Insertion reactions into Pd-O and Pd-N bonds: Preparation of alkoxycarbonyl, carbonato, carbamato, thiocarbamate, and thioureide complexes of palladium(II)

Article abstract of DOI:10.1021/ic0300058

Mononuclear palladium hydroxo complexes of the type [Pd(N-N)(C₆F₅)(OH)] [(N-N = 2,2′-bipyridine (bipy), 4,4′- dimethyl-2,2′-bipyridine (Me₂bipy), 1,10-phenanthroline (phen), or N,N,N′,N′-tetramethylethylenediamine (tmeda)] have been prepared by reaction of [Pd(N-N)(C₆F₅)(acetone)]ClO₄ with KOH in methanol. These hydroxo complexes react, in methanol, with CO (1 atm, room temperature) to yield the corresponding methoxycarbonyl complexes [Pd(N-N)(C₆F₅)(CO₂Me)]. Similar alkoxycarbonyl complexes [Pd(N-N)(C₆F₅)(CO₂R)] (N-N = bis(3,5-dimethylpyrazol-1-yl)methane); R = Me, Et, or ⁱPr) are obtained when [Pd(N-N)(C₆F₅)Cl] is treated with KOH in the corresponding alcohol ROH and CO is bubbled through the solution. The reactions of [Pd(N-N)(C₆F₅)(OH)] (N-N = bipy or Me₂bipy) with CO₂, in tetrahydrofuran, lead to the formation of the binuclear carbonate complexes [(N-N)(C₆F₅)- Pd(μ-η²-CO₃)Pd(C₆F₅) (N-N)]. Complexes [Pd(N-N)(C₆F₅)(OH)] react in alcohol with PhNCS to yield the corresponding N-phenyl-O-alkylthiocarbamate complexes [Pd(N-N)(C₆F₅){SC(OR)NPh}]. Similarly, the reaction of [Pd(bipy)(C₆F₅)-(OH)] with PhNCO in methanol gives the N-phenyl-O-methylcarbamate complex [Pd(bipy)(C₆F₅){NPhC(O)OR}]. The reactions of [(N-N)Pd(C₆F₅)(OH)] with PhNCS in the presence of Et₂NH yield the corresponding thioureidometal complexes [Pd(N-N)(C₆F₅){NPhCSNR₂}]. The crystal structures of [Pd(tmeda)(C₆F₅)(CO₂Me)], [Pd₂(Me₂bipy)₂(C₆ F₅)₂- (μ-η²-CO₃)]·2CH₂ Cl₂, and [Pd(tmeda)(C₆F₅){SC(OMe)NPh}] have been determined.

Full text of DOI:10.1021/ic0300058

Inorg. Chem. 2003, 42, 3650−3661
Insertion Reactions into Pd−O and Pd−N Bonds: Preparation of
Alkoxycarbonyl, Carbonato, Carbamato, Thiocarbamate, and Thioureide
Complexes of Palladium(II)
Jose´ Ruiz,* M. Teresa Mart´ınez, Fe´lix Florenciano, Venancio Rodr´ıguez, and Gregorio Lo´pez*
Departamento de Qu´ımica Inorga´nica, Facultad de Qu´ımica, UniVersidad de Murcia,
30071 Murcia, Spain
Jose´ Pe´rez
Departamento de Ingenier´ıa Minera, Geolo´gica y Cartogra´fica (Area de Qu´ımica Inorga´nica),
UniVersidad Polite´cnica de Cartagena, 30203 Cartagena, Spain
Penny A. Chaloner and Peter B. Hitchcock
School of Chemistry, Physics and EnVironmental Sciences, UniVersity of Sussex,
Brighton BN1 9QJ, U.K.
Received January 6, 2003
Mononuclear palladium hydroxo complexes of the type [Pd(N−N)(C F )(OH)] [(N−N ) 2,2′-bipyridine (bipy), 4,4′-
6
5
dimethyl-2,2′-bipyridine (Me2bipy), 1,10-phenanthroline (phen), or N,N,N′,N′-tetramethylethylenediamine (tmeda)]
have been prepared by reaction of [Pd(N−N)(C F )(acetone)]ClO with KOH in methanol. These hydroxo complexes
6
5
4
react, in methanol, with CO (1 atm, room temperature) to yield the corresponding methoxycarbonyl complexes
[Pd(N−N)(C F )(CO Me)]. Similar alkoxycarbonyl complexes [Pd(N−N)(C F )(CO R)] (N−N ) bis(3,5-dimethylpyrazol-
6
5
2
6
5
2
1-yl)methane); R ) Me, Et, or iPr) are obtained when [Pd(N−N)(C F )Cl] is treated with KOH in the corresponding
6
5
alcohol ROH and CO is bubbled through the solution. The reactions of [Pd(N−N)(C F )(OH)] (N−N ) bipy or
6
5
Me2bipy) with CO , in tetrahydrofuran, lead to the formation of the binuclear carbonate complexes [(N−N)(C F )-
2
6 5
Pd(µ-η2-CO )Pd(C F )(N−N)]. Complexes [Pd(N−N)(C F )(OH)] react in alcohol with PhNCS to yield the corresponding
3
6
5
6 5
N-phenyl-O-alkylthiocarbamate complexes [Pd(N−N)(C F ){SC(OR)NPh}]. Similarly, the reaction of [Pd(bipy)(C F )-
6
5
6 5
(OH)] with PhNCO in methanol gives the N-phenyl-O-methylcarbamate complex [Pd(bipy)(C F ){NPhC(O)OR}].
6
5
The reactions of [(N−N)Pd(C F )(OH)] with PhNCS in the presence of Et2NH yield the corresponding thioureidometal
6
5
complexes [Pd(N−N)(C F ){NPhCSNR }]. The crystal structures of [Pd(tmeda)(C F )(CO Me)], [Pd (Me bipy)2(C F ) -
6
5
2
6
5
2
2
2
6 5 2
(µ-η2-CO )]‚2CH Cl2, and [Pd(tmeda)(C F ){SC(OMe)NPh}] have been determined.
3
2
6 5
Introduction
nature of the deprotonated (L-L)- ligand. Aryloxo,3 ami-
do,4,5 N,N- or C,N-malononitrilato,6 acetonyl,7 hydrosulfide,8
and triazenide9 complexes have also been prepared by
reaction of hydroxo complexes with ROH, RNH2, CH2(CN)2,
Me2CO, H2S or RNdNNHR (R ) aryl), respectively. No
intermediate aqua complex has been detected in these acid-
Dimeric hydroxo complexes [M2R4(µ-OH)2]2- of the group
10 elements1 have been shown to be excellent precursors in
organic and organometallic synthesis of new compounds.1f,g,2
The acid-base reaction of these hydroxo complexes with a
protic electrophile [M(µ-OH)2M + H(L-L) f M(L-L) or
M(µ-L-L)2M + 2H2O] leads to the formation of mono- or
binuclear complexes depending on the endo- or exo-bidentate
base reactions [M-OH + H+X- f (M-OH2)+ + X-
f
M-X + H2O], but palladium aqua complexes have been
prepared when a palladium hydroxo complex is treated with
triflic acid,10 owing to the noncoordinating ability of triflate,
(CF3SO3)-. Pentacoordinate nickel(II) complexes11 contain-
* Authors to whom correspondence should be addressed. Fax: (+34)
968 36 41 48. E-mail: jruiz@um.es (J.R.); gll@um.es (G.L.).
3650 Inorganic Chemistry, Vol. 42, No. 11, 2003
10.1021/ic0300058 CCC: $25.00 © 2003 American Chemical Society
Published on Web 05/08/2003

Insertion Reactions into Pd-O and Pd-N Bonds
Scheme 1
ing N,S-donor and hydroxamate ligands have also been
prepared starting from the hydroxo complex [Ni2(macrocycle)2-
(µ-OH)2]2+. The synthesis and dehydrative condensation of
complexes [(Tp)(py)Pd(OH)] and [{(Tp)(H2O)Pd}2(µ-OH)2]
(Tp ) hydrotris(3,5-diisopropylpyrazolyl)borato) have also
been reported.12
In the reaction of [M2(C6F5)4(µ-OH)2]2- with amines in
the presence of CS2 to form dithiocarbamate complexes (M
) Pd, Pt),2a it was suggested that after deprotonation of the
amine by the hydroxo complex to give an intermediate amido
complex there was insertion of CS2 into the M-N bond to
give the dithiocarbamate complex. In fact, the amido complex
[Pd2(C6F5)4(µ-NHPh)2]2- reacts with CS2, yielding the N-
phenyldithiocarbamate complex [M(C6F5)2(S2CNHPh)]-.6b
We have now investigated the chemical behavior of the new
monomeric complexes [Pd(N-N)(C6F5)(OH)] toward CO,
CO2, PhNCS, and PhCNO. The insertion of CO into a Pd-
OMe bond is one of the fundamental steps in various
palladium-catalyzed organic reactions such as the hydro-
esterification of alkenes.13
Results and Discussion
Mononuclear Hydroxo Complexes [Pd(N-N)(C6F5)-
(OH)]. In methanol, the complexes [(N-N)(C6F5)Pd(Me2-
CO)]ClO4 [N-N ) bipy (2,2′-bipyridyl), Me2bipy (4,4′-
dimethyl-2,2′-bipyridyl), phen (1,10-phenanthroline), or tmeda
(tetramethylethylenediamine)] react with KOH to yield the
corresponding neutral hydroxo complexes [(N-N)(C6F5)-
Pd(OH)] (1-4) (Scheme 1) in 75-88% yields. Although
binuclear µ-methoxo complexes were obtained by treating
µ-hydroxo complexes with methanol1d and trans-[Pd(PPh3)2-
(C6F5)(OCH3)] has also been reported,14 no methoxo com-
pound was isolated in these reactions. The structures for the
pale yellow complexes 1-4 were assigned on the basis of
(1) (a) Lo´pez, G.; Garc´ıa, G.; Ruiz, J.; Garc´ıa, J.; Vicente, C. J. Chem.
Soc., Chem. Commun. 1989, 1046. (b) Lo´pez, G.; Ruiz, J.; Garc´ıa,
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Mart´ı, J. M.; Cutillas, N.; Garc´ıa, G.; Lo´pez, G. J. Organomet. Chem.
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Trans. 1994, 2353.
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V. J. Organomet. Chem. 1992, 436, 121. (b) Sa´nchez, G.; Ruiz, F.;
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M. C.; Lo´pez, G. HelV. Chim. Acta 1997, 80 , 2477. (f) Ruiz, J.;
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C.; Pe´rez, J. Eur. J. Inorg. Chem. 2000, 943.
1
microanalytical, IR, and H and 19F NMR data.
The IR spectra of complexes 1-4 show the characteristic
absorptions of the C6F5 group15 at ca. 1630, 1490, 1450,
1050, 950, and 790 cm-1. The latter absorption derives from
the so-called “X-sensitive” mode in C6F5-X molecules,16 and
it is observed as a single band, as expected from the presence
of only one C6F5 group in the coordination sphere of the
palladium atom.17-19 A band found at 3610-3605 cm-1 in
the IR spectra is assigned to ν(OH). The presence of the
hydroxo ligand is also established by the observation of a
high-field proton resonance (δ -0.75 to -2.00) which is in
accord with the results observed for hydroxo complexes of
the group 10 elements.1a,12 The characteristic resonances of
(3) Ruiz, J.; Rodr´ıguez, V.; Lo´pez, G.; Chaloner, P. A.; Hitchcock, P. B.
Organometallics 1996, 15, 1662.
1
(4) (a) Ruiz, J.; Mart´ınez, M. T.; Vicente, C.; Garc´ıa, G.; Lo´pez, G.;
Chaloner, P. A.; Hitchcock, P. B. Organometallics 1993, 12, 4321.
(b) Ruiz, J.; Rodr´ıguez, V.; Lo´pez, G.; Chaloner, P. A.; Hitchcock, P.
B. J. Chem. Soc., Dalton Trans. 1997, 4271. (c) Ruiz, J.; Cutillas, N.;
Torregrosa, J.; Garc´ıa, G.; Lo´pez, G.; Chaloner, P. A.; Hitchcock, P.
B.; Harrison, R. M. J. Chem. Soc., Dalton Trans. 1994, 2353. (d) Ruiz,
J.; Cutillas, N.; Sampedro, J.; Lo´pez, G.; Hermoso, J. A.; Mart´ınez-
Ripoll, M. J. Organomet. Chem. 1996, 526, 67.
(5) Driver, M. S.; Hartwig, J. F. J. Am. Chem. Soc. 1996, 118, 4206.
(6) (a) Lo´pez, G.; Sa´nchez, G.; Garc´ıa, G.; Ruiz, J.; Garc´ıa, J.; Mart´ınez-
Ripoll, M.; Vegas, A.; Hermoso, J. A. Angew. Chem., Int. Ed. Engl.
1991, 30, 716. (b) Ruiz, J.; Rodr´ıguez, V.; Lo´pez, G.; Casabo´, J.;
Molins, E.; Miravitlles, C. Organometallics 1999, 18, 1177.
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Chaloner, P. A.; Hitchcock, P. B. Organometallics 2001, 20, 1973.
(8) Ruiz, J.; Rodr´ıguez, V.; Vicente, C.; Mart´ı, J. M.; Lo´pez, G.; Pe´rez,
J. Inorg. Chem. 2001, 40, 5354.
the neutral ligands were also observed in the H NMR
spectra,20-23 and the assignments presented in the Experi-
(13) (a) Cavinato, G.; Vavasori, A.; Toniolo, L.; Benetollo, F. Inorg. Chim.
Acta 2003, 343, 183. (b) Huh, K.-T, Alper, H. Bull. Korean Chem.
Soc. 1994, 15, 304. (c) Kapteijn, G. M.; Verhoef, M. J.; van den Broek,
F. H.; Grove, D. M.; van Koten, G. J. Organomet. Chem. 1995, 503,
C26. (d) Bertoux, F.; Castanet, Y.; Civade, E.; Monflier, E.; Mortreux,
A. Catal. Lett. 1998, 54, 199.
(14) Yoshida, T.; Okano, T.; Otsuka, S. J. Chem. Soc., Dalton Trans. 1976,
993.
(15) Long, D. A.; Steel, D. Spectrochim. Acta 1963, 19, 1955.
(16) Maslowski, E. Vibrational Spectra of Organometallic Compounds;
Wiley: New York, 1977; p 437.
(17) Alonso, E.; Fornie´s, J.; Fortun˜o, C.; Toma´s, M. J. Chem. Soc., Dalton
Trans. 1995, 3777.
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M. C.; Lo´pez, G. J. Chem. Soc., Dalton Trans. 2001, 2683.
(10) Ruiz, J.; Florenciano, F.; Vicente, C.; Ram´ırez de Arellano, M. C.;
Lo´pez, G. Inorg. Chem. Commun. 2000, 3, 73.
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C.; Lo´pez, G. J. Chem. Soc., Dalton Trans. 2000, 619. (b) Santana,
M. D.; Garc´ıa, G.; Pe´rez, J.; Molins, E.; Lo´pez, G. Inorg. Chem. 2001,
40, 5701.
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P. A.; Hitchcock, P. B. Organometallics 1992, 11, 4091.
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P. A.; Hitchcock, P. B. Organometallics 1993, 12, 4321.
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Inorganic Chemistry, Vol. 42, No. 11, 2003 3651

Ruiz et al.
Scheme 2
Scheme 4
Scheme 3
resonance signal observed in the 1H NMR spectra at ca. 3.50
ppm is due to the CO2Me protons. The CO resonance of the
methoxycarbonyl ligand of complexes 5-7 could not be
observed in the 13C NMR spectra because of their low
solubility, but it was observed in CDCl3 solution for the more
soluble complex 8 as a triplet signal at δ 183.6 due to
coupling to the o-fluorine atoms of the C6F5 group [4J(CFo)
) 5.4 Hz].
mental Section are based on the atom numbering given in
Scheme 2. The low-field resonance (δ 8.8-9.3) is assigned
to the R-H atom,23 and the assignment of the signals
1
found in the range 9.3-7.01 was confirmed by the H-1H
COSY spectrum of complex 3. The 19F NMR spectra show
the expected three resonances for 2Fo:1Fp:2Fm of the C6F5
ligand.
Alkoxycarbonyl Complexes [(N-N)Pd(C6F5)(CO2R)].
Only a few palladium methoxycarbonyl complexes have been
prepared; these include [(bipy)Pd(CO2Me)2],23 [(PPh3)2PdCl-
(CO2Me)],24,25 [(PPh3)2Pd(CO2Me)2],26 [(PPh3)2Pd(OAc)-
(CO2Me)],27and [(PMe3)2Pd(CH2Ph)(CO2Me)].28 Others have
been detected by NMR spectroscopy, but they could not be
isolated: [(P-P)(PPh3)Pd(CO2Me)](SO3CF3),29 [(P-P)PdMe-
(CO2Me)],30 and [(P-P)PdMe{CO2CH(CF3)2}].31The car-
bonylation of [(PPh3)2Pd2(C6H5)2(µ-OH)2] in the presence
of PhI has been reported.32
When CO is bubbled through an alcoholic (MeOH, EtOH,
iPrOH) solution of [(N-N)Pd(C6F5)(OH)] [N-N ) bis(3,5-
dimethylpyrazol-1-yl)methane], generated in situ by the
addition of KOH to the complexes [(N-N)Pd(C6F5)Cl], the
corresponding bis(pyrazol-1-yl)methane complexes [(N-
i
N)Pd(C6F5)(CO2R)] [R ) Me (9), Et (10), or Pr (11)] are
obtained (Scheme 4).
The IR spectra of complexes 9-11 show a band at ca.
1640 cm-1 which is assigned to ν(CO), and a single band
located at 790 cm-1 is indicative of the presence of only
one C6F5 group in the coordination sphere of the palladium
atom. Two sets of 1H resonances are observed for the
C3HMe2N2 rings corresponding to one pyrazolate ligand trans
to CO2R and one pyrazolate ligand trans to C6F5; the lower
field set is assigned to the pyrazolate ligand trans to C6F5
(Scheme 4). The 19F NMR spectra of complexes 9-11 at
room temperature show the expected three resonances for
the C6F5 ligand, but those derived from the o-fluorine atoms
are observed as broad signals. Furthermore, the proton
resonances of the bridging methylene chain of the bis-
(pyrazol-1-yl)methane ligand and some of the proton reso-
nances of the OR groups appear as broad signals too. A
number of studies have been performed on bis(pyrazolyl)-
methane ligands coordinated to a metallic center,33and it is
found that the two conformers shown in Figure 1 may be in
When CO is bubbled through a solution of the mono-
meric hydroxo complexes 1-4 in methanol at room tem-
perature for 5-15 min, the methoxycarbonyl complexes
[(N-N)(C6F5)Pd(CO2Me)] (5-8) are obtained in 55-80%
yields (Scheme 3). Complexes 5-8 are all air-stable solids,
and the thermal analysis shows that they decompose above
140 °C in a dynamic N2 atmosphere. A very strong band in
the IR spectra at ca. 1650 cm-1 is assigned to ν(CO). The
(24) Cavinato, G.; Toniolo, L. J. Organomet. Chem. 1993, 444, C65.
(25) Otsuka, S.; Nakamura, A.; Yoshida, T.; Naruto, M.; Ataka, K. J. Am.
Chem. Soc. 1973, 95, 3180.
(26) Bryndza, H. E. Organometallics 1985, 4, 1686.
(27) Caglio, G. J. Chem. Soc. A 1970, 1836.
(28) Milstein, D. J. Chem. Soc., Chem. Commun. 1986, 817.
(29) Dekker: G. P. C. M.; Elsevier: C. J.; Vrieze, K.; Leeuwen, P. W. N.
M.; Roobeek, C. F. J. Organomet. Chem. 1992, 430, 357.
(30) Toth, I.; Elsevier: C. J. J. Chem. Soc., Chem. Commun. 1993, 529.
(31) Kim, Y.; Osakada, K.; Sugita, K.; Yamamoto, T.; Yamamoto, A.
Organometallics 1988, 7, 2182.
(33) Byers, P. K.; Canty, A. J.; Honeyman, R. T. AdV. Organomet. Chem.
1992, 34, 1.
(32) Grushin, V. V.; Alper, H. J. Am. Chem. Soc. 1995, 117, 4305.
3652 Inorganic Chemistry, Vol. 42, No. 11, 2003

Insertion Reactions into Pd-O and Pd-N Bonds
1
Figure 1. Variable-temperature H NMR spectra of [Pd{CH2(C3HMe2N2}2(C6F5){C(O)OEt}] in the C-CH2-O (left) and N-CH2-N (right) regions, and
the boat-to-boat inversion of the metallacycle Pd(N-N)2C.
a chemical exchange through a boat-to-boat inversion. The
variable-temperature H NMR spectrum of complex 10
solution was then evaporated under vacuum to dryness, and
1 equiv of KOH in methanol was added to the residue. The
solution was again evaporated to dryness and the residue
extracted with dichloromethane. Filtration, concentration
under vacuum, and addition of hexane gave a solid that was
investigated by 1H NMR spectroscopy in the solvent CDCl3.
The 1H spectrum (only the MeO and Me proton signals are
given below) showed that the product was a mixture of [(N-
N)Pd(C6F5)(OMe)] [δ 3.08 (s, 3H, MeO), 2.55 (s, 3H, Me3′),
2.37 (s, 6H, Me5 + Me5′), 1.83 (s, 3H, Me3)] and [(N-
N)Pd(C6F5)(OH)] [δ 2.59 (s, 3H, Me3′), 2.38 (s, 6H, Me5
+ Me5′), 1.81 (s, 3H, Me3)] together with small amounts
of six unidentified palladium species. The relative intensities
of the proton signals indicated a mole ratio of methoxo
complex to hydroxo complex =2:1. The observation of the
Pd-OMe signal at δ 3.08 is in agreement with the values
found in [(PPh3)2Pd(C6F5)(OMe)] (δ 3.08)14 and [(o-
Ph2PC6H4CHdNiPr)Pd(C6F5)(OMe)] (δ 3.4).34 The Pd-OH
signal, which should be found at high field between -2 and
-3 ppm,1b,14 could not be observed in the 1H spectrum, but
the infrared spectrum of the solid in Nujol mull showed a
sharp ν(OH) band at 3605 cm-1. Attempts made to isolate
1
(Figure 1) provides cogent evidence for the existence of the
aforementioned inversion of the metallacycle ring. At low
temperatures, when the inversion is frozen, protons A and
B are magnetically nonequivalent and give the expected
NMR pattern corresponding to two diastereotopic protons:
two doublets with 2J(HAHB) ) 15 Hz that collapse at 50 °C.
At lower temperatures two methylene resonances are also
observed for protons A′ and B′; each signal is observed as
a doublet (2J(HA′HB′) of quartets (3J(CH3/HA′ or HB′)) with
the quartets partly overlapped owing to accidental coinci-
dence of the two coupling constants. At higher temperatures
the HA′ and HB′ resonances coalesce, and at 50 °C the
resolution of the splitting between CH3 and CH2 is already
discernible in the spectrum.
The formation of complexes 5-11 is formally the insertion
of CO into the Pd-OR bond. Although no alkoxo complexes
have been isolated, they probably are formed in the alcoholic
solution, and a carbonyl insertion into Pd-OMe could be a
possible pathway to the formation of M-CO2R. The exist-
ence of an intermediate methoxopalladium complex was
shown by the following experiment. [(N-N)Pd(C6F5)Cl] was
treated with 1 equiv of AgClO4 in acetone, and the
suspension was filtered to remove the precipitated AgCl. The
(34) Sa´nchez, G.; Serrano, J. L.; Momblona, F.; Ruiz, F.; Garc´ıa, J.; Pe´rez,
J.; Lo´pez, G.; Chaloner, P. A.; Hitchcock, P. Polyhedron 2001, 20,
571.
Inorganic Chemistry, Vol. 42, No. 11, 2003 3653

Ruiz et al.
Scheme 5
pure samples of the hydroxo or the methoxo complexes were
unsuccessful.
Figure 2. Crystal structure of 8. Selected bond lengths (Å): Pd-N(1)
2.139(5), Pd-N(2) 2.176(6), Pd-C(6) 2.019(6), Pd-C(7) 1.961(6), C(7)-
O(1) 1.329(8), C(7)-O(2) 1.199(8).
Carbonyl insertion into a M-OMe bond has been dem-
onstrated to occur in [(dppe)PtMe(OMe)], which reacts with
CO at room temperature to yield [(dppe)Pt(Me)(CO2Me)],26
and the formation of the iridium carbomethoxy complex
[(PPh3)2(CO)2Ir(CO2Me)] by nucleophilic attack on coordi-
nated CO by methoxide has been reported,35 as well as the
reaction of the cationic complex trans-[(PPh3)2Pt(C6F5)(CO)]-
BF4 with methanol to give the methoxycarbonyl complex
trans-[(PPh3)2Pt(C6F5)(CO2Me)].36 Van Koten37 has sug-
gested a dissociative mechanism with displacement of RO-
by CO to form a cationic carbonyl complex followed by
nucleophilic attack of the methoxide anion on coordinated
CO. The reaction of CO with bis(µ-aryloxo) complexes
[(C6F5)2M(µ-OR)2(C6F5)2]2- (M ) Pd, Pt)16 has also been
studied and leads to the formation of [(C6F5)2M(OR)(CO)]-.
Detailed mechanistic information on the carbonylation reac-
tions of [(diphos)PtMe(OMe)]-type complexes indicates that
these reactions are best described as inner-sphere migratory
insertions involving precoordination of CO to the metal
center to generate a 5-coordinate intermediate.38 In fact, (i)
no reaction was observed when CO was bubbled through a
solution of 1 in tetrahydrofuran, and (ii) when NaOMe was
added to a solution of the previously reported carbonyl
Scheme 6
2.139(5) Å; Pd-N(2), 2.176(6) Å) distances are in agreement
with the higher trans influence of the CO2Me group
compared to C6F5. The CO2Me group is planar, and the Pd-
CO2Me distance (1.961(6) Å) is shorter than that found in
[(bipy)Pd(CO2Me)2] (1.989(9) Å).22 The C(7)-O(1) distance
of the CO2Me group (1.329(8) Å) is typical of a single bond,
and the C(7)-O(2) distance (1.199(8) Å) is representative
of double carbon-oxygen bonds.22 The Pd-C6F5 bond length
(2.019(6) Å) is in the range found in the literature for
(pentafluorophenyl)palladium complexes.23 The chelate angle
N(1)-Pd-N(2) (83.9(2)°) is similar to that found (84.8(5)°)
in [{Pd(tmeda)}2(µ-OH)(µ-HNC6H4Cl-p)]2+.40
Carbonate Complexes. When CO2 is bubbled through a
suspension of the monomeric hydroxo complex 1 or 2 in
tetrahydrofuran (1) or dichloromethane (2) at room temper-
ature for 5 min, the binuclear carbonate complexes [(N-
N)(C6F5)Pd(µ-CO3)Pd(C6F5)(N-N)] (N-N ) bipy (12) or
Me2bipy (13)) are obtained (Scheme 6). The IR spectra of
both compounds display strong absorptions at 1540 and 1300
cm-1 due to the Vasym(CO2) and Vsym(CO2) vibrational modes
39
complex[(bipy)(C6F5)Pd(CO)]ClO4 in methanol, we ob-
tained the neutral methoxycarbonyl complex [(bipy)-
(C6F5)Pd(CO2Me)] (5). According to the literature and
experimental data, the mechanism shown in Scheme 5 may
be proposed, although the alternative mechanism based on
the nucleophilic attack by external RO- on coordinated CO
cannot be discarded.
Crystal Structure of 8. Colorless crystals suitable for
X-ray diffraction studies were obtained by slow diffusion
of hexane into a benzene solution of 8. The crystal structure
of complex 8 is shown in Figure 2. The coordination around
Pd is distorted square-planar. The different Pd-N (Pd-N(1),
(35) Rees, M. W.; Churchill, M. R.; Fettinger, J. C.; Atwood, J. D.
Organometallics 1985, 4, 2179.
(36) Cherwinski, W. J.; Clark, H. C. Inorg. Chem. 1971, 10, 2263.
(37) Kapteijn, G. M.; Dervisi, A.; Verhoef, M. J.; van den Broek, M. A.
F. H.; Grove, D. M.; van Koten, G. J. Organomet. Chem. 1996, 517,
123.
(38) Bryndza, H. E.; Tam, W. Chem. ReV. 1988, 88, 1163 and references
therein.
(39) Uso´n, R.; Fornies, J.; Mart´ınez, F. J. Organomet. Chem. 1976, 112,
105.
(40) Sa´nchez, G.; Serrano, J. L.; Garc´ıa, J.; Lo´pez, G.; Pe´rez, J.; Molins,
E. Inorg. Chim. Acta 1999, 287, 37.
3654 Inorganic Chemistry, Vol. 42, No. 11, 2003

Insertion Reactions into Pd-O and Pd-N Bonds
Scheme 7
Figure 3. Crystal structure of 13. Selected bond lengths (Å): Pd(1)-
O(1) 2.014(2), Pd(2)-O(3) 1.995(2), C(19)-O(1) 1.309(4), C(19)-O(3)
1.308(4), C(19)-O(2) 1.235(4). Angle (deg) between the coordination planes
of Pd(1) and Pd(2): 66.54(8).
of the carbonate ligand, respectively.41-43 The crystal X-ray
structure of the related carbonato complex of rhodium,
[(C6F5)Rh(µ-CO3)Rh(C6F5)]2-, has been reported,43 and
monometallic bis(hydrogen carbonato) complexes of pal-
ladium of the types [Pd{OC(O)OH}2L2] and [Pd{OC(O)-
OH}2(L-L)2] have been prepared by insertion of carbon
dioxide into palladium-hydroxide bonds.44 However, the
recently reported [Pd(TMEDA)(η2-CO3)] (TMEDA )
N,N,N′,N′-tetramethylethylenediamine) was isolated by react-
make an interplanar angle of 66.54(8)°. The Pd(1)-O(1) and
Pd(2)-O(3) bond distances (2.014(2) and 1.995(2) Å,
respectively) are shorter than the Pt-O distance of 2.087(7)
Å reported for the carbonatoplatinum complex [(PBz3)4Pt2-
(Ph)2(η1,η1,µ-CO3)(toluene)],42 the Pd-O distance of 2.114(3)
Å reported for the monometallic bis(hydrogen carbonato)-
palladium complex [Pd(OCO2H)2(dppe)],44 and the Rh-O
distance of 2.154(9) Å found in the dimeric carbonato-
rhodium complex [{(C6F5)3Rh)}2(µ-CO3)]2-,43 but they are
comparable with the Pd-O distance found in [Pd(TMEDA)-
(η2-CO3)].45 The C(19)-O(1) (1.309(4) Å) and C(19)-O(3)
(1.308(4) Å) bond lengths in the carbonate complex 13 are
comparable with those observed for [(PBz3)4Pt2(Ph)2(η1,η1,µ-
CO3)(toluene)] (1.29(1) Å).42 On the other hand, the C(19)-
O(2) bond distance (1.235(4) Å) is shorter than the C(19)-
O(1) and C(19)-O(3) ones. The different Pd-N distances
(Pd(1)-N(1), 2.028(3) Å; Pd(1)-N(2), 2.067(3) Å; Pd(2)-
N(3), 2.024(3) Å; Pd(2)-N(4), 2.063(3) Å) are in agreement
with the higher trans influence of the C6F5 group compared
to the carbonato ligand. The Pd-C6F5 distances are similar
to those found in complex 8 and in the literature.23 The
chelate angles N(1)-Pd(1)-N(2) and N(3)-Pd(2)-N(4)
(80.04(11)° and 80.22(11)°, respectively) are smaller than
those found in complex 8.
t
ing [Pd(TMEDA)(OC6H4 Bu-p)2] with CO2 in the presence
of water.45
The insertion of CO2 into the Pd-OH bond, perhaps via
the formation of a pentacoordinate intermediate, [(N-N)-
Pd(C6F5)(CO2)(OH)], should give the hydrogen carbonato
complexes [(N-N)Pd(C6F5){OC(dO)OH}], and the carbon-
ato complexes 12 and 13 should be subsequently formed via
the acid-base reaction between the hydrogen carbonato
complexes and the unreacted hydroxo complex as shown in
Scheme 6.
Crystal Structure of 13. Crystals suitable for structural
determination were obtained by slow diffusion of hexane
into a dichloromethane-toluene solution of complex 13. The
crystal structure of 13 is shown in Figure 3. So far as we
aware this is the first carbonate-bridged palladium species
to be structurally characterized [3D search using the Cam-
bridge Structural Database, April 2002 release]. The structure
shows the planar carbonate anion acting as a symmetric
bridging bidentate ligand to both palladium(II) centers. The
mean plane defined by the carbonate group and the two
palladium atoms is close to planar with a maximum deviation
of 0.1 Å [O(3)]. The coordination planes of the two Pd atoms
Carbamate and Thiocarbamate Complexes. We have
demonstrated that in the reaction of amines with hydroxo-
bridged nickel(II), palladium(II), and platinum(II) complexes
in the presence of carbon disulfide, C-N bonds are formed
to give N,N-dialkyldithiocarbamate complexes.2a,46
The hydroxopalladium complexes 1-4 react with PhNCS
in alcohol (MeOH, EtOH, or PrOH) at room temperature,
yielding the corresponding N-phenyl-O-alkylthiocarbamate
metal complexes [(N-N)Pd(C6F5){SC(dNPh)OR}] (14-25)
(Scheme 7).
(41) Carmona, E.; Mar´ın, J. M.; Palma, P.; Paneque, M.; Poveda, M. L.
Inorg. Chem. 1989, 28, 1895.
(42) Michelin, R. A.; Strukul, G.; Bresciani-Pahor, N.; Zangrando, E.;
Randaccio, L. Inorg. Chim. Acta 1984, 84, 229.
(43) Garc´ıa, M. P.; Jime´nez, M. V.; Lahoz, F. J.; Oro, L. A. J. Chem.
Soc., Dalton Trans. 1995, 917.
(44) Ganguly, S.; Mague, J. T.; Roundhill D. M. Inorg. Chem. 1992, 31,
3831.
(45) Yasuda, H.; Choi, J.-C.; Lee, S.-C.; Sakakura, T. Organometallics
2002, 21, 1216.
(46) Lo´pez, G.; Sa´nchez, G.; Garc´ıa, G.; Garc´ıa, J.; Sanmart´ın, A.; Santana,
M. D. Polyhedron 1991, 10, 2821.
Inorganic Chemistry, Vol. 42, No. 11, 2003 3655

Ruiz et al.
The IR spectra of compounds 14-25 show the charac-
teristic absorptions of the C6F5 group at 1630, 1490, 1450,
1050, and 950 cm-1 and a single band at ca. 800 cm-1 for
the X-sensitive mode. The observation of the ν(CdN)
vibration at ca. 1580 cm-1 suggests that the thiocarbamate
ligand is coordinated to the metal through the S atom. The
1H NMR spectra show the characteristic resonances of the
neutral N-N ligand20 and the N-phenyl-O-alkylthiocarbamate
group. The observation of three or two signals for the
aromatic protons of the PhN groups indicates that rotation
of the aryl group about the C-N bond is rapid on the NMR
time scale. The 19F NMR spectra of complexes 14-25 reveal
a freely rotating pentafluorophenyl ring which gives the
expected three resonances in the ratio 2:1:2 for the o-, p-,
and m-fluorine atoms, respectively.
Figure 4. Crystal structure of 23. Selected bond lengths (Å) and angles
(deg): Pd-S 2.3099(10), Pd-C(7) 2.022(3), Pd-N(2) 2.153(3), Pd-N(3)
2.123(3), C(19)-N(1) 1.265(5), C(19)-N(1)-C(1) 122.5(3).
The hydroxopalladium complex 1 also reacts with PhNCO
in methanol solution at room temperature to yield the
N-phenyl-O-methylcarbamato complex [(bipy)Pd(C6F5)-
{NPhC(O)OR}] (26) (Scheme 7). The reaction between
trans-[PtH(OPh)(PEt3)2] and phenyl isocyanate, PhNCO, to
give the N,O-diphenylcarbamato complex trans-[PtH{PhNC-
(O)Ph}(PEt3)2], where phenyl isocyanate inserts cleanly into
the platinum-oxygen bond, has been reported,47 but the
related nickel complex trans-[NiH(PhNC(O)OPh)(PEt3)2],
although detected by 1H NMR, could not be isolated because
a reversible insertion reaction occurs.48 Insertion of PhNCO
into the metal-oxygen bond of fac-[(CO)3(dppe)M(OMe)]
(M ) Mn or Re) has also been reported.49 The 19F NMR
spectrum of complex 26 reveals that rotation of the penta-
fluorophenyl ring around the Pd-C6F5 bond is hindered.
Instead of the three resonances with relative intensities of
2Fo:1Fp:2Fm expected for a freely rotating C6F5 ring, four
1:1:1:1 resonance signals are observed in the o- and
m-fluorine atom regions. This experimental observation is
in agreement with the coordination of the carbamate ligand
through the N atom. The phenyl group at the N atom lies
adjacent to the C6F5 ring, preventing its free rotation.
The formation of complexes 14-25 and 26 is the result
of the insertion of PhNCS or PhNCO into the corresponding
Pd-OR bond. As with the formation of the alkoxycarbonyl
derivatives aforementioned, preformation of an alkoxometal
intermediate followed by insertion of the heterocumulene or
external attack by RO- of the coordinated heterocumulene
is an alternative pathway to the formation of 14-26.
Crystal Structure of 23. Crystals suitable for X-ray
diffraction studies were grown by slow diffusion of hexane
into a benzene solution of 23. The crystal structure of
complex 23 is shown in Figure 4. The donor atoms and the
metal are coplanar (maximum deviation of 0.01 Å). The
thiocarbamate group is not exactly planar, the C(1) atom
being 0.02 Å out of the plane of the three bonded atoms S,
O(1), and N(1). The N(1)-C(19) bond length (1.265(5) Å)
and the C(19)-N(1)-C(1) angle (122.5(3)°) indicate that
N(1) is sp2-hybridized and that a high N-C double bond
Scheme 8
character exists.50 Bond angles around the C(19) atom (128-
112°) and the total of the surrounding three bond angles
(359.9°) also clearly confirm the sp2 hybridization of the
C(19) atom. The Pd-S bond distance (2.3099(10) Å) is a
little shorter than those found in [Pd(C6F5)(SC6H5)(o-
Ph2PC6H4CHNiPr)] (2.357(2) Å)51 and [(CH2CH2CH2CH2-
NCS2)Pd(PEt3)(nPr)] (2.384(2) and 2.406(1) Å),52 and similar
to those found in [Pd3(Et2NCS2)4Cl2].53 The Pd-C6F5
distance (2.022(3) Å) and the chelate angle N(3)-Pd-N(2)
(83.96(12)°) are similar to those found in complex 8. The
different distances Pd-N (Pd-N(2), 2.153(3) Å; Pd-N(3),
2.123(3) Å) are in agreement with the higher trans influence
of the C6F5 group compared with the thiocarbamate ligand.
Thioureide Complexes. The hydroxopalladium complexes
1-4 react with PhNCS in the presence of Et2NH, afford-
ing the thioureidopalladium complexes [(N-N)Pd(C6F5)-
(NPhCSNR2)] (27-30) (Scheme 8). In this case, the reaction
between Et2NH and the hydroxopalladium complex should
give the amide complex [(N-N)Pd(C6F5)(Et2N)] followed
by insertion of PhNCS into the Pd-NEt2 bond. The crystal
(50) Lappert, M. F.; Pye, P. L.; McLaughlin, G. M. J. Chem. Soc., Dalton
Trans. 1977, 1272.
(51) Sa´nchez, G.; Serrano, J. L.; Momblona, F.; Ruiz, F.; Garc´ıa, J.; Pe´rez,
J.; Lo´pez, G.; Chaloner, P. A.; Hitchcock, P. B. Polyhedron 2001,
20, 571.
(47) Cowan, R. L.; Trogler, W. C. J. Am. Chem. Soc. 1989, 111, 4750.
(48) Seligson, A. L.; Cowan, R. L.; Trogler, W. C. Inorg. Chem. 1991,
30, 3371.
(52) Reger, D. L.; Garza, D. G.; Lebioda, L. Organometallics 1991, 10,
902.
(53) Sokolov, M.; Imoto, H.; Saito, T. Inorg. Chem. Commun. 1999, 2,
(49) Mandal, S. K.; Ho, D. M.; Orchin, M. Organometallics 1993, 12, 1714.
422.
3656 Inorganic Chemistry, Vol. 42, No. 11, 2003

Insertion Reactions into Pd-O and Pd-N Bonds
by the following method. To a solution of [Pd2(C6F5)2(tht)2(µ-Cl)2]55
(100 mg, 0.126 mmol; tht ) tetrahydrothiophene) in dichloro-
methane (15 mL) was added bis(3,5-dimethyl-pyrazol-1-yl)methane
(0.252 mmol). After being stirred at room temperature for 30 min,
the solution was concentrated under vacuum, and hexane was added
to give a yellow precipitate which was filtered off, air-dried, and
characterized as [Pd(N-N)(C6F5)Cl]. Yield: 82%.
Preparation of Complexes [(N-N)Pd(OH)(C6F5)] (N-N )
bipy (1), Me2bipy (2), phen (3), or tmeda (4)). To a solution of
the corresponding ionic perchlorate complex [(N-N)Pd(C6F5)-
(acetone)]ClO4 (0.96 mmol) in methanol (30 mL) was added KOH
(2.00 mmol). The resulting solution was stirred for 1 h and
concentrated under vacuum to dryness. The residue was treated
with CH2Cl2, the precipitate was removed by filtration, and the
filtrate was concentrated under vacuum. The addition of hexane
caused the precipitation of a pale yellow solid which was collected
by filtration and air-dried.
structure of the thioureido derivative [Rh(C5Me5)Cl{PhNC-
[N(C6H4Me-p)CHdNC6H4Me-p]S}] arising from the inser-
tion of PhNCS into the Rh-N bond has been reported.54
The molecule contains the four-membered chelate ring Rh-
N-C-S. The C-N and C-S bonds have a considerable
double bond character with a higher percentage for the
former. The IR spectra of complexes 27-30 show the
characteristic absorptions of the C6F5 ligand and a strong
absorption at 1555-1535 cm-1 which is in the range found
for the few thioureido complexes reported54 and is dependent
on the double bond character of the C-N bond. The 1H NMR
spectra show the resonance signals of the N-N ligands and
the Et2N and PhN groups, and the 19F NMR spectra show
the expected three signals with relative intensities of 2Fo:
1Fp:2Fm corresponding to the C6F5 ligand.
Data for Complex 1. Yield: 347 mg, 81%. Anal. Calcd for
C16H9N2F5OPd: C, 43.0; H, 2.0; N, 6.3. Found: C, 42.8; H, 2.1;
N, 6.1. Mp: 212 °C dec. IR (Nujol, cm-1): ν(OH), 3610; ν(Pd-
C6F5), 785. 1H NMR (CDCl3): δ(SiMe4) 9.00 (dd, 1H, HR, J(HRHâ)
) 4.9 Hz, J(HRHγ) ) 1.3 Hz), 8.00 (m, 5H, HR′ + Hγ + Hγ′ + Hδ
+ Hδ′), 7.60 (dd, 1H, Hâ, J(HâHγ) ) 8.2 Hz, J(HRHâ) ) 4.9 Hz),
7.26 (dd, 1H, Hâ′, J(Hâ′Hγ′) ) 8.2 Hz, J(HR′Hâ′) ) 4.9 Hz), -0.90
(s, 1H, OH). 19F NMR (CDCl3): δ(CFCl3) -117.1 (d, 2Fo, J(FoFm)
) 21.4 Hz), -159.4 (t, 1Fp, J(FmFp) ) 19.8 Hz), -162.5 (m, 2Fm).
Data for Complex 2. Yield: 387 mg, 85%. Anal. Calcd for
C18H13N2F5OPd: C, 45.5; H, 2.8; N 5.9. Found: C, 45.6; H, 2.7;
N, 5.8. Mp: 247 °C dec. IR (Nujol, cm-1): ν(OH), 3605; ν(Pd-
C6F5), 790. 1H NMR (CDCl3): δ(SiMe4) 8.83 (d, 1H, HR, J(HRHâ)
) 5.5 Hz), 7.79 (s, 2H, Hδ + Hδ′), 7.68 (d, 1H, HR′, J(HR′Hâ′) )
5.5 Hz), 7.34 (d, 1H, Hâ, J(HâHR) ) 5.5 Hz), 7.01 (d, 1H, Hâ′,
J(Hâ′HR′) ) 5.5 Hz), 2.44 (s, 3H, Me), 2.42 (s, 3H, Me), -0.92
(br, 1H, OH). 19F NMR (CDCl3): δ(CFCl3) -117.2 (d, 2Fo, J(FoFm)
) 21.4 Hz), -159.6 (t, 1Fp, J (FmFp) ) 20.0 Hz), -162.6 (m, 2Fm).
Data for Complex 3. Yield: 398 mg, 88%. Anal. Calcd for
C18H9N2F5OPd: C, 45.9; H, 1.9; N, 6.0. Found: C, 45.8; H, 2.0;
N, 5.8. Mp: 234 °C dec. IR (Nujol, cm-1): ν(OH), 3610; ν(Pd-
C6F5), 790. 1H NMR (CDCl3): δ(SiMe4) 9.27 (dd, 1H, HR, J(HRHâ)
) 4.9 Hz, J(HRHγ) ) 1.3 Hz), 8.51 (dd, 1H, Hγ, J(HâHγ) ) 8.2
Hz, J(HRHγ) ) 1.3 Hz), 8.43 (dd, 1H, Hγ′, J(Hâ′Hγ′) ) 8.2 Hz,
J(HRHγ) ) 1.3 Hz), 8.21 (dd, 1H, HR′, J(HR′Hâ′) ) 4.9 Hz, J(HR′Hγ′)
) 1.3 Hz), 7.91 (m, 3H, Hâ + Hδ + Hδ′), 7.60 (dd, 1H, Hâ′,
J(Hâ′Hγ′) ) 8.2 Hz, J(HR′Hâ′) ) 4.9 Hz), -0.75 (s, 1H, OH). 19F
NMR (CDCl3): δ(CFCl3) -117.1 (d, 2Fo, J(FoFm) ) 21.4 Hz),
-159.3 (t, 1Fp, J(FmFp) ) 19.8 Hz), -162.5 (m, 2Fm).
Conclusion
(Alkoxycarbonyl)palladium complexes are readily obtained
when CO is bubbled through an alcoholic solution of the
mononuclear hydroxo complex [Pd(N-N)(C6F5)(OH)]. The
reaction products are the result of the insertion of CO into
the Pd-OR bond of alkoxypalladium intermediates that have
not been isolated. These alkoxypalladium intermediates
should be formed from the acid-base reaction between the
hydroxopalladium complex and the corresponding alcohol
(Pd-OH + ROH f Pd-OR + H2O). With PhNCS and
PhNCO, similar reactions occur and the corresponding
thiocarbamate (Pd-SC(dNPh)OR) and carbamate (Pd-
N(Ph)C(dO)OR) complexes are obtained. When, instead of
ROH, Et2NH is used as the nucleophile, the thioureide
complex is formed: the insertion product of PhNCS into
the Pd-NEt2 bond (Pd-SC(dNPh)NEt2). In the absence of
a protic electrophile, insertion of CO2 into the Pd-OH bond
occurs and the hydrogen carbonate complex Pd-OC(dO)OH
that should be formed reacts with the initial hydroxo com-
plex to finally give the carbonato-bridged complex Pd-
OC(dO)O-Pd. The X-ray diffraction studies of some of
these complexes have been performed including the first
crystal structure of a binuclear carbonatopalladium complex.
Experimental Section
Instrumental Measurements. The C, H, N analyses were
performed with a Carlo Erba model EA 1108 microanalyzer.
Decomposition temperatures were determined with a Mettler TG-
50 thermobalance at a heating rate of 5 °C min-1 and the solid
samples under nitrogen flow (100 mL min-1). The NMR spectra
were recorded on a Bruker AC 200E or Varian Unity 300
spectrometer, using SiMe4 and CFCl3 as standards, respectively.
Infrared spectra were recorded on a Perkin-Elmer 1430 spectro-
photometer using Nujol mulls between polyethylene sheets. Solvents
were dried by the usual methods.
Data for Complex 4. Yield: 293 mg, 75%. Anal. Calcd for
C12H17N2F5OPd: C, 35.4; H, 4.2; N, 6.9. Found: C, 35.2; H, 4.3;
N, 6.6. Mp: 130 °C dec. IR (Nujol, cm-1): ν(OH), 3610; ν(Pd-
1
C6F5), 790. H NMR (CDCl3): δ(SiMe4) 2.68 (s, 6H, Me), 2.62
(m, 4H, CH2), 2.45 (s, 6H, Me), -1.97 (br, 1H, OH). 19F NMR
(CDCl3): δ(CFCl3) -117.6 (d, 2Fo, J(FoFm) ) 21.4 Hz), -160.1
(t, 1Fp, J(FmFp) ) 19.8 Hz), -163.1 (m, 2Fm).
Preparation of Complexes [(N-N)Pd(CO2Me)(C6F5)] (N-N
) bipy (5), Me2bipy (6), phen (7), or tmeda (8)). A CO stream
was passed through a solution of the corresponding hydroxo
complex [(N-N)Pd(OH)(C6F5)] (0.130 mmol) in methanol (10 mL)
for 5-15 min to give a white precipitate (for 5-7) which was
collected by filtration and air-dried. For the more soluble complex
8, the resulting solution was concentrated under vacuum until
Materials. The starting complexes [(N-N)Pd(C6F5)(acetone)]-
ClO4 (N-N ) bipy, Me2bipy, phen, and tmeda) were prepared by
procedures described elsewhere.39 The precursor [(N-N)Pd(C6F5)-
Cl] (N-N ) bis(3,5-dimethyl-pyrazol-1-yl)methane) was prepared
(54) Piraino, P.; Bruno, G.; Tresodi, G.; Faraone, G.; Bombieri, G. J. Chem.
Soc., Dalton Trans. 1983, 2391.
(55) Uso´n, R.; Fornie´s, J.; Navarro, R.; Garc´ıa, M. P. Inorg. Chim. Acta
1979, 33, 69.
Inorganic Chemistry, Vol. 42, No. 11, 2003 3657

Ruiz et al.
dryness and the residue was extracted with dichloromethane.
Addition of hexane caused the precipitation of a solid which was
collected by filtration and air-dried.
caused the precipitation of a white solid which was collected by
filtration, washed with water, and air-dried.
Data for Complex 9. Yield: 70 mg, 65%. Anal. Calcd for
Data for Complex 5. Yield: 41 mg, 65%. Anal. Calcd for
C18H11N2F5O2Pd: C, 44.2; H, 2.3; N, 5.7. Found: C, 44.2; H, 2.1;
N, 5.7. Mp: 209 °C dec. IR (Nujol, cm-1): ν(CO), 1635; ν(Pd-
C19H19N4F5O2Pd: C, 42.5; H, 3.5; N, 10.4. Found: C, 42.2; H,
3.6; N, 10.1. Mp: 146 °C dec. IR (Nujol, cm-1): ν(CO), 1640;
ν(Pd-C6F5), 790. 1H NMR (CDCl3, ambient temperature): δ(SiMe4)
7.20 (br, 1H, CH2), 6.10 (br, 1H, CH2), 5.91 (s, 1H, H4′), 5.77 (s,
1H, H4), 3.52 (s, 3H, CO2Me), 2.39 (s, 3H, Me3′), 2.35 (s, 3H,
Me5), 2.30 (s, 3H, Me5′), 1.68 (s, 3H, Me3). 19F NMR (CDCl3):
δ(CFCl3) -116.3 (br, 2Fo), -162.3 (t, 1Fp, J(FmFp) ) 20.3 Hz),
-164.7 (m, 2Fm).
1
C6F5), 780. H NMR (CDCl3): δ(SiMe4) 8.82 (d, HR, J(HRHâ) )
4.9 Hz), 8.04 (m, 4H, Hγ + Hγ′ + Hδ + Hδ′), 7.83 (d, 1H, HR′,
J(HR′Hâ′) ) 4.9 Hz), 7.50 (dd, Hâ, J(HâHγ) ) 8.2 Hz, J(HRHâ) )
4.9 Hz), 7.33 (dd, 1H, Hâ′, J(Hâ′Hγ′) ) 8.2 Hz, J(HR′Hâ′) ) 4.9
Hz), 3.55 (s, 3H, OMe). 19F NMR (CDCl3): δ(CFCl3) -115.5 (d,
2Fo, J(FoFm) ) 21.6 Hz), -160.9 (t, 1Fp, J(FmFp) ) 19.8), -163.1
(m, 2Fm). 13C{1H} NMR (CDCl3): δ(SiMe4) 154.6-121.9 (CH of
bipy), 51.14 (CH3 of CO2Me).
Data for Complex 6. Yield: 50 mg, 79%. Anal. Calcd for
C20H15N2F5O2Pd: C, 46.5; H, 2.9; N, 5.4. Found: C, 46.3; H, 3.0;
N, 5.3. Mp: 204 °C dec. IR (Nujol, cm-1): ν(CO), 1655; ν(Pd-
C6F5), 785. 1H NMR (CDCl3): δ(SiMe4) 8.67 (d, 1H, HR, J(HRHâ)
) 5.5 Hz), 7.86 (s, 1H, Hδ or Hδ′), 7.83 (s, 1H, Hδ or Hδ′), 7.67 (d,
1H, HR′, J(HR′Hâ′) ) 5.5 Hz), 7.30 (d, 1H, Hâ, J(HâHR) ) 5.5 Hz),
7.01 (d, 1H, Hâ′, J(Hâ′HR′) ) 5.5 Hz), 3.60 (s, 3H, OMe), 2.53 (s,
3H, Me), 2.48 (s, 3H, Me). 19F NMR (CDCl3): δ(CFCl3) -115.5
(d, 2Fo, J(FoFm) ) 22.9 Hz), -161.2 (t, 1Fp, J(FmFp) ) 21.2 Hz),
-163.2 (m, 2Fm). 13C{1H} NMR (CDCl3): δ(SiMe4) 151.6-122.4
(Me2bipy), 50.9 (CO2Me), 21.6 (Me2bipy).
Data for Complex 10. Yield: 82 mg, 78%. Anal. Calcd for
C20H21N4F5O2Pd: C, 43.6; H, 3.8; N, 10.2. Found: C, 43.4; H,
3.6; N, 9.9.
Mp: 157 °C dec. IR (Nujol, cm-1): ν(CO), 1632; ν(Pd-C6F5),
1
790. H NMR (CDCl3, ambient temperature): δ(SiMe4) 7.05 (br,
1H, CH2), 5.90 (br, 1 H, CH2), 5.85 (s, 1H, H4′), 5.70 (s, 1H, H4),
3.9 (br, 2H, CH2 of CO2Et), 2.32 (s, 3H, Me3′), 2.29 (s, 3H, Me5),
2.26 (s, 3H, Me5′), 1.79 (s, 3H, Me3), 1.02 (t, 3H, CH3 of CO2Et,
J(HH) ) 7.1 Hz). 19F NMR (CDCl3): δ(CFCl3) -116.2 (br, 2Fo),
-162.5 (t, 1Fp, J(FmFp) ) 20.3 Hz), -165.0 (m, 2Fm).
Data for Complex 11. Yield: 60 mg, 56%. Anal. Calcd for
C21H23ClN4F5O2Pd: C, 44.6; H, 4.0; N, 9.9. Found: C, 44.3; H,
3.8; N, 10.1. Mp: 174 °C dec. IR (Nujol, cm-1): ν(CO), 1638;
ν(Pd-C6F5), 792. 1H NMR (CDCl3, ambient temperature): δ(SiMe4)
7.1 (br, 1H, CH2), 5.9 (br, 1H, CH2), 5.85 (s, 1H, H4′), 5.69 (s,
1H, H4), 5.01 (sept, 1H, CH(CH3)2, J(HH) ) 6.3 Hz), 2.32 (s, 3H,
Me3′), 2.29 (s, 6H, Me5 and Me5′), 1.79 (s, 3H, Me3), 1.0 (br,
6H, CH(CH3)2). 19F NMR (CDCl3): δ(CFCl3) -115.8 (br, 2Fo),
-162.6 (t, 1Fp, J(FmFp) ) 20.3 Hz), -165.2 (br, 2Fm).
Preparation of Complexes [(N-N)(C6F5)Pd(µ-CO3)Pd(C6F5)-
(N-N)] [N-N ) bipy (12) or Me2bipy (13)]. CO2 was bubbled
through a suspension containing the hydroxo complex 1 (60 mg,
0.134 mmol) in tetrahydrofuran (15 mL) for 5 min. After partial
evaporation of the solvent, the pale yellow precipitate of 12 was
filtered off and air-dried. The experimental procedure for 13 was
similar but using the hydroxo complex 2 (60 mg, 0.126 mmol) and
dichloromethane (5 mL).
Data for Complex 12. Yield: 51 mg, 83%. Anal. Calcd for
C33H16N4F10O3Pd2: C, 43.1; H, 1.8; N, 6.1. Found: C, 43.2; H,
1.9; N, 6.0. Mp: 199 °C. IR (Nujol, cm-1): νasym(OCO of CO3),
1540; νsym(OCO of CO3), 1300; ν(Pd-C6F5), 785. 1H NMR
((CD3)2SO): δ(SiMe4) 8.60 (d, 4H, HR + HR′, J(HRHâ) = J(HR′Hâ′)
= 7 Hz), 8.33-8.25 (m, 6H, Hγ + Hγ′ + Hδ), 7.90 (d, 2H, Hδ′,
J(Hγ′Hδ′) ) 4.6 Hz), 7.61 (dd, 2H, Hâ, J(HRHâ = J(HâHγ) = 7
Hz), 7.50 (dd, 2H, Hâ′, J(HR′Hâ′) = J(Hâ′Hγ′) = 7 Hz); 19F NMR:
δ(CFCl3) -116.9 (d, 4Fo, J(FoFm) ) 24.6 Hz), -161.3 (t, 2Fp,
J(FmFp) ) 19.8 Hz), -163.3 (m, 4Fm).
Data for Complex 7. Yield: 37 mg, 55%. Anal. Calcd for
C20H11N2F5O2Pd: C, 46.9; H, 2.2; N, 5.5. Found: C, 46.8; H, 2.3;
N, 5.3. Mp: 190 °C dec. IR (Nujol, cm-1): ν(CO), 1640; ν(Pd-
C6F5), 780. 1H NMR (CDCl3): δ(SiMe4) 9.18 (dd, 1H, HR, J(HRHâ)
) 4.9 Hz, J(HRHγ) ) 1.3 Hz), 8.48 (dd, 1H, Hγ, J(HâHγ) ) 8.2
Hz, J(HRHγ) ) 1.3 Hz), 8.39 (dd, 1H, Hγ′, J(Hâ′Hγ′) ) 8.2 Hz,
J(HR′Hγ′) ) 1.3 Hz), 8.16 (dd, 1H, HR′, J(HR′Hâ′) ) 4.9 Hz, J(HR′Hγ′)
) 1.3 Hz), 7.91 (s, 1H, Hδ or Hδ′), 7.90 (s, 1H, Hδ or Hδ′), 7.80
(dd, 1H, Hâ, J(HâHγ) ) 8.2 Hz, J(HRHâ) ) 4.9 Hz), 7.64 (dd, 1H,
Hâ′, J(Hâ′Hγ′) ) 8.2 Hz, J(HR′Hâ′) ) 4.9 Hz), 3.60 (s, 3H, Me). 19
F
NMR (CDCl3): δ(CFCl3) -115.2 (d, 2Fo, J(FoFm) ) 22.9 Hz),
-161.0 (t, 1Fp, J(FmFp) ) 20.0 Hz), -163.2 (m, 2Fm). 13C{1H}
NMR (CDCl3): δ(SiMe4) 152.5-125.2 (phen), 20.0 (CO2Me).
Data for Complex 8. Yield: 47 mg, 80%. Anal. Calcd for
C14H19N2F5O2Pd: C, 37.5; H, 4.3; N, 6.2. Found: C, 37.3; H, 4.4;
N, 6.0. Mp: 140 °C dec. IR (Nujol, cm-1): ν(CO), 1650; ν(Pd-
C6F5), 780. 1H NMR (CDCl3): δ(SiMe4) 3.40 (s, 3H, OMe), 2.71
(s, 6H, Me), 2.65 (m, 2H, CH2), 2.54 (m, 2H, CH2), 2.27 (s, 6H,
Me). 19F NMR (CDCl3): δ(CFCl3) -116.6 (d, 2Fo, J(FoFm) ) 22.9
Hz;), -161.5 (t, 1Fp, J(FmFp) ) 19.8 Hz), -163.7 (m, 2Fm). 13C{1H}
NMR (CDCl3): δ(SiMe4) 183.6 (CO2Me), 60.7-59.6 (CH2 of
tmeda), 50.5 (CO2Me), 49.8-48.6 (CH3 of tmeda).
Reaction of [(bipy)Pd(CO)(C6F5)]ClO4 with NaOMe. To a
solution of [(bipy)Pd(CO)(C6F5)]ClO4 (80 mg, 0.152 mmol) in
methanol (15 mL) was added NaOMe (16.5 mg, 0.304 mmol). The
resulting solution was stirred for 1.5 h and then concentrated under
vacuum until precipitation of complex 5, which was collected by
filtration and air-dried. Yield: 60%.
Data for Complex 13. Yield: 47 mg, 76%. Anal. Calcd for
C35H20N4F10O3Pd2: C, 45.56; H, 2.48; N, 5.74. Found: C, 45.38;
H, 2.51; N, 5.75. Mp: 226°C dec. IR (Nujol, cm-1): νasym(OCO of
CO3), 1548; νsym(OCO of CO3), 1300; ν(Pd-C6F5), 790. 1H NMR
(CDCl3): δ(SiMe4) 8.88 (d, 2H, HR, J(HRHâ) ) 5.4 Hz), 7.82 (s,
4H, Hδ + Hδ′), 7.80(d, 2H, HR′, J(HR′Hâ′) ) 5.5 Hz), 7.46 (d, 2H,
Hâ, J(HRHâ) ) 5.4 Hz), 7.11 (d, 2H, Hâ′, J(HR′Hâ′) ) 5.4 Hz),
2.58 (s, 6H, Me), 2.50 (s, 6H, Me′). 19F NMR (CDCl3): δ(CFCl3)
-117.0 (m, 4Fo), -159.6 (t, 2Fp, J(FmFp) ) 20.7 Hz), -162.6 (m,
4Fm).
Preparation of Complexes [(N-N)Pd(C6F5)(COOR)] [N-N
) Bis(3,5-dimethylpyrazol-1-yl)methane, CH2(C3HMe2N2)2; R
i
) Me (9), Et (10), or Pr (11)]. To a suspension of [(N-N)Pd-
(C6F5)Cl] (100 mg, 0.19 mmol) in the corresponding alcohol ROH
i
(R ) Me, Et, or Pr) (15 mL) was added KOH(aq) (11 mg, 0.19
mmol). The suspension was stirred for 15 min, and a CO stream
was then passed through the resulting mixture for 5 min. Stirring
was continued for 30 min, and the mixture was then filtered through
Celite to remove some KCl and traces of palladium metal. The
filtrate was concentrated under vacuum. The addition of water
Preparation of Complexes [(N-N)Pd(C6F5){SC(OR)NPh}]
[N-N ) bipy, R ) Me (14), Et (15), or Pr (16); N-N )
Me2bipy, R ) Me (17), Et (18), or Pr (19); N-N ) phen, R )
Me (20), Et (21), or Pr (22); N-N ) tmeda, R ) Me (23), Et
(24), or Pr (25)]. To a solution of the corresponding hydroxo-
3658 Inorganic Chemistry, Vol. 42, No. 11, 2003

Insertion Reactions into Pd-O and Pd-N Bonds
palladium complex [(N-N)Pd(OH)(C6F5)] (0.134 mmol) in alcohol
(MeOH, EtOH, or PrOH) (10 mL) was added PhNCS (0.134 mmol).
The resulting solution was stirred at room temperature for 1 h, and
then solvent was partially eliminated under reduced pressure to give
a yellow suspension. The solid was collected by filtration and air-
dried.
δ(CFCl3) -119.7 (d, 2Fo, J(FoFm) ) 22.8 Hz), -160.7 (t, 1Fp,
J(FmFp) ) 19.8 Hz), -163.5 (m, 2Fm).
Data for Complex 19. Yield: 56 mg, 64%. Anal. Calcd for
C28H24N3F5OPd: C, 51.6; H, 3.7; N, 6.4; S, 4.9. Found: C, 51.3;
H, 3.5; N, 6.6; S, 5.1. Mp: 204 °C dec. IR (Nujol, cm-1): ν(CdN),
1580; ν(Pd-C6F5), 795. 1H NMR (CDCl3): δ(SiMe4) 8.86 (d, 1H,
HR, J(HRHâ) ) 5.4 Hz), 7.81 (s, 1H, Hδ or Hδ′), 7.77 (s, 1H, Hδ or
Hδ′), 7.65 (d, 1H, HR′, J(HR′Hâ′) ) 5.5 Hz), 7.27 (d, 1H, Hâ, J(HRHâ)
) 5.4 Hz), 7.15 (m, 3H, Hâ′ of Me2bipy + Ho of NPh), 6.82 (m,
3H, Hp + Hm of NPh), 3.94 (t, 2H, OCH2CH2CH3, J ) 6.8 Hz),
2.45 (s, 3H, Me2bipy), 2.42 (s, 3H, Me2bipy), 1.43 (m, 2H,
OCH2CH2CH3), 0.68 (t, 3H, OCH2CH2CH3, J ) 7.3 Hz). 19F NMR
(CDCl3): δ(CFCl3) -117.1 (d, 2Fo, J(FoFm) ) 22.8 Hz), -160.8
(t, 1Fp, J(FmFp) ) 19.8 Hz), -163.5 (m, 2Fm).
Data for Complex 20. Yield: 53 mg, 64%. Anal. Calcd for
C26H16N3F5OPdS: C, 50.4; H, 2.6; N, 6.8; S, 5.2. Found: C, 50.2;
H, 2.8; N, 6.6; S, 5.1. Mp: 217 °C dec. IR (Nujol, cm-1): ν(Cd
N), 1572; ν(Pd-C6F5), 799. 1H NMR (CDCl3): δ(SiMe4) 9.29 (dd,
1H, HR, J(HRHâ) ) 5.0 Hz, J(HRHγ) ) 1.3 Hz), 8.46 (d, 2H, Hγ
+Hγ′, J(HâHγ) ) J(Hâ′Hγ′) ) 8.2 Hz), 8.20 (dd, 1H, HR′, J(HR′Hâ′)
) 5.0 Hz, J(HR′Hγ′) ) 1.3 Hz), 7.92 (m, 2H, Hδ + Hδ′), 7.80 (dd,
1H, Hâ, J(HâHγ) ) 8.2 Hz, J(HRHâ) ) 5.0 Hz), 6.92 (dd, 1H, Hâ′,
1H, J(Hâ′Hγ′) ) 8.2 Hz, J(HR′Hâ′) ) 5.0 Hz), 7.12 (m, 2H, Ho of
NPh), 6.84 (m, 3H, Hp + Hm of NPh), 3.62 (s, 3H, OCH3). 19F
NMR (CDCl3): δ(CFCl3) -117.2 (d, 2Fo, J(FoFm) ) 21.5 Hz),
-160.2 (t, 1Fp, J(FmFp) ) 19.8 Hz), -163.4 (m, 2Fm).
Data for Complex 14. Yield: 54 mg, 68%. Anal. Calcd for
C24H16N3F5OPdS: C, 48.4; H, 2.7; N, 7.1; S, 5.4. Found: C, 48.0;
H, 2.5; N, 6.9; S, 5. Mp: 209 °C dec. IR (Nujol, cm-1): ν(CdN),
1
1600, 1580; ν(Pd-C6F5), 790. H NMR (CDCl3): δ(SiMe4) 9.03
(d, 1H, HR, J(HRHâ) ) 5.0 Hz), 8.01 (m, 4H, Hγ + Hγ′ + Hδ +
Hδ′), 7.89 (d, 1H, HR′, J(HR′Hâ′) ) 5.0 Hz), 7.50 (dd, 1H, Hâ,
J(HâHγ) ) 8.2 Hz, J(HRHâ) ) 5.0 Hz), 7.36 (dd, 1H, Hâ′, J(Hâ′Hγ′)
) 8.2 Hz, J(HR′Hâ′) ) 5.9 Hz), 7.14 (d, 2H, Ho of NPh, J ) 7.7
Hz), 6.80 (m, 3H, Hp + Hm of NPh), 3.60 (s, 3H, OCH3). 19F NMR
(CDCl3): δ(CFCl3) -117.3 (d, 2Fo, J(FoFm) ) 22.8 Hz), -160.3
(t, 1Fp, J(FmFp) ) 20.0 Hz), -163.4 (m, 2Fm).
Data for Complex 15. Yield: 51 mg, 63%. Anal. Calcd for
C25H18N3F5OPdS: C, 49.2; H, 3.0; N, 6.9; S, 5.3. Found: C, 48.9;
H, 3.0; N, 6.6; S, 5.1. Mp: 181 °C dec. IR (Nujol, cm-1): ν(CdN),
1
1600, 1584; ν(Pd-C6F5), 790. H NMR (CDCl3): δ(SiMe4) 9.02
(d, 1H, HR, J(HRHâ) ) 5.2 Hz), 8.00 (m, 4H, Hγ + Hγ′ + Hδ +
Hδ′), 7.88 (d, 1H, HR′, J(HR′Hâ′) ) 5.0 Hz), 7.46 (dd, 1H, Hâ,
J(HγHâ) ) 8.2, J(HRHâ) ) 5.2 Hz), 7.35 (dd, 1H, Hâ′, J(Hâ′Hγ′) )
8.2 Hz, J(HR′Hâ′) ) 5.0 Hz), 7.10 (d, 2H, Ho of NPh, J ) 7.9 Hz),
6.81 (m, 3H, Hp + Hm of NPh), 4.06 (q, 2H, OCH2CH3, J ) 7.1
Hz), 1.10 (t, 3H, OCH2CH3, J ) 7.1 Hz). 19F NMR (CDCl3): δ-
(CFCl3) -116.9 (d, 2F, Fo, J(FoFm) ) 21.4 Hz), -160.4 (t, 1F, Fp,
J(FmFp) ) 20.0 Hz), -163.3 (m, 2F, Fm).
Data for Complex 21. Yield: 54 mg, 64%. Anal. Calcd for
C27H18N3F5OPdS: C, 51.2; H, 2.9; N, 6.6; S, 5.1. Found: C, 51.1;
H, 2.9; N, 6.4; S, 5.1. Mp: 209 °C dec. IR (Nujol, cm-1): ν(CdN),
Data for Complex 16. Yield: 58 mg, 69%. Anal. Calcd for
C26H20N3F5OPdS: C, 50.1; H, 3.2; N, 6.7; S, 5.1. Found: C, 50.2;
H, 3.2; N, 6.5; S, 5.0. Mp: 169°C dec. IR (Nujol, cm-1): ν(CdN),
1
1574; ν(Pd-C6F5), 796. H NMR (CDCl3): δ(SiMe4) 9.18 (dd,
1H, HR, J(HRHâ) ) 5.0 Hz, J(HRHγ) ) 1.3 Hz), 8.44 (d, 2H, Hγ +
Hγ′, J ) 8.1 Hz), 8.17 (dd, 1H, HR′, J(HR′Hâ′) ) 5.0 Hz, J(HR′Hγ′)
) 1.3 Hz), 7.90 (m, 2H, Hδ + Hδ′), 7.80 (dd, 1H, Hâ, J(HâHγ) )
8.2 Hz, J(HRHâ) ) 5.0 Hz), 6.92 (dd, 1H, Hâ′, J(Hâ′Hγ′) ) 8.2 Hz,
J(HR′Hâ′) ) 5.0 Hz), 7.12 (m, 2H, Ho of NPh), 6.84 (m, 3H, Hp +
Hm of NPh), 4.07 (q, 2H, OCH2CH3, J ) 7.0 Hz), 1.07 (t, 3H,
OCH2CH3, J ) 7.0 Hz). 19F NMR (CDCl3): δ(CFCl3) -116.7 (d,
2Fo, J(FoFm) ) 22.8 Hz), -160.4 (t, 1Fp, J(FoFm) ) 19.8 Hz),
-163.3 (m, 2Fm).
Data for Complex 22. Yield: 51 mg, 59%. Anal. Calcd for
C28H20N3F5OPdS: C, 51.9; H, 3.1; N, 6.5; S, 5.0. Found: C, 51.8;
H, 2.9; N, 6.2; S, 4.7. Mp: 204 °C dec. IR (Nujol, cm-1): ν(CdN),
1574; ν(Pd-C6F5), 796. 1H NMR (CDCl3): δ(SiMe4) 9.22 (d, 1H,
HR, J(HRHâ) ) 5.0 Hz), 8.44 (d, 2H, Hγ +Hγ′, J(HâHγ) ) J(Hâ′Hγ′)
) 8.2 Hz), 8.16 (d, 1H, HR′, J(HR′Hâ′) ) 5.0 Hz), 7.92 (d, 1H, Hδ
or Hδ′, J(HδHδ′) ) 8.1 Hz), 7.88 (d, 1H, Hδ or Hδ′, J(HδHδ′) ) 8.1
Hz), 7.75 (dd, 1H, Hâ, J(HâHγ) ) 8.2 Hz, J(HRHâ) ) 5.0 Hz),
7.63 (dd, 1H, Hâ′, J(Hâ′Hγ′) ) 8.2 Hz, J(HR′Hâ′) ) 5.0 Hz), 7.12
(m, 2H, Hm of NPh), 6.90 (d, 2H, Ho of NPh, J ) 7.2 Hz), 6.84 (t,
1H, Hp of NPh, J ) 7.2 Hz), 3.96 (t, 2H, OCH2 CH2CH3, J ) 7.0
Hz), 1.43 (m, 2H, OCH2CH2CH3), 0.60 (t, 3H, OCH2CH2CH3, J
) 7.3 Hz). 19F NMR (CDCl3): δ(CFCl3) -116.9 (d, 2Fo, J(FoFm)
) 19.1 Hz), -160.5 (t, 1Fp, J(FmFp) ) 21.0 Hz), -163.2 (m, 2Fm).
1
1600, 1588; ν(Pd-C6F5), 788. H NMR (CDCl3): δ(SiMe4) 9.06
(d, 1H, HR, J(HRHâ) ) 5.2 Hz), 7.97 (m, 4H, Hγ + Hγ′ + Hδ +
Hδ′), 7.86 (d, 1H, HR′, J(HR′Hâ′) ) 5.2 Hz), 7.46 (dd, 1H, Hâ,
J(HâHγ) ) 8.2 Hz, J(HRHâ) ) 5.2 Hz), 7.34 (dd, 1H, Hâ′, J(Hâ′Hγ′)
) 8.2 Hz, J(HR′Hâ′) ) 5.2 Hz), 7.16 (d, 2H, Ho of NPh, J(Hâ′Hγ′)
) 7.9 Hz), 6.82 (m, 3H, Hp + Hm of NPh), 3.95 (t, 2H, OCH2-
CH2CH3, J ) 6.8 Hz), 1.43 (m, 2H, OCH2CH2CH3, J ) 7.1 Hz),
0.67 (t, 3H, OCH2CH2CH3, J ) 7.3 Hz). 19F NMR (CDCl3):
δ(CFCl3) -1172 (d, 2Fo, J(FoFm) ) 23.1 Hz), -160.5 (t, 1Fp,
J(FmFp) ) 19.8 Hz), -163.2 (m, 2Fm).
Data for Complex 17. Yield: 46 mg, 55%. Anal. Calcd for
C26H20N3F5OPdS: C, 50.1; H, 3.2; N, 6.7; S, 5.1. Found: C, 49.9;
H, 3.0; N, 6.6; S, 5.0. Mp: 204 °C dec. IR (Nujol, cm-1): ν(CdN),
1
1608, 1588; ν(Pd-C6F5), 788. H NMR (CDCl3): δ(SiMe4) 8.80
(d, 1H, HR, J(HRHâ) ) 5.4 Hz), 7.80 (s, 1H, Hδ or Hδ′), 7.76 (s,
1H, Hδ or Hδ′), 7.65 (d, 1H, HR′, J(HR′Hâ′) ) 5.4 Hz), 7.24 (d, 1H,
Hâ, J(HRHâ) ) 5.4 Hz), 7.14 (d, 2H, Ho of NPh, J ) 8.0 Hz), 7.07
(d, 1H, Hâ′, J(HR′Hâ′) ) 5.4 Hz), 6.86 (t, 1H, Hp of NPh, J ) 8.0
Hz), 6.76 (m, 2H, Hm of NPh), 3.58 (s, 3H, OCH3), 2.45 (s, 3H,
Me2bipy), 2.42 (s, 3H, Me2bipy). 19F NMR (CDCl3): δ(CFCl3)
-117.2 (d, 2Fo, J(FoFm) ) 19.8 Hz), -160.5 (t, Fp, J(FmFp) ) 19.8
Hz), -163.5 (m, 2Fm).
Data for Complex 23. Yield: 51 mg, 69%. Anal. Calcd for
C20H24N3F5OPdS: C, 43.2; H, 4.4; N, 7.6; S, 5.8. Found: C, 43.0;
H, 4.2; N, 7.4; S, 5.6. Mp: 155 °C dec. IR (Nujol, cm-1): ν(CdN),
Data for Complex 18. Yield: 58 mg, 68%. Anal. Calcd for
C27H22N3F5OPdS: C, 50.8; H, 3.5; N, 6.6; S, 5.0. Found: C, 50.3;
H, 3.5; N, 6.4; S, 5.1. Mp: 206 °C. IR (Nujol, cm-1): ν(CdN),
1580; ν(Pd-C6F5), 795. 1H NMR (CDCl3): δ(SiMe4) 8.78 (d, 1H,
HR, J(HRHâ) ) 5.4 Hz), 7.81 (s, 1H, Hδ or Hδ′), 7.76 (s, 1H, Hδ or
Hδ′), 7.64 (d, 1H, HR′, J(HR′Hâ′) ) 5.5 Hz), 7.20 (m, 4H, Hâ + Hâ′
of Me2bipy + Ho of NPh), 6.81 (m, 3H, Hp + Hm of NPh), 2.46 (s,
3H, Me2bipy), 2.43 (s, 3H, Me2bipy), 4.01 (q, 2H, OCH2CH3, J )
7.0 Hz), 1.08 (t, 3H, OCH2CH3, J ) 7.0 Hz). 19F NMR (CDCl3):
1
1602, 1588; ν(Pd-C6F5), 786. H NMR (CDCl3): δ(SiMe4) 7.13
(m, 2H, Hm of NPh), 6.86 (t, 1H, Hp of NPh, J ) 7.5 Hz), 6.60 (d,
2H, Ho of NPh, J ) 7.6 Hz), 3.64 (s, 3H, OCH3), 2.61 (m, 4H,
CH2 of tmeda), 2.55 (s, 3H, CH3 of tmeda), 2.44 (s, 3H, CH3 of
tmeda). 19F NMR (CDCl3): δ(CFCl3) -118.7 (d, 2Fo, J(FoFm) )
22.8 Hz), -161.2 (t, 1Fp, J(FmFp) ) 19.8 Hz), -164.1 (m, 2Fm).
Inorganic Chemistry, Vol. 42, No. 11, 2003 3659

Ruiz et al.
Table 1. Crystal Data and Structure Refinement for 8, 13‚2CH2Cl2, and 23
8
13‚2CH2Cl2
23
empirical formula
MT
C14H19F5N2O2Pd
448.7
C37H24F10N4O3Pd2‚2CH2Cl2
1145.25
C20H24F5N3OPdS
555.88
T (K)
293
173
293
λ (Å)
space group
a (Å)
b (Å)
c (Å)
0.71073
P2(1)/c
11.792(2)
13.370(3)
11.498(2)
90
96.37(2)
90
1801.5(6)
4
1.65
1.07
2-25
-14 e h e +14
0 e k e 15
0 e l e 13
3469
ψ scans
3311/0/217
1.5
0.71073
P-1
0.71073
P2(1)/n
11.297(2)
12.697(2)
16.825(3)
90
108.791(15)
90
2284.7(8)
4
1.616
0.960
2-25
0 e h e 13
0 e k e 15
-19 e l e +18
4216
ψ scans
4008/0/280
1.059
11.1311(6)
11.6741(7)
17.0116(8)
70.810(4)
84.557(4)
84.114(4)
2072.34(19)
2
1.835
1.215
3-25
-13 e h e +5
-13 e k e +13
-20 e l e +20
10850
none
7209/1/564
0.869
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
F (Mg m-3
)
µ (mm-1
)
θ range (deg)
index ranges
no. of reflns collected
absorption correction
no. of data/restraints/params
GOF on F2
final R indices [I > 2σ(I)]
R1 ) 0.047
R1 ) 0.032
wR2 ) 0.083
R1 ) 0.043
wR2 ) 0.087
R1 ) 0.033
wR2 ) 0.080
R1 ) 0.043
wR2 ) 0.085
R indices (all data)
R1 ) 0.054
Data for Complex 24. Yield: 52 mg, 68%. Anal. Calcd for
C21H26N3F5OPdS: C, 44.3; H, 4.6; N, 7.4; S, 5.6. Found: C, 44.0;
H, 4.7; N, 7.6; S, 5.9. Mp: 157 °C dec. IR (Nujol, cm-1): ν(CdN),
Preparation of Complexes [(N-N)Pd(C6F5){SC(NEt2)NPh}]
[N-N ) bipy (27), Me2bipy (28), or phen (29)]. To a suspension
of [(N-N)Pd(OH)(C6F5)] (60 mg, 0.134 mmol) in acetone (20 mL)
was added diethylamine (0.160 mmol). After 5 min of stirring,
PhNCS (0.134 mmol) was also added. The resulting suspension
was stirred for 2 h to give a yellow solution. Then solvent was
partially eliminated under reduced pressure to yield a yellow
precipitate. The solid was collected by filtration and air-dried.
1
1598, 1586; ν(Pd-C6F5), 786. H NMR (CDCl3): δ(SiMe4) 7.15
(m, 2H, Hm of NPh), 6.85 (t, 1H, Hp of NPh, J ) 7.3 Hz), 6.61 (d,
2H, Ho of NPh, J ) 7.5 Hz), 4.11 (q, 2H, OCH2CH3, J ) 7.1 Hz),
2.66 (s, 4H, CH2 of tmeda), 2.60 (s, 3H, CH3 of tmeda), 2.56 (s,
3H, CH3 of tmeda), 1.33 (t, 3H, OCH2CH3, J ) 7.1 Hz). 19F NMR
(CDCl3): δ(CFCl3) -118.7 (d, 2Fo, J(FoFm) ) 22.8 Hz), -161.2
(t, 1Fp, J(FmFp) ) 19.8 Hz), -164.1 (m, 2Fm).
Data for Complex 27. Yield: 47 mg, 55%. Anal. Calcd for
C27H23N4F5PdS: C, 50.9; H, 3.6; N, 8.8; S, 5.0. Found: C, 50.5;
H, 3.7; N, 8.8; S, 4.8. Mp: 262 °C dec. IR (Nujol, cm-1): ν(CdN),
1538; ν(Pd-C6F5), 788. 1H NMR (CDCl3): δ(SiMe4) 8.64 (m, 1H,
HR), 8.0-7.8 (m, 5H, Hγ + Hγ′ + HR′ + Hδ + Hδ′), 7.30 (m, 2H,
Hâ + Hâ′), 6.89 (d, 2H, Ho of NPh, J ) 7.5 Hz), 6.59 (dd, 2H, Hm
of NPh, J ) 7.5 Hz), 6.07 (t, 1H, Hp of NPh, J ) 7.5 Hz), 3.32 (q,
4H, NCH2, J ) 7.5 Hz), 0.97 (t, 6H, NCH2CH3, J ) 7.5 Hz). 19F
NMR (CDCl3): δ(CFCl3) -117.1 (d, 2Fo, J(FoFm) ) 23.7 Hz),
-161.4 (t, 1Fp, J(FmFp) ) 21.6 Hz), -163,7 (m, 2Fm).
Data for Complex 28. Yield: 48 mg, 54%. Anal. Calcd for
C29H27N4F5PdS: C, 52.4; H, 4.1; N, 8.4; S, 4.8. Found: C, 52.1;
H, 4.1; N, 8.4; S, 4.6. Mp: 182 °C dec. IR (Nujol, cm-1): ν(CdN),
1548; ν(Pd-C6F5), 786. 1H NMR (CDCl3): δ(SiMe4) 8.42 (d, 1H,
HR, J(HRHâ) ) 5.4 Hz), 7.74 (s, 1H, Hδ or Hδ′), 7.63 (m, 2H, Hδ
or Hδ′ + HR′), 7.05 (d, 2H, Hâ + Hâ′, J(HR′Hâ′) ) J(HRHâ) ) 5.4
Hz), 6.87 (d, 2H, Ho of NPh, J ) 7.5 Hz), 6.62 (dd, 2H, Hm of
NPh, J ) 7.5 Hz), 6.11 (t, 1H, Hp of NPh, J ) 7.5 Hz), 3.33 (q,
4H, NCH2, J ) 7.5 Hz), 2.43 (s, 6H, Me2bipy), 0.95 (t, 6H,
NCH2CH3, J ) 7.5 Hz). 19F NMR (CDCl3): δ(CFCl3) -117.0 (d,
2Fo, J(FoFm) ) 22.2 Hz), -161.6 (t, 1Fp, J(FmFp) ) 20.4 Hz),
-163.8 (m, 2Fm).
Data for Complex 25. Yield: 53 mg, 68%. Anal. Calcd for
C22H28N3F5OPdS: C, 45.3; H, 4.8; N, 7.2; S, 5.5. Found: C, 45.0;
H, 4.7; N, 7.5; S, 5.7. Mp: 151 °C dec. IR (Nujol, cm-1): ν(CdN),
1
1604, 1590; ν(Pd-C6F5), 786. H NMR (CDCl3): δ(SiMe4) 7.16
(m, 2H, Hm of NPh), 6.66 (t, 1H, Hp of NPh, J ) 7.5 Hz), 6.60 (d,
2H, Ho of NPh, J ) 7.5 Hz), 4.09 (t, 2H, OCH2CH2CH3, J ) 7.2
Hz), 2.66 (s, 4H, CH2 of tmeda), 2.62 (s, 3H, CH3 of tmeda), 2.49
(s, 3H, CH3 of tmeda), 1.81 (m, 2H, OCH2CH2CH3), 1.08 (t, 3H,
OCH2CH2CH3, J ) 7.2 Hz). 19F NMR (CDCl3): δ(CFCl3) -118.7
(d, 2Fo, J(FoFm) ) 22.8 Hz), -161.4 (t, 1Fp, J(FmFp) ) 19.8 Hz),
-164.0 (m, 2Fm).
Preparation of the Complex [(bipy)Pd(C6F5){N(Ph)C(O)-
OR)}] (26). To a solution of [(bipy)Pd(OH)(C6F5)] (50 mg, 0.111
mmol) in methanol (15 mL) was added PhNCO (0.111 mmol). The
resulting solution was stirred at room temperature for 1 h to give
a yellow suspension which was partially concentrated under reduced
pressure. The solid was collected by filtration and air-dried.Yield:
58%. Anal. Calcd for C24H16N3F5O2Pd: C, 49.7; H, 2.8; N, 7.3.
Found: C, 49.5; H, 2.7; N, 7.1. Mp: 206 °C dec. IR (Nujol, cm-1):
ν(CO), 1644; ν(Pd-C6F5), 786. 1H NMR (CDCl3): δ(SiMe4) 8.64
(d, 1H, HR, J(HRHâ) ) 5.0 Hz), 8.09 (m, 4H, Hγ + Hγ′ + Hδ +
Hδ′), 7.94 (d, 1H, HR′, J(HR′Hâ′) ) 5.0 Hz), 7.56 (m, 3H, Ho of
NPh + Hâ), 7.35 (dd, 1H, Hâ′, J(Hâ′Hγ′) ) 8.2 Hz, J(HR′Hâ′) ) 4.9
Hz), 7.06 (m, 2H, Hm of NPh), 6.81 (t, 1H, Hp of NPh, J ) 7.4
Hz), 3.66 (s, 3H, OCH3). 19F NMR (CDCl3): δ(CFCl3) -119.3
(m, 1Fo), -120.0 (m, 1Fo), -160.3 (t, 1Fp, J(FmFp) ) 19.8 Hz),
-162.9 (m, 1Fm), -163.4 (m, 1Fm).
Data for Complex 29. Yield: 58 mg, 65%. Anal. Calcd for
C29H23N4F5PdS: C, 52.7; H, 3.5; N, 8.5; S, 4.9. Found: C, 52.8;
H, 3.0; N, 8.4; S, 4.6. Mp: 204 °C dec. IR (Nujol, cm-1): ν(CdN),
1552; ν(Pd-C6F5), 790. 1H NMR (CDCl3): δ(SiMe4) 8.80 (d, 1H,
HR, J(HRHâ) ) 5.0 Hz), 8.42 (d, 1H, Hγ, J(HâHγ) ) 8.2 Hz), 8.30
(d, 1H, Hγ′, J(Hâ′Hγ′) ) 8.2 Hz), 8.14 (d, 1H, HR′, J(HR′Hâ′) ) 5.0
Hz), 7.86 (m, 2H, Hδ + Hδ′), 7.60 (m, 2H, Hâ + Hâ′), 6.90 (d, 2H,
3660 Inorganic Chemistry, Vol. 42, No. 11, 2003

Insertion Reactions into Pd-O and Pd-N Bonds
Ho of NPh, J ) 7.5 Hz), 6.38 (dd, 2H, Hm of NPh, J ) 7.5 Hz),
5.82 (t, 1H, Hp of NPh, J ) 7.5 Hz), 3.37 (q, 4H, NCH2, J ) 7.5
Hz), 0.98 (t, 6H, NCH2CH3, J ) 7.5 Hz). 19F NMR (CDCl3): δ-
(CFCl3) -116.9 (d, 2Fo, J(FoFm) ) 24.0 Hz), -161.3 (t, 1Fp, J(FmFp)
) 21.6 Hz), -163.7 (m, 2Fm).
data collection was performed with a Enraf-Nonius CAD4 diffrac-
tometer for 8 and 23 and with a Siemens P4 diffractometer for 13.
The scan mode was θ-2θ for 8 and 23 and ω-2θ for 13. The
structures were solved by heavy atom methods, SHELXS-8656
(complex 8), and by direct methods, SHELXS-9757 (complexes 13
and 23). The structures were refined by full-matrix least-squares
Enraf-Nonius MOLEN programs58 (complex 8) and SHELXL-9757
(complexes 13 and 23). In the three structures hydrogen atoms were
included using a riding model.
Preparation of the Complex [(tmeda)Pd(C6F5){SC(NEt2)-
NPh}] (30). To a solution of [(tmeda)Pd(OH)(C6F5)] (60 mg, 0.134
mmol) in acetone (20 mL) was added diethylamine (0.160 mmol).
After 5 min of stirring, PhNCS (0.134 mmol) was also added. The
resulting solution was stirred for 2 h. Then solvent was partially
eliminated under reduced pressure. Addition of hexane caused the
precipitation of a solid which was collected by filtration and air-
dried. Yield: 68 mg, 85%. Anal. Calcd for C23H31N4F5PdS: C,
46.3; H, 5.2; N, 9.4; S, 5.4. Found: C, 46.0; H, 5.0; N, 9.0; S, 5.1.
Mp: 110 °C dec. IR (Nujol, cm-1): ν(CdN), 1556; ν(Pd-C6F5),
788. 1H NMR (CDCl3): δ(SiMe4) 7.13 (d, 2H, Ho of NPh, J ) 7.5
Hz), 6.88 (dd, 2H, Hm of NPh, J ) 7.5 Hz), 6.74 (t, 1H, Hp of
NPh, J ) 7.5 Hz), 3.25 (q, 4H, NCH2CH3, J ) 7.5 Hz), 2.49 (m,
4H, CH2 of tmeda), 2.33 (s, 6H, CH3 of tmeda), 2.13 (s, 6H, CH3
of tmeda), 0.89 (t, 6H, NCH2CH3, J ) 7.5 Hz); 19F NMR
(CDCl3): δ(CFCl3) -117.5 (d, 2Fo, J(FoFm) ) 23.4 Hz), -161.8
(t, 1Fp, J(FmFp) ) 19.5 Hz), -163.8 (m, 2Fm).
Acknowledgment. Financial support of this work by the
Direccio´n General de Investigacio´n del Ministerio de Ciencia
y Tecnolog´ıa (Project No. BQU2001-0979-C02-01), Spain,
is acknowledged.
Supporting Information Available: X-ray crystallographic files
in CIF format for the structure determination of compounds 8, 13,
and 23. This material is available free of charge via the Internet at
http://pubs.acs.org.
IC0300058
(56) Program for Crystal Structure Solution: G. M. Sheldrick, Institu¨t fu¨r
Anorganische Chemie der Universita¨t, Tammanstrasse 4, D-3400
Go¨ttingen, Germany, 1986.
(57) Sheldrick, G. M. SHELX-97. Programs for Crystal Structure Analysis,
Release 97-2; University of Go¨ttingen: Go¨ttingen, Germany, 1998.
(58) MOLEN, CAD4 Software, Version 5.0; Enraf-Nonius: Delft, The
Netherlands, 1989.
X-ray Crystal Structure Analysis. Suitable crystals of 8, 13‚
2CH2Cl2, and 23 were grown from benzene/hexane (complexes 8
and 23) or from dichloromethane/toluene/hexane (complex 13).
Details of the data collection and refinement are given in Table 1.
The crystals were mounted onto the tip of a glass fiber, and the
Inorganic Chemistry, Vol. 42, No. 11, 2003 3661