Synthesis and characterization of monomeric aryloxo palladium complexes of the type [Pd(N-N)(OAr)(C6F5)]. Crystal structure of [Pd(tmeda)(C6F5)(OC6H4NO 2-p)]

Article abstract of DOI:10.1002/zaac.200570048

Mononuclear palladium-hydroxo complexes of the type [Pd(N-N)(C ₆F₅)(OH)][(N-N) = 2,2′-bipyridine (bipy), 4,4′-dimethyl-2,2′-bipyridine (Me₂bipy), 1,10-phenantroline (phen) or N,N,N′,N′-tetramethylethylenediamine (tmeda) react with phenols ArOH in tetrahydrofuran giving the corresponding aryloxo complexes [Pd(N-N)(C₆F₅)(OAr)]. Elemental analyses and spectroscopic (IR, ¹H and ¹⁹F) methods have been used to characterize the new complexes. The X-ray crystal structure of [Pd(tmeda)-(C₆F₅)(OC₆H₄NO ₂-p)] has been determined. In the crystal packing the planes defined by two C₆H₄ rings show a parallel orientation. There are also intermolecular C-H...F and C-H...O hydrogen bonds.

Full text of DOI:10.1002/zaac.200570048

Synthesis and Characterization of Monomeric Aryloxo Palladium Complexes of
the Type [Pd(N؊N)(OAr)(C6F5)].
Crystal Structure of [Pd(tmeda)(C6F5)(OC6H4NO2-p)]
a,
a
a
a
a
b
´
´
´
´
´
´
Jose Ruiz *, M. Teresa Martınez , Consuelo Vicente , Venancio Rodrıguez , Gregorio Lopez , Jose Perez ,
Penny A. Chalonerc, and Peter B. Hitchcockc
a
´
´
´
Murcia/Spain, Departamento de Quımica Inorganica, Facultad de Quımica, Universidad de Murcia
b
´
´
´
´
´
Cartagena/Spain, Departamento de Ingenierıa Minera, Geologica y Cartografica (Area de Quımica Inorganica), Universidad
´
Politecnica de Cartagena
c Brighton/U.K., School of Life Sciences, University of Sussex
Received December 16th, 2004; accepted February 28th, 2005.
Dedicated on the memory of Professor Antonio Jerez
Abstract. Mononuclear palladium-hydroxo complexes of the type
[Pd(NϪN)(C6F5)(OH)][(NϪN) ϭ 2,2Ј-bipyridine (bipy), 4,4Ј-di-
methyl-2,2Ј-bipyridine (Me2bipy), 1,10-phenantroline (phen) or
N,N,NЈ,NЈ-tetramethylethylenediamine (tmeda) react with phenols
ArOH in tetrahydrofuran giving the corresponding aryloxo com-
plexes [Pd(NϪN)(C6F5)(OAr)]. Elemental analyses and spectros-
copic (IR, 1H and 19F) methods have been used to characterize the
new complexes. The X-ray crystal structure of [Pd(tmeda)-
(C6F5)(OC6H4NO2-p)] has been determined. In the crystal packing
the planes defined by two C6H4 rings show a parallel orientation.
There are also intermolecular CϪH···F and C-H···O hydrogen bonds.
Keywords: Palladium; Aryloxo; Mononuclear complexes; Crystal
structure
Introduction
[Pd(NϪN)(OH)(C6F5)] (NϪN ϭ 2,2Ј-bipyridine (bipy),
4,4Ј-dimethyl-2,2Ј-bipyridine (Me2bipy), 1,10-phenantroline
(phen) or N,N,NЈ,NЈ-tetramethylethylenediamine (tmeda))
and their reactions with CO in methanol or SO2 in alcohols
at room temperature to yield the corresponding methoxy
carbonyl [17] complexes [Pd(NϪN)(CO2Me)(C6F5)] or
alkyl sulfito [18] complexes [(NϪN)Pd(SO2OR)(C6F5)],
respectively. We now have studied the reactions of
[(NϪN)Pd(OH)(C6F5)] (NϪN ϭ bipy, Me2bipy, phen or
tmeda) with phenols ArOH.
The chemistry of late transition metal aryloxides [1] is re-
cently attracting growing attention partly because of their
characteristic chemical properties such as CϪO bond for-
mation reactions [2, 3] and partly because of their recently
discovered unique chemical reactivities such as CO inser-
tion into metal phenoxide bonds [1, 4Ϫ7] and adduct for-
mation with alcohols through strong hydrogen bonding
[8Ϫ13]. Unfortunately, the synthesis and reactivity of pal-
ladium and platinum alkoxide and aryloxide complexes
have been little explored, probably because it was thought
that PdϪO and PtϪO bonds would be weak due to an un-
favorable interaction between the “hard” alkoxide ligand
and the “soft” metal centre [14]. The thermochemical
studies of Bryndza and Bercaw have shown that this is a
misconception [1]. We have reported [15] on the synthesis of
the di-μ-methoxo complex [NBu4]2[{Pt(C6F5)2(μ-OMe)}2]
and binuclear aryloxo complexes of the type
[NBu4]2[{M(C6F5)2(μ-OAr)}2] (M ϭPd, Pt) and monomeric
aryloxo complexes of the type [NBu4][M(C6F5)2(OAr)L]
(L ϭ PPh3, M ϭ Pd, Pt;L ϭ CO, M ϭ Pt) [16]. We have
also recently described [17] the synthesis of monomeric
Results and Discussion
The ready reactivity of the monomeric hydroxo complexes
[Pd(NϪN)(OH)(C6F5)] (NϪN ϭ 2,2Ј-bipyridine (bipy),
4,4Ј-dimethyl-2,2Ј-bipyridine (Me2bipy), 1,10-phenantroline
(phen) or N,N,NЈ,NЈ-tetramethylethylenediamine (tmeda)
towards protic electrophiles is in agreement with the
highϪfield proton resonance of the OH group [17] and they
react smoothly in tetrahydrofuran with phenols ArOH at
room temperature in a 1:1 molar ratio to yield the mono-
meric aryloxo complexes 1-12 shown in Scheme 1. The
acidic proton of the phenol is abstracted by the correspond-
ing hydroxo-complex generating the anionic ligand
ArOϪwhich is subsequently trapped by the organometallic-
moiety [Pd(NϪN)(C6F5)]ϩ to form complexes1-12 and the
concomitant release of water. Complexes 1-12 are all air-
stable solids and the thermal analysis shows that they de-
compose above 180 °C in a dynamic N2 atmosphere. The
structures were assigned on the basis of microanalytical, IR,
hydroxo
palladium(II)
complexes
of
the
type
´
* Prof. Dr. Jose Ruiz
Universidad de Murcia
Departamento de Quımica Inorganica
E-30071 Murcia/Spain
´
´
E-mail: jruiz@um.es
Z. Anorg. Allg. Chem. 2005, 631, 2227Ϫ2231
DOI: 10.1002/zaac.200570048
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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J. Ruiz, M. T. Martınez, C. Vicente, V. Rodrıguez, G. Lopez, J. Perez, P. A. Chaloner, P. B. Hitchcock
coordinated nature of the anionic group adyacent to it [24].
The 19F NMR spectra of complexes 1-12 reveals the pres-
ence of a freely rotating pentafluorophenyl ring which gives
three resonances (in the ratio 2:2:1) for the o-, m-, and
p-fluorine atoms, respectively.
Description of the Crystal Structure of complex 12
Colourless crystals suitable for X-ray diffraction studies
were obtained by slow diffusion of hexane into a benzene
solution of 12. The crystal structure of complex 12 is shown
in Figure 1. Selected bond distances and angles are pre-
sented in Table 1.
Scheme 1
and 1H and 19F NMR data. The IR spectra show the
characteristic absorption bands of the C6F5 group [19] at
1630, 1490, 1450, 1050, 950 and a single band at ca.
800 cmϪ1 which is derived from the so-called X-sensitive
mode [20] in C6F5 halogen molecules, which is character-
istic of the presence of only one C6F5 group in the coordi-
nation sphere of the palladium atom and behaves like a
Figure 1 ORTEP drawing of complex 12 showing the atom num-
bering scheme. Displacement ellipsoids are drawn at the 50 % pro-
bability level.
1
ν(MϪC) band [21Ϫ23]. The H NMR spectra (Experimen-
tal Section) show the characteristic resonances due to the
unsymmetrical neutral ligand [17, 24-27] and the resonance
at lowest field in complexes 1-9 is assigned to Hα
(Scheme 2) and its chemical shift is very sensitive to the
˚
Table 1 Selected bond distances/A and bond angles/° for com-
plex 12
PdϪC(1)
PdϪN(1)
PdϪN(2)
PdϪO(1)
2.018(6)
2.068(5)
2.120(4)
2.012(4)
C(1)ϪPdϪN(1)
C(1)ϪPdϪN(2)
N(1)ϪPdϪN(2)
O(1)ϪPdϪC(1)
O(1)ϪPdϪN(1)
O(1)ϪPdϪN(2)
94.5(2)
178.7 (2)
85.1(2)
89.3(2)
174.09(18)
91.03(18)
The coordination about palladium is approximately
˚
square planar. The PdϪO bond length (2.012(4) A) is typi-
cal for phenoxide ligands to this metal ion trans to a N-
donor [13, 28, 29]. The different PdϪN (PdϪN(2),
˚
˚
2.120(4) A; Pd-N(1), 2.068(5) A) distances are in agreement
with the higher trans influence of the group C6F5 compared
to OAr. The chelate angle N(1)ϪPdϪN(2) (85.1(2)°) is a bit
higher to that found in [Pd(tmeda)(CO2Me)(C6F5)]
(83.9(2)°) [17]. In complex 12 there are some intercon-
Scheme 2
2228
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 2227Ϫ2231

Monomeric Aryloxo Palladium Complexes of the Type [Pd(NϪN)(OAr)(C6F5)]
nections by hydrogen bonds involving some of the fluorine
atoms as proton acceptors, with short intermolecular
CϪH···F distances (Table 2) [30, 31]. There are also inter-
Preparation of Complexes [Pd(N؊N)(C6F5)(OAr)]
[N؊N ؍ bipy, Ar ؍ C6H5 (1), p-MeC6H4 (2),
p-NO2C6H4 (3), p-ClC6H4 (4) or p-NCC6H4 (5);
N؊N ؍ Me2bipy, Ar ؍ p-MeC6H4 (6),p-NO2C6H4
(7); N؊N ؍ phen, Ar ؍ p-MeC6H4 (8),
p-NO2C6H4 (9)]
˚
Table 2 Hydrogen bonds for complex 12/A and °
D-H
0.96
0.96
0.96
0.96
0.96
0.96
H···A
2.66
2.48
2.57
2.62
2.56
2.66
D···A
<(DHA)
110.5
169.9
167.4
129.8
127.3
124.0
3.128(8)
3.434(8)
3.515(8)
3.322(8)
3.232(10)
3.297(10)
C8-H8C···F1(i)
To a suspension of the corresponding hydroxo palladium complex
C11-H11C···F5(ii)
C7-H7B···F5(ii)
C8-H8A···O1(i)
C11-H11B···O2(iii)
C12-H12A···O2(iii)
[Pd(NϪN)(C6F5)(OH)] (NϪN
ϭ bipy, Me2bipy or phen)
(0.134 mmol) in tetrahydrofuran(15 mL) was added the corre-
sponding phenol (0.134 mmol) to yield an orange solution which
was stirred at room temperature for 1-2 h, then solvent was par-
tially eliminated under reduced pressure. On addition of hexane
an orange or yellowish precipitate formed which was separated by
filtration and air-dried.
i: x, 0.5Ϫy, Ϫ0.5ϩz
ii: x, 0.5Ϫy, 0.5ϩz
iii: 1Ϫx,1Ϫy,1Ϫz
Complex 1: Yield: 60 mg (85 %). Anal. Calcd. for C22H13N2F5OPd:
C 50.6, H 2.5, N 5.4. Found: C 50.3, H 2.5, N 5.3 %. Mp: 212 °C
dec.
molecular CϪH···O hydrogen bonds. Furthermore, in the
crystal packing (Figure 2) the planes defined by two C6H4
IR (Nujol, cmϪ1): 792 ν(PdϪC6F5). 1H NMR (CDCl3): δ 8.68 (dd, 1 H, Hα,
J(HαHβ) ϭ 5.1 Hz, J(HαHγ) ϭ 1.5 Hz), 7.97 (m, 4 H, HγϩHγЈϩHδϩHδЈ),
7.50 (dd, 1 H, HαЈ, J(HαЈHβЈ) ϭ 5.1 Hz, J(HαЈHγЈ) ϭ 1.5 Hz), 7.48 (dd, 1 H,
Hβ, J(HβHγ) ϭ 9.3 Hz, J(HαHβ) ϭ 4.8 Hz), 7.29 (dd, 1 H, HβЈ, J(HβЈHγЈ) ϭ
9.3 Hz, J(HαЈHβЈ) ϭ 4.8 Hz), 7.08 (d, 2 H, Ho of OC6H5, J(HoHm) ϭ
8.0 Hz), 6.91 (dd, 2 H, Hm of OC6H5, J ϭ 8.0 Hz), 6.43 (t, 1 H, Hp of
OC6H5, J(HmHp)
ϭ δ Ϫ119.3 (d, 2Fo,
8.0 Hz). 19F NMR (CDCl3):
J(FoFm) ϭ 21.5 Hz), Ϫ160.0 (t, 1Fp, J(FmFp) ϭ 19.8 Hz), Ϫ166.1 (m, 2Fm).
Complex 2: Yield: 62 mg (86 %). Anal. Calcd. for C23H15N2F5OPd:
C 51.5, H 2.8, N 5.2. Found: C 51.3, H 2.7, N 5.3 %. Mp: 250 °C
dec.
IR (Nujol, cmϪ1): 790 ν(PdϪC6F5). 1H NMR (CDCl3): δ 8.66 (dd, 1 H, Hα,
J(HαHβ)
ϭ
5.1 Hz, J(HαHγ)
ϭ
1.5 Hz ), 7.97 (m, 5 H,
HγϩHγЈϩHδϩHδЈϩHαЈ), 7.48 (dd, 1 H, Hβ, J(HβHγ) ϭ 9.0 Hz, J(HαHβ) ϭ
4.5 Hz), 7.30 (dd, 1 H, HβЈ, J(HβЈHγЈ) ϭ 9.0 Hz, J(HαЈHβЈ) ϭ 4.5 Hz), 6.98
(d, 2 H, Ho of OC6H4Me-p, J(HoHm) ϭ 8.3 Hz), 6.91 (d, 2 H, Hm of
OC6H4Me-p, J ϭ 8.3 Hz), 2.08 (s, 3 H, CH3 of OC6H4Me-p). 19F NMR
(CDCl3): δ Ϫ119.2 (d, 2Fo, J(FoFm) ϭ 21.4 Hz), Ϫ160.0 (t, 1Fp, J(FmFp) ϭ
19.8 Hz), Ϫ162.8 (m, 2Fm).
Figure 2 View of the crystal packing of complex 12 showing two
p-NO2C6H4O ligands in a parallel orientation.
Complex 3: Yield: 53 mg (70 %). Anal. Calcd. for
C22H12N3F5O3Pd: C 46.5, H 2.1, N 7.4. Found: C 46.2, H 2.1, N
7.2 %. Mp: 213 °C dec.
IR (Nujol, cmϪ1): 790 ν(PdϪC6F5). 1H NMR (CDCl3): δ 8.46 (d, 1 H, Hα,
J(HαHβ) ϭ 4.9 Hz), 7.97 (m, 5 H, HγϩHγЈϩHδϩHδЈϩHαЈ), 7.91 (d, 2 H, Ho
of OC6H4NO2-p, J(HoHm) ϭ 9.2 Hz), 7.60 (dd, 1 H, Hβ, J(HβHγ) ϭ 9.2 Hz,
J(HαHβ) ϭ 4.9 Hz), 7.42 (dd, 1 H, HβЈ, J(HβЈHγЈ) ϭ 9.2 Hz, J(HαЈHβЈ) ϭ
4.9 Hz), 7.05 (d, 2 H, Hm of OC6H4NO2-p, J(HoHm) ϭ 9.2 Hz). 19F NMR
(CDCl3): δ Ϫ119.9 (d, 2Fo, J(FoFm) ϭ 22.8 Hz), Ϫ158.6 (t, 1Fp, J(FmFp) ϭ
21.0 Hz), Ϫ161.9 (m, 2Fm).
rings show a parallel orientation. The distance between
˚
these planes are 3.594 A. The distance between the centro-
˚
ids defined by the two C6H4 rings is 4.498 A.
Experimental Section
General
Complex 4: Yield: 55 mg (74 %). Anal. Calcd. for
C22H12N2ClF5OPd: C 47.4, H 2.2, N 5.0. Found: C 47.2, H 2.1, N
5.2 %. Mp: 208 °C dec.
IR (Nujol, cmϪ1): 794 ν(PdϪC6F5). 1H NMR (CDCl3): δ 8.56 (d, 1 H, Hα,
J(HαHβ) ϭ 4.7 Hz), 7.98 (m, 5 H, HγϩHγЈϩHδϩHδЈϩHαЈ), 7.49 (dd, 1 H,
Hβ, J(HβHγ) ϭ 9.4 Hz, J(HαHβ) ϭ 4.7 Hz), 7.31 (dd, 1 H, HβЈ, J(HβЈHγЈ) ϭ
9.4 Hz, J(HαЈHβЈ) ϭ 4.7 Hz), 6.98 (d, 2 H, Ho of OC6H4Cl-p, J(HoHm) ϭ
8.7 Hz), 6.93 (d, 2 H, Hm of OC6H4Cl-p, J (HoHm) ϭ 8.7 Hz). 19F NMR
(CDCl3): δ Ϫ119.4 (d, 2Fo, J(FoFm) ϭ 21.4 Hz), Ϫ159.6 (t, 1Fp, J(FmFp) ϭ
20.0 Hz), Ϫ162.5 (m, 2Fm).
The C, H, N analyses were performed with a Carlo Erba
model EA 1108 microanalyzer. Decomposition tempera-
tures were determined with a Mettler TG-50 thermobalance
at a heating rate of 5 °C minϪ1 and the solid samples under
nitrogen flow (100 mL minϪ1). The 1H and 19F NMR spec-
tra were recorded on a Bruker AC 200E, Varian Unity 300
or Bruker AV-400 spectrometer, using SiMe4 and CFCl3as
standards respectively. Infrared spectra were recorded on a
Perkin-Elmer 16F PC FT-IR spectrophotometer using
Nujol mulls between polyethylene sheets. Solvents were
dried by the usual methods. The starting complexes
[Pd(NϪN)(C6F5)(OH)](NϪN ϭ bipy, Me2bipy, phen and
tmeda) were prepared by procedures described elsewhere
[17].
Complex 5: Yield: 51 mg (69 %). Anal. Calcd. for C23H12N3F5OPd:
C 50.4, H 2.2, N 7.7. Found: C 50.7, H 2.4, N 7.5 %. Mp: 213 °C
dec.
IR (Nujol, cmϪ1): 792 ν(PdϪC6F5). 1H NMR (CDCl3): δ 8.45 (d, 1 H, Hα,
J(HαHβ) ϭ 5.0 Hz), 8.03 (m, 4 H, HγϩHγЈϩHδϩHδЈ), 7.95 (d, 1 H, HαЈ
,
J(HαЈHβЈ) ϭ 5.5 Hz), 7.49 (dd, 1 H, Hβ, J(HβHγ) ϭ 9.6 Hz, J(HαHβ) ϭ
4.7 Hz), 7.36 (dd, 1 H, HβЈ, J(HβЈHγЈ) ϭ 9.6 Hz, J(HαЈHβЈ) ϭ 4.7 Hz), 7.18
Z. Anorg. Allg. Chem. 2005, 631, 2227Ϫ2231
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© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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(d, 2 H, Ho of OC6H4CN-p, J(HoHm) ϭ 8.6 Hz), 7.04 (d, 2 H, Hm of
4H, CH2 of tmeda), 2.57 (s, 6H, Me of tmeda), 2.53 (s, 6H, Me of tmeda).
19F NMR (CDCl3): δ Ϫ119.2 (d, 2Fo, J(FoFm) ϭ 24.5 Hz), Ϫ160.5 (t, 1Fp,
J(FmFp) ϭ 19.8 Hz), Ϫ163.3 (m, 2Fm).
OC6H4CN-p, J(HoHm) ϭ 8.6 Hz). 19F NMR (CDCl3): δ Ϫ119.7 (d, 2Fo,
J(FoFm) ϭ 21.4 Hz), Ϫ158.9 (t, 1Fp, J(FmFp) ϭ 19.8 Hz), Ϫ162.2 (m, 2Fm).
Complex 11: Yield: 64 mg (75 %). Anal. Calcd. for
C19H23N2F5OPd: C 45.9, H 4.7, N 5.6. Found: C 45.6, H 4.5, N
5.5 %. Mp: 182 °C dec.
IR (Nujol, cmϪ1): 786 ν(PdϪC6F5). 1H NMR (CDCl3): δ 6.86 (d, 2 H, Ho
of OC6H4Me-p, J(HoHm) ϭ 8.2 Hz), 6.69 (d, 2 H, Hm of OC6H4Me-p,
J(HoHm) ϭ 8.2 Hz), 2.63 (s, 4H, CH2 of tmeda), 2.58 (s, 6H, Me of tmeda),
2.52 (s, 6H, Me of tmeda), 2.07 (s, 3 H, CH3 of OC6H4Me-p). 19F NMR
(CDCl3): δ Ϫ119.1 (d, 2Fo, J(FoFm) ϭ 24.3 Hz), Ϫ160.6 (t, 1Fp, J(FmFp) ϭ
21.3 Hz), Ϫ163.3 (m, 2Fm).
Complex 6: Yield: 57 mg (75 %). Anal. Calcd. for C25H19N2F5OPd:
C 53.2, H 3.4, N 5.0. Found: C 53.5, H 3.2, N 5.2 %. Mp: 227 °C
dec.
IR (Nujol, cmϪ1): 792 ν(PdϪC6F5). 1H NMR (CDCl3): δ 8.46 (d, 1 H, Hα,
J(HαHβ)
ϭ 5.1 Hz), 7.74 (m, 3 H, HδϩHδЈϩHαЈ), 7.24 (d, 1 H, Hβ,
J(HβHα) ϭ 5.7 Hz), 7.06 (d, 1 H, HβЈ, J(HβЈHαЈ) ϭ 5.7 Hz), 6.90 (d, 2 H,
Ho of OC6H4Me-p, J(HoHm) ϭ 7.6 Hz), 6.70 (d, 2 H, Hm of OC6H4Me-p,
J(HoHm) ϭ 7.6 Hz), 2.45 (s, 3 H, CH3 of Me2bipy), 2.44 (s, 3 H, CH3 of
Me2bipy), 2.07 (s, 3 H, CH3 of OC6H4Me-p). 19F NMR (CDCl3): δ Ϫ119.2
(d, 2Fo, J(FoFm) ϭ 21.4 Hz), Ϫ160.5 (t, 1Fp, J(FmFp) ϭ 19.7 Hz), Ϫ163.0
(m, 2Fm).
Complex 12: Yield: 61 mg (78 %). Anal. Calcd. for
C18H20N3F5O3Pd: C 41.0, H 3.8, N 8.0. Found: C 40.7, H 3.7, N
7.8 %. Mp: 207 °C dec.
IR (Nujol, cmϪ1): 788 ν(PdϪC6F5). 1H NMR (CDCl3): δ 7.85 (d, 2 H, Ho
of OC6H4NO2-p, J(HoHm) ϭ 9.3 Hz), 6.69 (d, 2 H, Hm of OC6H4NO2-p, J
(HoHm) ϭ 9.3 Hz), 2.86 (s, 4H, CH2 of tmeda), 2.58 (s, 6H, Me of tmeda),
2.57 (s, 6H, Me of tmeda). 19F NMR (CDCl3): δ Ϫ119.9 (d, 2Fo, J(FoFm) ϭ
22.7 Hz), Ϫ159.1 (t, 1Fp, J(FmFp) ϭ 21.3 Hz), Ϫ162.4 (m, 2Fm).
Complex 7: Yield: 66 mg (83 %). Anal. Calcd. for
C24H16N3F5O3Pd: C 48.4, H 2.7, N 7.1. Found: C 48.1, H 2.9, N
6.9. Mp: 235 °C dec.
IR (Nujol, cmϪ1): 780 ν(PdϪC6F5). 1H NMR (CDCl3): δ 8.24 (d, 1 H, Hα,
J(HαHβ) ϭ 5.4 Hz), 7.92 (m, 3 H, HδϩHδЈϩHo of OC6H4NO2-p), 7.78 (d,
1 H, HαЈ, J(HαЈHβЈ) ϭ 5.4 Hz), 7.34 (d, 1 H, Hβ, J(HβHα) ϭ 5.7 Hz), 7.17
(d, 1 H, HβЈ, J(HβЈHαЈ) ϭ 5.7 Hz), 7.06 (d, 2 H, Hm of OC6H4NO2-p, J ϭ
9.3 Hz), 2.44 (s, 6 H, CH3 of Me2bipy). 19F NMR (CDCl3): δ Ϫ119.8 (d, 2Fo,
J(FoFm) ϭ 21.2 Hz), Ϫ159.0 (t, 1Fp, J(FmFp) ϭ 19.8 Hz), Ϫ162.1 (m, 2Fm).
X-ray data collection and structure determination
Complex 8: Yield: 55 mg (73 %). Anal. Calcd. for C25H15N2F5OPd:
C 53.5, H 2.7, N 5.0. Found: C 53.2, H 2.6, N 4.9 %. Mp: 215 °C
dec.
IR (Nujol, cmϪ1): 796 ν(PdϪC6F5). 1H NMR (CDCl3): δ 8.95 (d, 1 H, Hα,
J(HαHβ) ϭ 4.9 Hz), 8.50 (m, 2 H, HδϩHδЈ), 8.28 (d, 1 H, HαЈ, J(HαЈHβЈ) ϭ
4.9 Hz), 7.96 (m, 2 H, HγϩHγЈ), 7.82 (dd, 1 H, Hβ, J(HβHγ) ϭ 8.2 Hz,
J(HαHβ) ϭ 4.9 Hz), 7.65 (dd, 1 H, HβЈ, J(HβЈHγЈ) ϭ 8.2 Hz, J(HαЈHβЈ) ϭ
4.9 Hz), 7.13 (d, 2 H, Ho of OC6H4Me-p, J(HoHm) ϭ 8.2 Hz), 6.79 (d, 2 H,
Hm of OC6H4Me-p, J(HoHm)ϭ 8.2 Hz), 2.13 (s, 3 H, CH3 of OC6H4Me-p).
19F NMR (CDCl3): δ Ϫ119.1 (d, 2Fo, J(FoFm) ϭ 22.8 Hz), Ϫ160.1 (t, 1Fp,
J(FmFp) ϭ 19.8 Hz), Ϫ162.7 (m, 2Fm).
Data collection was performed on an Enraf-Nonius CAD4 dif-
fractometer. The scan mode was θ-2θ and psi-scan absorption cor-
rection was applied. The crystallographic data are shown in
Table 3.
Table 3 Crystal data and summary of data collection and refine-
ment for 12
3
˚
Empirical formula
Formula weight
Crystal system
C18H20F5N3O3Pd Unit cell volume /A
2054.8 (6)
527.77
monoclinic
Temperature /K
Space group
Z
293
P21/c
4
Unit cell dimensions
Complex 9: Yield: 66 mg (83 %). Anal. Calcd. for
C24H12N3F5O3Pd: C 48.7, H 2.0, N 7.1. Found: C 48.9, H 2.2, N
7.0 %. Mp: 214 °C dec.
IR (Nujol, cmϪ1): 794 ν(PdϪC6F5). 1H NMR (CDCl3): δ 8.87 (dd, 1H, Hγ,
J(HβHγ) ϭ 8.2 Hz, J(HαHγ) ϭ 1.3 Hz), 8.82 (dd, 1H, HγЈ, J(HβЈHγЈ) ϭ
˚
a /A
10.309 (2)
17.008 (3)
12.199 (2)
90
106.120 (10)
90
μ /mmϪ1
0.972
3811
˚
b /A
˚
c /A
Reflections collected
Independent reflections 3607
Ͱ /°
β /°
γ /°
R(int)
R1 [I > 2σ(I)]
wR2 (all data)
0.0360
0.0517
0.1033
8.2 Hz, J(HαHγ)
ϭ 1.3 Hz), 8.61 (dd, 1 H, Hα, J(HαHβ) ϭ 4.9 Hz,
J(HαHγ) ϭ 1.3 Hz ), 8.37 (dd, 1 H, HαЈ, J(HαЈHβЈ) ϭ 4.9 Hz, J(HαЈHγЈ) ϭ
1.3 Hz), 8.20 (m, 2 H, HδϩHδЈ), 8.04 (dd, 1 H, Hβ, J(HβHγ) ϭ 8.2 Hz,
J(HαHβ) ϭ 4.9 Hz), 7.83 (dd, 1 H, HβЈ, J(HβЈHγЈ) ϭ 8.2 Hz, J(HαЈHβЈ) ϭ
4.9 Hz), 7.73 (d, 2 H, Ho of OC6H4NO2-p, J(HoHm) ϭ 9.3 Hz), 6.99 (d, 2 H,
Hm of OC6H4NO2-p, J(HoHm) ϭ 9.3 Hz). 19F NMR (CDCl3): δ Ϫ119.8 (d,
2Fo, J(FoFm) ϭ 21.4 Hz), Ϫ158.5 (t, 1Fp, J(FmFp) ϭ 19.8 Hz), Ϫ161.9 (m,
2Fm).
The structure was solved by direct methods [32] and refined aniso-
tropically on F2 [32]. Hydrogen atoms were introduced in calcu-
lated positions. Crystallographic data (excluding structure factors)
reported in this paper have been deposited with Cambridge
Crystallographic Data Centre as supplementary publication no.
CCDC-258170. Copies of the data can be obtained free of charge
on application to CCDC, 12 Union Road, Cambridge CB21EZ
(fax: (ϩ44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
Preparation of Complexes [Pd(N؊N)(C6F5)(OAr)]
[N؊N ؍ tmeda, Ar ؍ C6H5 (10), p-MeC6H4 (11),
p-NO2C6H4 (12)
´
Acknowledgements. This work was supported by the Direccion
To a solution of the hydroxo palladium complex [Pd(tmeda)(C6-
F5)(OH)] (60 mg, 0.147 mmol) in tetrahydrofuran(15 mL) was ad-
ded the corresponding phenol (0.147 mmol) to yield an orange
solution which was stirred at room temperature for 1 h, then sol-
vent was partially eliminated under reduced pressure. On addition
of hexane an orange or yellowish precipitate formed which was
separated by filtration and air-dried.
Complex 10: Yield: 62 mg (87 %). Anal. Calcd. for
C18H21N2F5OPd: C 44.8, H 4.4, N 5.8. Found: C 44.6, H 4.5, N
5.5 %. Mp: 190 °C dec.
´
´
General de Investigacion del Ministerio de Ciencia y Tecnologıa
´
(Project No. BQU2001-0979-C02-01), Spain, and the Fundacion
´
´
´
Seneca de la Comunidad Autonoma de la Region de Murcia
(Project No. 00448/PI/04).
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