
C2,N](Cl)}2(m-Ph2PCH2CH2AsPh2)] (9)
Yield: 43%. Anal. Found: C, 56.4; H, 4.8; N, 2.4.
C54H56AsCl2N2O2PPd2 requires: C, 56.2; H, 4.9; N,
IR: n(CÄ
[Mꢃ
Cy]ꢂ, 291 [(Lꢃ
Ha), 7.10 (dd, H4, 3J(H3H4)ꢀ
/
O): 1693s, n(CÄ
COH)Pd]ꢂ. 1H-NMR: 9.78 (s,
7.8 Hz, 4J(H4H6)ꢀ
/
N): 1618m. FAB-Mass: 790
/
/
2.4%. IR: n(CÄ
/
O): 1693s, n(CÄ
/
N): 1625m. FAB-Mass:
762 [LPd(PAs)]ꢂ. 1H-NMR: 9.74, 9.73 (s, Ha/Ha?), 8.21
/
/
4
4
4
5
2.0 Hz), 6.63 (m, H3, J(PbH3)ꢀ
/
7.3 Hz, J(PaH3)ꢀ
/
(dd, Hi, J(PHi)ꢀ
/
8.8 Hz, J(HiH7)ꢀ
/
1.0 Hz), 8.16 (d,
4.9 Hz), 4.80, 4.67, 4.32, 3.59 (d, Hferrocene). 31P-{1H}-
5
4
Hi?, J(HiH7)ꢀ
1.9 Hz), 7.00, 6.97 (dd, H4/H4?, J(H3H4)ꢀ
6.66 (d, H3?), 6.60 (dd, H3, 4J(PH3)ꢀ7.0 Hz). 31P-
{1H}-NMR: 38.85 (s). 13C-NMR: 191.4, 191.3 (s, COH,
COH?), 170.5 (s, C?ÄN), 170.3 (b, CÄN), 149.7, 149.6 (s,
C2, C2?), 138.1 (s, C3?), 137.8 (d, C3, J(PC3)ꢀ
Hz), 135.4 (s, C4?), 135.2 (d, C4, 4J(PC4)ꢀ
3.6 Hz),
/
1.0 Hz), 7.70 (d, H6/H6?, J(H4H6)ꢀ
/
2
3
NMR: 40.09 (d, Pa, J(PP)ꢀ
/
29.9 Hz), 23.69 (d, Pb).
/8.3 Hz),
13C-NMR: 191.2 (s, COH), 185.5 (dd, CÄ
7.8 Hz, 3J(PbC)ꢀ4.3 Hz), 175.8 (dd, C2, 3J(PbC)ꢀ
124.2 Hz, J(PaC)ꢀ2.1 Hz), 151.4 (s, C1), 139.0 (dd,
/
N, J(PaC)ꢀ
/
3
/
/
/
3
/
/
/
3
3
3
C3, J(PaC)ꢀ
2J(PC)ꢀ12.8 Hz), 133.8 (s, C5), 133.6 (d, Co, 2J(PC)ꢀ
12.8 Hz), 132.4 (d, Cp, J(PC)ꢀ
4J(PC)ꢀ2.2 Hz), 130.9 (dd, C4, 4J(PaC)ꢀ
4J(PbC)ꢀ
129.2 (d, Cm, J(PC)ꢀ
Cferrocene
2J(PC)ꢀ
2J(PC)ꢀ
73.3 (d, Cferrocene, 3J(PC)ꢀ
C8, C12), 29.7 (s, C9, C11), 29.8 (s, C10).
/
9.0 Hz, J(PbC)ꢀ3.5 Hz), 135.3 (d, Co,
/
/
10.6
/
/
/
4
134.4 (d, Co, 2J(PCo)ꢀ
11.4 Hz), 134.0 (s, Co), 132.7 (s,
?
/
/
2.8 Hz), 132.2 (d, Cp,
9.2 Hz,
4
/
/
?
C5, C5?), 131.2 (s, Cp), 130.4 (d, Cp, J(PCp)ꢀ
/1.4 Hz),
/
4.3 Hz), 129.6 (d, Cm, 3J(PC)ꢀ
/
9.9 Hz),
3
?
128.9 (s, Cm), 128.6 (d, Cm, J(PCm)ꢀ
/10.6 Hz), 126.8,
3
/11.4 Hz), 129.1 (s, C6), 75.7 (d,
126.7 (s, C6, C6?), 62.7 (s, C7, C7?), 33.5 (s, C8, C8?,
1
,
/
14.1 Hz), 75.5 (d, Cferrocene
,
C12, C12?), 30.5 (d, PCH2, J(PC)ꢀ5.4 Hz), 25.7 (s,
/
3
/
10.6 Hz), 75.3 (d, Cferrocene, J(PC)ꢀ
/
7.8 Hz),
C9, C9?, C11, C11?), 25.4 (s, C10, C10?), 24.7 (s,
AsCH2).
/
7.1 Hz), 69.5 (s, C7), 30.9 (s,
4.1.9. Preparation of [Pd{5-(COH)C6H3C(H)Ä
/NCy-
C2,N}{Ph2P(CH2)4PPh2-P,P}][PF6] (10)
4.1.12. [Pd{5-(COH)C6H3C(H)Ä
/
NCy-C2,N}{1,2-
To a solution of 1 (20.00 mg, 0.028 mmol) in acetone
(ca. 15 ml), dppb (23.95 mg, 0.056 mmol) was added.
The mixture was stirred for 2 h at r.t., after which
ammonium hexafluorophosphate (13.69 mg, 0.084
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
(Ph2P)2C6H4-P,P}][PF6] (13)
Yield: 70%. Anal. Found: C, 57.9; H, 4.2; N, 1.3.
C44H40F6NOP3Pd requires: C, 57.9; H, 4.4; N, 1.5%. IR:
n(CÄ
/
O): 1693m, n(CÄ
COHꢃ
Cy]ꢂ. H-NMR: 9.87 (s, Ha),
8.70 (d, Hi, J(PHi)ꢀ5.0 Hz), 8.06 (b, H6), 7.10 (m,
H3). 31P-{1H}-NMR: 55.76 (d, Pa, J(PP)ꢀ
43.39 (d, Pb).
/
N): 1618m. FAB-Mass: 766
[M]ꢂ, 655 [Mꢃ
/
/
1
4
/
2
/
25.4 Hz),
formed was filtered off, washed with water (2ꢄ5 ml)
/

R. Ares et al. / Journal of Organometallic Chemistry 665 (2003) 76ꢁ
/
86
85
4.1.13. Preparation of [Pd{5-(COH)C6H3C(H)Ä
/NCy-
4.2. X-ray crystallographic study
C2,N}(cis-Ph2PCHÄCHPPh2-P,P)][PF6] (14)
/
To a solution of 1 (40.00 mg, 0.056 mmol) in acetone
(ca. 15 cm3), silver trifluorosulfonate (14.42 mg, 0.056
mmol) was added. The mixture was stirred for 1 h and
filtered through Celite to eliminate the silver chloride
Three-dimensional, r.t. X-ray data were collected on a
Siemens Smart CCD diffractometer by the v scan
method using graphite-monochromated MoꢁKa radia-
/
tion. All the measured reflections were corrected for
Lorentz and polarization effects and for absorption by
semi-empirical methods based on symmetry-equivalent
and repeated reflections. The structures were solved by
direct methods and refined by full matrix least squares
on F2. The formyl oxygen atom in compound 16 was
found to be disordered over two positions [O(1) and
O(2)]. The occupancies of the pairs of positions were
tied to give an overall value of 1.0 and then refined
giving values of, ca. 0.5 for each component. Hydrogen
atoms were included in calculated positions and refined
precipitate, cis-dppe (44ꢁ50 mg, 0.112 mmol) and
/
NH4PF6 (27.38 mg, 0.168 mmol) were added to the
resultant solution, stirred for 12 h, and the precipitate
formed filtered off, yielding a pale yellow solid which
was recrystallized in chloroformꢁn-hexane.
/
Yield: 57% (55.61 mg). Anal. Found: C, 56.1; H, 3.9;
N, 1.6. C40H38F6NOP3Pd requires: C, 55.7; H, 4.4; N,
1.6%. IR: n(CÄ
716 [M]ꢂ, 688 [Mꢃ
NMR: 9.84 (s, Ha), 8.54 (d, Hi, J(PHi)ꢀ
(t, H6, 4J(H4H6)ꢀ2.0 Hz, 5J(PH6)ꢀ
2.0 Hz), 7.82 (dd,
8.0 Hz), 7.17 (m, H3). 31P-{1H}-NMR:
62.32 (d, Pa, 2J(PP)ꢀ11.0 Hz), 53.71 (d, Pb). 13C-NMR:
191.4 (s, COH), 178.4 (dd, CÄ 7.8 Hz,
N, 3J(PaC)ꢀ
3J(PbC)ꢀ
4.0 Hz), 150.3 (s, C1), 174.5 (d, C2,
3J(PbC)ꢀ CH, 1J(PC)ꢀ
119.2 Hz), 146.0 (dd, HCÄ
49.7 Hz, 2J(PC)ꢀ
34.1 Hz), 142.8 (dd, HCÄCH,
1J(PC)ꢀ41.2 Hz, 2J(PC)ꢀ
22.0 Hz), 138.0 (dd, C3,
3J(PaC)ꢀ9.9 Hz, 3J(PbC)ꢀ
2.8 Hz), 134.5 (s, C5),
133.8 (d, Co, 2J(PC)ꢀ
12.8 Hz), 133.2 (d, Co,
2J(PC)ꢀ
12.8 Hz), 133.0, 132.8 (b, Cp), 131.8 (dd, C4,
4J(PaC)ꢀ12.8 Hz, 4J(PbC)ꢀ
5.0 Hz), 130.2 (d, Cm,
3J(PC)ꢀ9.9 Hz), 130.0 (d, Cm, 3J(PC)ꢀ
10.6 Hz),
126.3 (d, Ci, 1J(PC)ꢀ
41.2 Hz), 125.6 (d, Ci,
1J(PC)ꢀ
55.4 Hz), 69.0 (s, C7), 33.8 (s, C8, C12), 25.1
/
O): 1695s, n(CÄ
/
N): 1614m. FAB-Mass:
1
/
COH]ꢂ, 291 [(Lꢃ
/
COH)Pd]ꢂ. H-
4
/
8.3 Hz), 7.99
/
/
in riding mode. Refinement converged at a final Rꢀ
0.0617, 0.0593, 0.0490 and 0.0545 (for complexes 3, 6, 9
and 16, respectively, observed data, F) and wR2ꢀ
/
3
H4, J(H3H4)ꢀ
/
/
/
/
/
0.1766, 0.1847, 0.2049 and 0.1727 (for complexes 3, 6,
9 and 16, 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 [60].
/
/
/
/
/
/
/
/
/
/
/
/
5. Supplementary material
/
/
/
/
Full details of data collection and structure refine-
ment have been deposited with the Cambridge Crystal-
lographic Data Center, CCDC reference numbers
185153, 185154, 185152 and 185155 for compounds 3,
6, 9 and 16, respectively. Copies of this information may
be obtained free of charge from the Director, CCDC, 12
/
/
(s, C9, C11), 24.6 (s, C10).
Compounds 15 and 16 were obtained in a similar
fashion to 10, but using dppa and arphos, respectively,
as appropriate.
Union Road, Cambridge, CB2 1EZ, UK (Fax: ꢂ44-
/
1223-336033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
4.1.14. [Pd{5-(COH)C6H3C(H)Ä
/NCy-
C2,N}(Ph2PNHPPh2-P,P)][PF6] (15)
Yield: 71%. Anal. Found: C, 53.3; H, 4.4; N, 3.4.
C38H37F6N2OPdP3 requires: C, 53.6; H, 4.4; N, 3.3%.
Acknowledgements
IR: n(CÄ
[M]ꢂ, 677 [Mꢃ
Hi, 4J(PHi)ꢀ7.8 Hz), 7.90 (b, H6). 31P-{1H}-NMR:
/
O): 1694s, n(CÄ
/
N): 1617m. FAB-Mass: 705
We thank the DGES (Proyecto PB98-0638-C02-01/
02) and the Xunta de Galicia (Proyecto PGIDT99P-
XI20907B) for financial support. D.V.G. acknowledges
a fellowship from the Xunta de Galicia.
/
COH]ꢂ. 1H-NMR: 9.86 (s, Ha), 8.34 (d,
/
2
43.77 (d, Pa, J(PP)ꢀ67.8 Hz), 32.59 (d, Pb).
/
4.1.15. [Pd{5-(COH)C6H3C(H)Ä
/NCy-
C2,N}(Ph2PCH2CH2AsPh2-P,As)][PF6] (16)
Yield: 86%. Anal. Found: C, 52.6; H, 4.5; N, 1.5.
C40H40AsF6NOP2Pd requires: C, 52.9; H, 4.4; N, 1.5%.
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COHꢃ
Cy]ꢂ, 291 [(Lꢃ
Ha), 7.29 (dd, H4, J(H3H4)ꢀ
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