(Phenylalkyl)palladium complexes containing β-hydrogen atoms: Synthesis and characterization of [PdR2(dppe)], [PdR(SPh)(dppe)] (R = CH2CH2Ph, CH2CH2CH2Ph, CH2CHMePh), and [Pd(CH2CH2CH2Ph)X(dppe)] (X = I, Br, Cl)

Article abstract of DOI:10.1002/1099-0682(200211)2002:11<2868::AID-EJIC2868>3.0.CO;2-S

Reactions of HgR₂ (R = CH₂CH₂Ph, 1a; CH₂CH₂CH₂Ph, 1b; CH₂CHMePh, 1c) (prepared from HgCl₂ and the requisite Grignard compounds) with lithium in toluene afforded (phenylalkyl)lithium compounds LiR (2a-c) in yields of between 64 and 81%. At -30 °C, they react with [PdCl₂(dppe)] [dppe = 1,2-bis(diphenylphosphanyl)ethane] yielding bis(phenylalkyl)palladium(II) complexes [PdR₂(dppe)] (3a-c) which were isolated (T_dec = 159 °C, 3a; 80 °C, 3b; 145 °C, 3c) and fully characterized by ¹H, ¹³C, and ³¹P NMR spectroscopy. Single-crystal X-ray diffraction of [Pd(CH₂CH₂Ph)₂(dppe)] (3a) showed that the palladium atom is square-planar coordinated by two 2-phenylethyl ligands and the dppe ligand. The two CH₂CH₂Ph ligands exhibite nearly a fully staggered conformation. Overall, a good approximation for the complex is that it has C₂ symmetry with the C₂ axis defined by the Pd atom and the midpoint of the central C-C bond of the dppe ligand. Bis(phenylalkyl)palladium complexes 3a and 3b reacted with PhSH in a 1:1 ratio yielding [PdR(SPh)(dppe)] (R = CH₂CH₂Ph, 5a; CH₂CH₂CH₂Ph, 5b), whereas in the case of complex 3c, besides [Pd(CH₂CHMePh)(SPh)(dppe)] (5c), a considerable amount of [Pd(SPh)₂(dppe)] (6a) was formed. Reactions of 3b with the less acidic alkanethiols iPrSH and tBuSH resulted in the formation of [Pd(CH₂CH₂CH₂Ph)(SR′)(dppe)] (R′ = iPr, 5d; tBu, 5e) along with smaller amounts of [Pd(SR′)2(dppe)] (6) and [Pd(dppe)₂] (7). Furthermore, complex 3b was found to react in THF with disulfides R′SSR′ (R· = Ph, Bz, Me), yielding [Pd(CH₂CH₂CH₂Ph)(SR′)(dppe)] (R′ = Ph, 5b; Bz, 5f, Me, 5g) with small amounts (3-13%) of [Pd(SR′)₂(dppe)] (6) as side products. The corresponding reaction with MeSe-SeMe afforded [Pd(CH₂CH₂CH₂Ph)(SeMe)(dppe)] (8a) and 3% of [Pd(SeMe)₂(dppe)] (9a) and [Pd(dppe)₂] (7). Reactions of complex 5b with MeI and H₂C=CHCH₂Br in tetrahydrofuran and with neat H₂C=CHCH₂Cl readily proceeded at -30 °C to give halo(3-phenylpropyl)palladium complexes [Pd(CH₂CH₂CH₂Ph)X(dppe)] (X = I, 10a; Br, 10b; Cl, 10c). They were isolated as pale yellow powdery/microcrystalline substances and fully characterized by ¹³C and ³¹P NMR spectroscopy. Solutions of complexes 10 in THF decompose rapidly above -30 °C. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.

Full text of DOI:10.1002/1099-0682(200211)2002:11<2868::AID-EJIC2868>3.0.CO;2-S

FULL PAPER
(Phenylalkyl)palladium Complexes Containing β-Hydrogen Atoms: Synthesis
and Characterization of [PdR2(dppe)], [PdR(SPh)(dppe)] (R ؍ CH2CH2Ph,
CH2CH2CH2Ph, CH2CHMePh), and [Pd(CH2CH2CH2Ph)X(dppe)]
(X ؍ I, Br, Cl)
Thomas Spaniel,[a] Harry Schmidt,[a] Christoph Wagner,[a] Kurt Merzweiler,[a] and
Dirk Steinborn*[a]
Keywords: Phenylalkyl complexes / Palladium / β-Hydrogen-containing alkyl ligands / P ligands
Reactions of HgR2 (R = CH2CH2Ph, 1a; CH2CH2CH2Ph, 1b;
CH2CHMePh, 1c) (prepared from HgCl2 and the requisite
Grignard compounds) with lithium in toluene afforded
(phenylalkyl)lithium compounds LiR (2a−c) in yields of be-
tween 64 and 81%. At −30 °C, they react with [PdCl2(dppe)]
[dppe = 1,2-bis(diphenylphosphanyl)ethane] yielding bis-
amount of [Pd(SPh)2(dppe)] (6a) was formed. Reactions of 3b
with the less acidic alkanethiols iPrSH and tBuSH resulted
in the formation of [Pd(CH2CH2CH2Ph)(SRЈ)(dppe)] (RЈ = iPr,
5d; tBu, 5e) along with smaller amounts of [Pd(SRЈ)2(dppe)]
(6) and [Pd(dppe)2] (7). Furthermore, complex 3b was found
to react in THF with disulfides RЈSSRЈ (RЈ = Ph, Bz, Me),
yielding [Pd(CH2CH2CH2Ph)(SRЈ)(dppe)] (RЈ = Ph, 5b; Bz, 5f,
Me, 5g) with small amounts (3−13%) of [Pd(SRЈ)2(dppe)] (6)
as side products. The corresponding reaction with MeSe-
SeMe afforded [Pd(CH2CH2CH2Ph)(SeMe)(dppe)] (8a) and
3% of [Pd(SeMe)2(dppe)] (9a) and [Pd(dppe)2] (7). Reactions
of complex 5b with MeI and H2C=CHCH2Br in tetrahydrofu-
(phenylalkyl)palladium(II) complexes [PdR2(dppe)] (3a−c)
which were isolated (Tdec = 159 °C, 3a; 80 °C, 3b; 145 °C, 3c)
and fully characterized by 1H, 13C, and 31P NMR spectros-
copy.
Single-crystal
X-ray
diffraction
of
[Pd(CH2CH2Ph)2(dppe)] (3a) showed that the palladium
atom is square-planar coordinated by two 2-phenylethyl li-
gands and the dppe ligand. The two CH2CH2Ph ligands ex- ran and with neat H2C=CHCH2Cl readily proceeded at −30
hibite nearly a fully staggered conformation. Overall, a good
approximation for the complex is that it has C2 symmetry
with the C2 axis defined by the Pd atom and the midpoint of
the central C−C bond of the dppe ligand. Bis(phenylalkyl)-
palladium complexes 3a and 3b reacted with PhSH in a
1:1 ratio yielding [PdR(SPh)(dppe)] (R = CH2CH2Ph, 5a;
CH2CH2CH2Ph, 5b), whereas in the case of complex 3c, be-
°C to give halo(3-phenylpropyl)palladium complexes
[Pd(CH2CH2CH2Ph)X(dppe)] (X = I, 10a; Br, 10b; Cl, 10c).
They were isolated as pale yellow powdery/microcrystalline
substances and fully characterized by 13C and 31P NMR spec-
troscopy. Solutions of complexes 10 in THF decompose
rapidly above −30 °C.
( Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany,
sides [Pd(CH2CHMePh)(SPh)(dppe)] (5c),
a considerable 2002)
1. Introduction
known.[3] Contrary to type I, those of type II, (2-phenyl-
ethyl)- and (3-phenylpropyl)palladium complexes, have not
yet been described. Due to β-hydrogen atoms in the
phenylalkyl ligands the thermal stability of these complexes
can be expected to be low. Facile β-hydride elimination re-
actions, in Heck-type catalysts, are discussed as a reason for
the alkylation of olefins being restricted to special cases.
Alkyl halides RЈCHϪCH2X react to form intermediates I
[LxPd(CH2ϪCHRЈ)X], which undergo β-hydride elimina-
tion more easily than insertion of the olefin, giving interme-
diate II and opening the reaction channel to the desired
products.
The Heck reaction has been proven to be a powerful
method for the arylation and vinylation of olefins
(Scheme 1).[1] Despite the continuous debate on its
mechanism,[2] oxidative addition of RX (R ϭ aryl, vinyl,
heteroaryl, ...; X ϭ halide, tosylate, triflate, ...) to the Pd
catalyst complex yielding an LxPd(R)X complex (I,
Scheme 1) followed by olefin insertion (II, Scheme 1) are
crucial reaction steps in the classic Heck cycle. The reac-
tions of ethene with phenyl and benzyl halides yielding styr-
ene and allylbenzene, respectively, can be considered as the
most simple prototypic model reactions for Heck reactions.
Complexes of type I in Scheme 1 (R ϭ Ph, Bz) are well
Several mononuclear palladium complexes with β-hydro-
gen-containing acyclic alkyl ligands have been isolated as
solids and characterized. These include: (i) dialkylϪ and
alkyl/arylϪPdII complexes [PdR2L2] [R ϭ Et, nPr, nBu;
L2 ϭ (PRЈ3)2, dppe, bpy, ...; R2 ϭ Et/Ar, nBu/Ar, Ar ϭ
Aryl],[4] (ii) monoalkylϪPdII complexes with an anionic
[a]
Institut für Anorganische Chemie der Martin-Luther-
Universität Halle-Wittenberg,
Kurt-Mothes-Straße 2, 06120 Halle (Saale), Germany
Fax: (internat.) ϩ 49-345/552-7028
E-mail: steinborn@chemie.uni-halle.de
2868  2002 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/02/1111Ϫ2868 $ 20.00ϩ.50/0 Eur. J. Inorg. Chem. 2002, 2868Ϫ2877

(Phenylalkyl)palladium Complexes Containing β-Hydrogen Atoms
FULL PAPER
Here we report on the synthesis and characterization of
(2-phenylethyl)- as well as (2- and 3-phenylpropyl)palla-
dium complexes with bis(diphenylphosphanyl)ethane
(dppe) as a stabilizing co-ligand. Reactions of [PdCl2(dppe)]
with LiR (R
ϭ
CH2CH2Ph, CH2CH2CH2Ph,
CH2CHMePh) afforded the diorgano complexes
[PdR2(dppe)]. Partial protolysis with phenylthiol resulted in
formation of mono(phenylalkyl) complexes [PdR(SPh)-
(dppe)], whose reactions with organo halides, disulfides and
diselenides are described. Furthermore, the molecular struc-
ture of the first palladium complex with two β-hydrogen-
containing alkyl ligands, [Pd(CH2CH2Ph)2(dppe)], is pre-
sented.
2. Results and Discussion
2.1. Synthesis and Characterization of (Phenylalkyl)lithium
and -mercury Compounds
Scheme 1
The synthesis of (2-phenylethyl)lithium was described in
the literature by either a direct synthesis (PhCH2CH2Br ϩ
Li),[15] or a lithium/iodide exchange reaction (PhCH2CH2I
ϩ tBuLi)[16] in diethyl ether. We and others[16b] failed to
obtain LiCH2CH2Ph by direct synthesis. By a lithium/
iodide exchange reaction we succeeded to obtain
LiCH2CH2Ph, although severe impurities due to ether
cleavage prevented its use as starting material for the syn-
thesis of organopalladium complexes. Thus, we prepared
(phenylalkyl)lithium compounds by transmetalation ac-
cording to Scheme 2.
ligand trans-[PdEt(X)(PRЈ3)2] (X ϭ Cl, Br, I, SPh, OPh,
O2CRЈ),[5]
[Pd(CH2CH2CHϭCH2)Cl(dppe)],[6]
and
[PdR(S2CNRЈ2)(PRЈ3)] (R ϭ nPr, iPr, nBu, sBu, ...),[7] and
(iii) cationic PdII complexes [PdR{N(CH2CH2PPh2)3}]X
(R ϭ Et, nPr, nBu; X ϭ I, BPh4)[8] and [PdEt(η2-
C2H4)(phen)][B{C6H3(CF3)2}4];[9] furthermore, (iv) alkyl-
(Et, nPr)ϪPdIV complexes with tripodal N-donor and bi-
pyridine co-ligands have been synthesized.[10] Only a few of
these complexes could be structurally characterized, namely
trans-[PdEt(X)(PMe3)2] (X ϭ Br,[5b] SPh[5c]), [PdR{S2CN-
(CH2)4}(PEt3)] (R
ϭ
nPr, iPr),[7b] and [PdEtMe2-
{(pz)3BH}].[10d]
Palladium complexes with acyclic β-hydrogen-containing
alkyl ligands cover a wide range of stability: PdEtI without
supporting ligands already decompose at Ϫ100 °C[11]
whereas toluene solutions of complexes with dithiocarbam-
ato[7] and tris(pyrazolyl)borate[10d] co-ligands were found to
be stable to 60 °C and to at least 80 °C, respectively. On the
other hand, many of the above-mentioned complexes are
Scheme 2
The bis(phenylalkyl)mercury compounds 1aϪc were ob-
unstable in solution even at room temperature. Preferred tained (Scheme 2) by reaction of the Grignard compounds
decomposition pathways are β-hydrogen elimination and/or with mercury chloride in THF/diethyl ether as colorless li-
reductive elimination in the case of dialkyl complexes. For quids in moderate to good yields (66Ϫ84%). They were
1
stereoelectronic reasons organopalladium complexes with characterized by H and 13C NMR spectroscopy; all chem-
n
β-hydrogen-containing cycloalkyl ligands are thermally ical shifts and couplings (nJHg,H and JHg,C, see Exp. Sect.)
more stable.[4b,4c,4f,6,12]
are in full agreement with expectations. Due to its two
(Phenylalkyl)palladium complexes containing the struc- equivalent substituted stereogenic centers, the 13C NMR
tural unit PdϪ[CH2]nPh with n Ͼ 1 [benzyl complexes (n ϭ spectrum of Hg(CH2CHMePh)2 (1c) shows two sets of sig-
1), for which β-hydrogen elimination is lacking, will not be nals of equal intensity corresponding to rac and meso
1
considered here] have not yet been synthesized. forms. Comparison of the JHg,C coupling constants
Pd(CH2CH2Ph)Cl was proposed as an intermediate in reac- (706 Hz, 1a; 692 Hz, 1b; 720 Hz, 1c) with those of the cor-
tions of PdCl2/HgPhCl with ethene and [PdCl4]2Ϫ with responding non-phenyl-substituted compounds HgEt2
Hg(CH2CH2Ph)Cl followed by cleavage of the PdϪC bond (647 Hz)[17] and Hg(nPr)2 (660 Hz),[17] shows that phenyl
with CuCl2/LiCl.[13] Furthermore, complexes with substitution in the 2- (1a/1c) and 3-position (1b) gives rise
1
CH2ϪCH2Ph and CHPhϪCH2Ph ligands were detected by to an increase of the JHg,C coupling constants by 59/60 Hz
NMR spectroscopy as intermediates in reactions of phenyl- and 32 Hz, respectively. In terms of Bent’s model[18] this
palladium complexes with ethene and styrene, respec- indicates a higher electronegativity of phenylalkyl ligands
tively.[14]
compared with their pure alkyl analogues.
Eur. J. Inorg. Chem. 2002, 2868Ϫ2877
2869

T. Spaniel, H. Schmidt, C. Wagner, K. Merzweiler, D. Steinborn
FULL PAPER
Reactions of bis(phenylalkyl)mercury compounds 1aϪc 159 °C (3a), 80 °C (3b) and 145 °C (3c). Solutions of these
with lithium in toluene resulted in the formation of (phenyl- complexes in toluene are stable at Ϫ30 °C for several days
alkyl)lithium compounds 2aϪc in moderate to good yields although decomposition occurs at room temperature within
(64Ϫ81%) (Scheme 2). The compounds are stable in toluene several hours.
at room temperature for days. Despite the use of highly
The identities of complexes 3 were unambiguously con-
1
toxic organomercury compounds these transmetalation re- firmed by H, 13C and 31P NMR spectroscopy and also by
actions are superior to all other methods[15,16] because they X-ray crystallography for 3a. Selected NMR spectroscopic
essentially proceed without side reactions and can be per- data are shown in Table 1 along with the data of the di-
formed in a solvent (toluene) in which the organolithium methyl complex [PdMe2(dppe)] (4) for comparison. As for
1
reagents 2aϪc are stable.
the mercury compound 1c, H, 13C, and 31P NMR spectra
Instead of toluene as a solvent, n-pentane can be used for of the 2-phenylpropyl complex [Pd(CH2CHMePh)2(dppe)]
the synthesis of (3-phenylpropyl)lithium (2b). This is due to (3c) show two sets of signals in a 1:1 ratio due to the exist-
the excellent solubility of 2b in aliphatic hydrocarbons at ence of rac and meso forms. Furthermore, in the 13C NMR
room temperature. Without obvious reason the homolog- spectrum of 3c a further signal splitting for the phenyl car-
ous compounds 2a and 2c are insoluble in aliphatic hydro- bon atoms of the dppe ligand (e.g. four different Co signals
carbons and the transmetalation in these solvents failed. with coupling to the phosphorus atom, see Exp. Sect.) was
The 13C NMR spectrum of 2b in perdeuterated n-hexane observed indicating a pairwise inequivalence of the phenyl
gave evidence for its identity. The signal of the carbon atom groups of the dppe ligand. This was expected as the two
attached to the lithium atom is broadened (b1/2 ഠ 75 Hz) asymmetric carbon atoms reduce the symmetry (C2v in
due to dynamic processes and/or the quadrupole moment terms of the NMR time scale) of simple [PdR2(dppe)] com-
of Li (7Li: I ϭ 3/2, 92.6% rel. abund.). Its chemical shift plexes to C2 in the rac form and Cs in the meso form.
(δ ϭ 10.1 ppm) is in the expected range as compared with
Coupling with the magnetically inequivalent P atoms re-
other alkyllithium compounds [δ(13Cα), median: 12.5 ppm; sulted in higher order multiplets of AAЈX or Ϫ taking into
lower/upper quartile: 10.2/17.0 ppm; 17 observations[19]]. account the isotopic shift of 13C Ϫ ABX spin systems (A,
The lithium-induced shift in 2b [δ(13Cα) in LiR Ϫ δ(13Cα) B ϭ 31P; X ϭ 13C) for the 13C resonances. For the dimethyl
in HR] amounts to δ ϭ 10.1Ϫ14.6 ppm[20] ϭ Ϫ4.5 ppm, compound [PdMe2(dppe)] (4) a complete set of J(31P,13C)
n
and is somewhat larger than expected for the correlation coupling constants was obtained by spectral analysis using
1
given in ref.[19] The JC,H coupling constant (ca. 94 Hz) is the program package PERCH[22] (cf. Table 1 and Exp.
in the range expected for alkyllithium compounds (1JC,H in Sect.). For the methyl carbon atoms (signal pattern ‘dd’,
LiCH3: 98 Hz[21]).
pseudo-doublet of doublet with roof effect) and the methyl-
ene carbon atoms (signal pattern ‘t’, pseudo-triplet) the re-
sults obtained by computer analysis are very similar to the
results obtained when the signals are handled as first-order
2.2. Synthesis and Characterization of
Bis(phenylalkyl)palladium Complexes
multiplets: CH3: 2J(P,Ctrans) ϭ 107.3 Hz vs. 107.5 Hz,
The (phenylalkyl)lithium compounds 2aϪc reacted
with [PdCl2(dppe)] in toluene at Ϫ30 °C to give
bis(phenylalkyl){bis(diphenylphosphanyl)ethane}palladium
complexes 3aϪc (Scheme 3). Addition of n-pentane resulted
in the precipitation of complexes 3aϪc. Note that the cho-
ice of solvent determins the success of the synthesis: Despite
its low vapor pressure at Ϫ30 °C, resulting in a long-lasting
procedure to remove it in vacuo at that temperature, toluene
is the most preferable one. The (phenylalkyl)lithium com-
pounds 2 are freely soluble in toluene even at Ϫ78 °C and
they are indefinitely stable in toluene, which is not the case
for ethereal solvents.
1ϩ4
2J(P,Ccis) ϭ 10.1 Hz vs. 9.7 Hz; CH2:
J
/
2ϩ3JP,C ϭ 19.7/
P,C
21.9 Hz (with opposite sign, assignment tentative) vs.
21.5 Hz. Thus, it seems to be justified to obtain approxim-
ate coupling constants by a ‘‘first-order treatment’’ as was
done for complexes 3 (cf. Table 1).
The α-carbon signals in (phenylalkyl)palladium com-
plexes 3aϪc are strongly lowfield-shifted compared with
that in [PdMe2(dppe)] (4) (δ ϭ 24.9Ϫ33.6 ppm vs. 1.9 ppm).
In the couplings of α-carbon atoms to phosphorus atoms
(2JP,C) only smaller differences between 3aϪc (trans coup-
ling 100Ϫ101 Hz; cis coupling 9 Hz) and the dimethyl com-
plex 4 (trans coupling 107.3 Hz; cis coupling 10.1 Hz) were
found. The phosphorus chemical shifts are in the order 2-
phenyl-substituted alkyl (3a/c: δ ϭ 38.6Ϫ40.3 ppm) Ͻ 3-
phenyl-substituted alkyl (3b: δ ϭ 43.6 ppm) Ͻ Me (4: δ ϭ
45.6 ppm).
Single crystals of the 2-phenylethyl complex 3a, which
were suitable for X-ray diffraction analysis were grown from
THF/pentane. The molecular structure of complex 3a is
shown in Figure 1, and selected bond lengths and angles
Scheme 3
Complexes 3aϪc were isolated in yields between 68 and are compiled in Table 2. Complex 3a crystallizes as separate
84% as colorless (3a/b) and yellowish (3c) microcrystalline molecules without unusual intermolecular interactions; the
substances that are moderately air-sensitive. Heating by a shortest ones between non-hydrogen atoms are C···C dis-
˚
rate of about 4 K/min resulted in decomposition at about tances of more than 3.5 A. The palladium atom, to a good
2870
Eur. J. Inorg. Chem. 2002, 2868Ϫ2877

(Phenylalkyl)palladium Complexes Containing β-Hydrogen Atoms
FULL PAPER
Table 1. Selected NMR spectroscopic data (δ in ppm, J in Hz) for complexes [PdR2(dppe)] (3); data of [PdMe2(dppe)] (4) are given
for comparison
R
Me (4)[a]
CH2CH2Ph (3a)
CH2CH2CH2Ph (3b)
CH2CHMePh (3c)
C1, δ(13C)
2JP,C trans
2JP,C cis
1.9
107.3
10.1
28.6
101
9
24.9
101
9
35.9
44.0
11
1.44 (m)
43.6
33.5/33.6
100/101
9/9
42.4/42.5
25.9/26.6
C2, δ(13C)
C3, δ(13C)
4JP,C trans
PdCH2, δ(1H)
δ(31P)
39.7
0.41 (m)
45.6
1.62 (m)
40.3
1.22Ϫ2.49 (m)[b]
38.6/39.7
[a]
Coupling constants of complex 4 were calculated by spectral analysis. Couplings given for complexes 3 are only approximate values
[b]
because they were derived from line distances, see text. Superimposed by other signals.
As shown by the torsion angles PdϪC1ϪC2ϪC3
[178.0(4)°] and PdϪC9ϪC10ϪC11 [165.0(4)°] the two 2-
phenylethyl ligands exhibit a nearly fully staggered con-
formation. The PdϪC1ϪC2/PdϪC9ϪC10 [112.6(4)/
111.2(3)°] and C1ϪC2ϪC3/C9ϪC10ϪC11 [112.6(5)/
114.8(4)°] angles are nearly tetrahedral. The phenyl groups
of the 2-phenylethyl ligands are nearly parallel to the com-
plex plane [Ph3/PdP2C2 10.8(2)°; Ph11/PdP2C2 14.2(3)°]
and nearly perpendicular to the face-positioned phenyl
groups of the dppe ligand [Ph3/Ph19 80.7(3)°; Ph11/Ph37
89.8(3)°]. Thus, the complex, to a good approximation, is
C2-symmetric with the C2 axis defined by the Pd atom and
the midpoint of the central C17ϪC18 bond of the dppe li-
gand.
Figure 1. Molecular structure in the solid state with atomic label-
ling scheme for [Pd(CH2CH2Ph)2(dppe)] (3a); hydrogen atoms are
omitted for clarity; thermal ellipsoids are drawn with 50% probabil-
ity
2.3. Synthesis and Characterization of
(Phenylalkyl)(thiolato)palladium Complexes
˚
Table 2. Selected bond lengths [A], bond angles [°] and dihedral
Yamamoto[5b,25] showed that trans-[PdEt2(PMe3)2] and
[PdMe2(dppe)] react selectively with equimolar amounts
of PhSH with protolytic cleavage of one of the two
PdϪC bonds yielding trans-[PdEt(SPh)(PMe3)2] and
[PdMe(SPh)(dppe)], respectively. The analogous reaction of
bis(phenylalkyl)palladium complexes 3aϪc proceeded ac-
cording to Scheme 4. In the case of the 2-phenylethyl (3a)
and 3-phenylpropyl (3b) complexes the protolytic cleavage
of the first PdϪC bond proceeded faster than that of the
second one. Thus, at Ϫ30 °C using a 1:1 ratio of 3a/3b and
PhSH the desired (phenylalkyl)(thiolato) complexes 5a and
5b were obtained. On the other hand, under the same reac-
tion conditions the 2-phenylpropyl complex 3c reacted with
PhSH (1:1) to yield both the mixed complex 5c (15%) and
[Pd(SPh)2(dppe)] (6a) to a remarkable extent (16%) as
shown by 31P NMR spectroscopy. Successive additions of
further quantities of PhSH (calculated 1:1 in relation to the
amount of unchanged starting complex 3c detected in the
angles [°] of complex 3a
PdϪC1
PdϪC9
PdϪP1
PdϪP2
2.096(5) C1ϪC2
2.107(6) C2ϪC3
2.288(3) C9ϪC10
2.291(1) C10ϪC11
1.526(6)
1.515(7)
1.524(8)
1.511(8)
C1ϪPdϪC9
P1ϪPdϪP2
C1ϪPdϪP1
C9ϪPdϪP2
C1ϪPdϪP2
85.8(2)
85.53(8)
93.1(2)
95.5(2)
177.8(2)
C9ϪPdϪP1
PdϪC1ϪC2
PdϪC9ϪC10
C1ϪC2ϪC3
C9ϪC10ϪC11
178.7(1)
112.6(4)
111.2(3)
112.6(5)
114.8(4)
PdϪC1ϪC2ϪC3 178.0(4)
PdϪC9ϪC10ϪC11 165.0(3)
approximation, is square-planar coordinated by two carbon
atoms and two phosphorus atoms [greatest deviation of the
least-squares plane: Pd 0.018(1) A]. The five-membered
˚
PdP2C2 ring is twisted about C17ϪC18. The phenyl rings of
the dppe ligand are arranged in a typical ‘‘face-to-edge’’[23]
position (face: Ph37/Ph19; edge: Ph31, Ph25; phenyl groups
are designated by Phx, where x is the number of the ipso-
carbon atom). The bite of the dppe ligand [P1ϪPdϪP2
85.53(8)°] is as expected (median: 85.0°; lower/higher quart-
ile: 84.3/85.6°; number of values: 52[24]). The opposite
C1ϪPdϪC9 angle [85.8(2)°] is also markedly smaller than
90°.
[a]
Scheme 4. [Pd(SPh)2(dppe)] (6a) was also formed
Eur. J. Inorg. Chem. 2002, 2868Ϫ2877
2871

T. Spaniel, H. Schmidt, C. Wagner, K. Merzweiler, D. Steinborn
FULL PAPER
31P NMR spectrum) until 3c had been completely con- whereas for reactions of BzSSBz and MeSSMe, the temper-
sumed resulted in a mixture of 5c and 6a of about 3:1. ature had to be increased to 0 °C and 15 °C, respectively.
The less acidic alkanethiols iPrSH and tBuSH reacted Side products were the bis(thiolato) complexes
slower with the 3-phenylpropyl complex 3b than with PhSH [Pd(SRЈ)2(dppe)] (6) in all cases.
(Scheme 5): At Ϫ30 °C the reaction was incomplete even
after six days of reaction time. Increasing the temperature
to Ϫ15 °C for one day and to 0 °C for eight days, resulted
in the formation of [Pd(CH2CH2CH2Ph)(SRЈ)(dppe)] in
77% (RЈ ϭ iPr, 5d) and 82% yield (RЈ ϭ tBu, 5e). Side
products were the bis(thiolato) complexes 6b (RЈ ϭ iPr;
13%) and 6c (RЈ ϭ tBu; 8%), and [Pd(dppe)2] (7; 2% for
RЈ ϭ iPr; 7% for RЈ ϭ tBu) as the reduction product. Com-
paring iPrSH and tBuSH, the protolytic cleavage of the se-
cond PdϪC bond yielding 6c is less favoured, although the
[a]
Scheme 6. R ϭ CH2CH2CH2Ph;
composition of reaction mix-
[b]
reduction yielding 7 is more favoured with tBuSH, which
might be explained because of its lower acidity and its
greater bulkiness.
ture in %; small amounts of [Pd(dppe)2] (7) were formed
In analogous reactions diorgano diselenides exhibited a
higher reactivity than diorgano disulfides. Thus, at Ϫ30 °C,
in tetrahydrofuran, reactions of MeSeSeMe with
[Pd(CH2CH2CH2Ph)2(dppe)] (3b) afforded the formation of
[Pd(CH2CH2CH2Ph)(SeMe)(dppe)] (8a) (73%) and [Pd(Se-
Me)2(dppe)] (9a) (3%), within one day. Formation of 3%
[Pd(dppe)2] (7) after a further day of reaction indicated a
relatively low stability of 8a. [PdMe2(dppe)] (4) reacted with
PhSeSePh at Ϫ30 °C completely, yielding 91% [PdMe-
(SePh)(dppe)] (8b) and 9% [Pd(SePh)2(dppe)] (9b), within
one day. No indication for the formation of organo-
palladium() complexes as intermediates was found in any
of the reactions. Analogous reactions between [PdMe2L2]
(L2 ϭ bpy, phen) and PhEEPh (E ϭ S, Se) afforded com-
plexes [PdMe2(EPh)2L2] that are unstable for E ϭ S and
moderately stable for E ϭ Se.[26] This is further support
for the far greater versatility of nitrogen-donor ligands in
stabilizing palladium() than that of phosphane ligands.[27]
Scheme 5. R ϭ CH2CH2CH2Ph; [a] temperature regime, see text; [b]
composition of reaction mixture in % for RЈ ϭ iPr/tBu
The (phenylalkyl)(thiolato) complexes 5a and 5b were
isolated as colorless (5a) and pale pink (5b) slightly air-sens-
itive, microcrystalline substances. The solids decomposed at
145 °C (5a) and 90 °C (5b). Solutions in tetrahydrofuran
were stable at Ϫ30 °C; at room temperature they decom-
posed slowly. The identities of (phenylalkyl)(thiolato) com-
1
plexes 5a and 5b were confirmed by H, 13C and 31P NMR
spectroscopy. The bis(thiolato) complexes 6 were character-
ized by 31P NMR spectroscopy and by comparison with
authentic samples prepared by reaction of [PdCl2(dppe)]
with LiSRЈ. Substitution of a phenylalkyl ligand by PhS
(3a/b Ǟ 5a/b) gives rise to a slight (δ ϭ 1.5/4.1 ppm) low-
field shift of the C1 signal of the remaining phenylalkyl
ligand. In complexes 5a/b the signals of the P atoms
trans to the carbon atoms are shifted to higher field [5a/b:
δ(31Ptrans to C) ϭ 34.5/34.0 ppm] relative to those in the ana-
logous bis(phenylalkyl) complexes [3a/b: δ(31P) ϭ 40.3/
43.6 ppm] and those trans to sulfur atoms are lowfield-
shifted [5a/b: δ(31Ptrans to S) ϭ 53.2/53.1 ppm]. Very similar
to the latter one is the phosphorus shift in the bis(thiolato)
complex [Pd(SPh)2(dppe)] (6a) (δ ϭ 55.4 ppm).
2.4. Synthesis and Characterization of Halo(3-
phenylpropyl)palladium Complexes
The (3-phenylpropyl)(phenylthiolato) complex 5b reacted
with organo halides RX with substitution of the phenylthi-
olato ligand by the halide yielding halo(3-phenylpropyl)pal-
ladium complexes 10aϪc (Scheme 7). Due to the low ther-
mal stability of the products, reactions were performed at
Ϫ30 °C in tetrahydrofuran as solvent or in neat RX. The
reactivity of RX followed the expected order of X (I Ͼ Br
Ͼ Cl) and R (allyl Ͼ alkyl). To obtain a complete degree
Apart from protolytic cleavage of the PdϪC bonds with
alkanethiols (vide supra), reactions of bis(phenylalkyl)pal-
ladium complexes 3 with diorgano disulfides are another
access to (phenylalkyl)(thiolato)palladium complexes 5.
Thus, reactions of RЈSSRЈ (RЈ ϭ Ph, Bz, Me) with the (3-
phenylpropyl)palladium complex 3b were performed
(Scheme 6). PhSSPh exhibited the highest reactivity. It re-
acted already at Ϫ30 °C (to a small extent even at Ϫ50 °C) Scheme 7
2872
Eur. J. Inorg. Chem. 2002, 2868Ϫ2877

(Phenylalkyl)palladium Complexes Containing β-Hydrogen Atoms
FULL PAPER
were recorded with Gemini 200, VXR 400 and Unity 500 NMR
spectrometers (Varian). For 1H and 13C NMR spectra the protio
impurities of the deuterated solvent or the solvent signals were used
as internal references. For 31P NMR spectra H3PO4 (85%) was used
as the external reference. In higher order multiplets N gives the
distance between the two most intense lines. In pseudo-triplets (‘t’)
and pseudo-doublets of doublets (‘dd’) N was derived like coup-
lings in first-order triplets and doublets of doublets, respectively. A
CP9000 chromatograph (Chrompack) was used for chromato-
graphic analyses. GC/MS investigations were carried out with an
of conversion, a threefold excess of methyl iodide was neces-
sary; ethyl bromide did not react at all. Allyl bromide re-
acted quantitatively when a 50-fold excess was used. In neat
allyl chloride complex 10c was obtained with a 94% degree
of conversion whereas allyl fluoride did not react at all.
trans-[PdEt(SPh)(PMe3)2] proved to be more reactive than
complex 5b and reacted with MeI, PhCH2Br and H2Cϭ
CHCH2Cl in a 1:1 ratio yielding trans-[PdEt(X)(PMe3)2]
(X ϭ I, Br, Cl) in Ͼ 80% yields.[5b]
The iodo (10a), bromo (10b) and chloro (10c) complexes HP 5890 Series II/HP 5972 (HewlettϪPackard). [PdCl2(dppe)] and
[Pd(dppe)2] were prepared according to literature methods.[28,29]
Reactions of LiSR (R ϭ Ph, iPr, tBu, Bz, Me) [obtained from
were isolated as yellow (10a) and pale yellow (10b, c) pow-
dery/microcrystalline substances that are moderately air-
sensitive. Heating by about 4 K/min results in a decomposi-
RSSR and (nBuLi)] with [PdCl2(dppe)] afforded complexes
[Pd(SR)2(dppe)] (6aϪe) in yields between 40 and 85%. 31P NMR
tion at about 80 °C (10b) and 140 °C (10c). Solids can be
(81 MHz, [D8]THF): δ ϭ 55.4 (in CDCl3; R ϭ Ph, 6a), 56.7 (R ϭ
handled at room temperature without noticeable decom-
iPr, 6b), 54.3 (R ϭ tBu, 6c), 58.2 (R ϭ Bz, 6d), 57.6 (R ϭ Me, 6e)
position for a short period of time. Solutions in tetrahy-
ppm. Other chemicals were commercially available.
drofuran decompose rapidly above Ϫ30 °C, turning intens-
ively violet.
2. HgR2 (R ؍ CH2CH2Ph, 1a; CH2CH2CH2Ph, 1b; CH2CHMePh,
1c): Solutions of Grignard compounds RMgBr in diethyl ether
(0.7Ϫ0.9 ) were prepared following a standard procedure[30] from
Mg and RBr. Yields (93Ϫ97%) were determined by acidimetric ti-
tration. Only solutions of Grignard compounds free from un-
changed RBr (checked by GC/MS) were used. These solutions of
RMgBr (40.5 mmol) were added dropwise to a solution of HgCl2
(5.0 g, 18.4 mmol) in THF (20 mL) at Ϫ78 °C. The reaction mix-
ture was slowly warmed to room temperature and stirred for 2 days.
At Ϫ78 °C, water (20 mL) was added dropwise. The organic phase
The identities of complexes 10 were confirmed by 13C
and 31P NMR spectroscopy. Selected values are shown in
Table 3. Substitution of the 3-phenylpropyl ligand by brom-
ide and chloride (3b Ǟ 10b/c) gives rise to a lowfield shift
of C1 by 4.1 and 6.1 ppm, respectively, whereas substitution
by iodide (3b Ǟ 10a) leaves the C1 chemical shift practically
unchanged. Analogous to mono(phenylalkyl)(thiolato)
complexes 5, P atoms trans to the carbon atom resonate
at higher fields than those trans to the halide ligand (δ ϭ was separated, washed with water and dried with Na2SO4. The
solvent was removed in vacuo. Finally, the temperature was raised
to 50 °C (0.1 Torr) to remove all volatile substances. Warning! All
manipulations with the highly toxic organomercurials were done in
a separate fume hood using appropriate safety requirements, above
all, a special combination of gloves.[31] All glassware used in these
syntheses was treated with a solution of bromine in methanol to
convert highly toxic organomercurials into less toxic HgBr2.
27.7Ϫ30.2 vs. 56.1Ϫ59.5 ppm).
Table 3. Selected NMR spectroscopic data (δ in ppm, J in Hz) for
complexes [Pd(CH2CH2CH2Ph)X(dppe)] (10)
X
I (10a)
Br (10b)
Cl (10c)
C1, δ(13C)
2JP,C trans
C2, δ(13C)
3JP,C trans
C3, δ(13C)
4JP,C trans
4JP,C cis
24.3
100.6
35.8
29.0
100.4
34.6
31.0
101.2
34.0
4.5
42.2
15.3
3.2
27.7
59.4
29.5
Compound 1a (R ؍ CH2CH2Ph): Colorless oil. Yield: 5.3 g (70%).
1H NMR (200 MHz, CDCl3): δ ϭ 1.29 (‘t’ ϩ dt, N ϭ 7.7, 2JHg,H ϭ
96.7 Hz, 4 H, HgCH2), 3.05 (‘t’ ϩ dt, N ϭ 7.7, 3JHg,H ϭ 112.3 Hz,
4 H, HgCH2CH2), 7.12Ϫ7.33 (m, 10 H, Ph) ppm. 13C NMR
(100 MHz, CDCl3): δ ϭ 34.8 (s, HgCH2CH2), 45.0 (s ϩ d, 1JHg,C ϭ
706.5 Hz, HgCH2), 125.4 (s, m-C),[32] 127.9 (s, p-C), 128.4 (s, o-C),
147.3 (s, i-C).
42.9
13.9
42.4
15.3
P trans to C, δ(31P)
30.2
56.1
29.3
28.9
59.5
29.5
P trans to X, δ(31P)
2ϩ3
J
P,P
Compound 1b (R ؍ CH2CH2CH2Ph): Colorless oil. Yield: 5.3 g
1
(66%). H NMR (400 MHz, CDCl3): δ ϭ 0.77 (‘t’ ϩ dt, N ϭ 7.2,
2JHg,H ϭ 100.0 Hz, 4 H, HgCH2), 2.13 (‘quint’ ϩ dt, N ϭ 7.2,
In the present investigation (2- and 3-phenylalkyl)palla-
dium complexes have been prepared and fully characterized 3JHg,H ϭ 112.3 Hz, 4 H, HgCH2CH2), 2.58 (‘t’, N ϭ 7.2 Hz, 4 H,
HgCH2CH2CH2), 7.13Ϫ7.19 (m, 6 H, Ph), 7.27Ϫ7.30 (m, 4 H, Ph)
for the first time. All of them contain β-hydrogen atoms
and proved to be Ϫ at least in solution Ϫ of low thermal
stability. This is especially pronounced in the cis-halo(3-
phenylpropyl)palladium complexes [Pd(CH2CH2CH2Ph)X-
(dppe)] (10aϪc; X ϭ I, Br, Cl) that are Ϫ most likely Ϫ
intermediates in the catalytic Heck cycle.[1b]
2
ppm. 13C NMR (100 MHz, CDCl3): δ ϭ 30.5 (s ϩ d, JHg,C
ϭ
3
33.2 Hz, HgCH2CH2), 40.2 (s
HgCH2CH2CH2), 41.7 (s ϩ d, JHg,C ϭ 692.0 Hz, HgCH2), 125.7
(s, p-C), 128.3/128.6 (s/s, o-, m-C), 142.9 (s, i-C) ppm.
ϩ
d, JHg,C
ϭ
83.8 Hz,
1
Compound 1c (R ؍ CH2CHMePh, 1:1 Mixture of Two Diastereo-
mers): Colorless oil. Yield: 6.8 g (84%). 1H NMR (400 MHz,
3
CDCl3): δ ϭ 1.22 (d, JH,H ϭ 7.0 Hz, 2 ϫ 6 H, CH3), 1.28 (cent-
ered, m, 2 ϫ 4 H, HgCH2), 3.41Ϫ3.52 (m, 2 ϫ 2 H, HgCH2CH),
7.11Ϫ7.18, 7.22Ϫ7.28 (m, 2 ϫ 10 H, Ph) ppm. 13C NMR
(100 MHz, CDCl3): δ ϭ 26.50/26.51 (s/s, CH3), 39.46/39.49 (s/s,
HgCH2CH), 54.46/54.49 (s ϩ d/s ϩ d, JHg,C ϭ 720.2/720.2,
HgCH2), 2 ϫ 125.6 (s, p-C), 2 ϫ 126.3/128.3/128.4 (s/s/s, o-, m-C),
Experimental Section
1. General Comments: All reactions were performed under argon
using standard Schlenk techniques. Solvents were dried prior to
use: Et2O, THF, and toluene with Na/benzophenone, n-hexane, n-
1
pentane and [D8]THF with LiAlH4. 1H, 13C, and 31P NMR spectra 151.66/151.68 (s/s, i-C) ppm.
Eur. J. Inorg. Chem. 2002, 2868Ϫ2877
2873

T. Spaniel, H. Schmidt, C. Wagner, K. Merzweiler, D. Steinborn
FULL PAPER
3. Synthesis of LiR (R ؍ CH2CH2Ph, 2a; CH2CH2CH2Ph, 2b;
microcrystalline precipitate that was filtered off, washed with n-
CH2CHMePh, 2c): A solution of HgR2 (1) (ca. 7 mmol) in toluene pentane (2 ϫ 5 mL) and dried in vacuo at Ϫ30 °C. Yield: 3.56 g
(ca. 15 mL) was stirred for 2 days with freshly cut lithium chips
(ca. 75 mmol) at room temperature. The lithium amalgam formed
was allowed to settle and the supernatant was filtered [yield (acidi-
(84%). 1H NMR (400 MHz, [D8]THF): δ ϭ 1.44 (m, 4 H, PdCH2),
1.67 (m, 4 H, PdCH2CH2), 2.20 (m, N ϭ 17.8 Hz, 4 H, PCH2),
2.31 (‘t’, N ϭ 7.8 Hz, 4 H, PdCH2CH2CH2), 6.87Ϫ7.60 (m, 30 H,
metric): 64%, 2a; 81%, 2b; 80%, 2c]. For isolation of compound 2b, Ph) ppm. 13C NMR (125 MHz, [D8]THF, Ϫ30 °C): δ ϭ 24.9 (‘dd’,
the reaction was performed in n-pentane. Removal of solvent in
vacuo resulted in an orange oil that was dissolved in [D14]n-hexane
for NMR spectroscopic investigations.
N ϭ 100.7/9.1 Hz, PdCH2), 28.2 (‘t’, N ϭ 20.9 Hz, PCH2), 35.9 (s,
PdCH2CH2), 44.0 (m, N ϭ 10.9 Hz, PdCH2CH2CH2), 125.3 (s, p-
CPh), 128.3/129.1 (s/s, o-CPh, m-CPh), 129.3 (m, N ϭ 9.9 Hz, m-
Cdppe), 130.6 (s, p-Cdppe), 134.1 (m, N ϭ 12.9 Hz, o-Cdppe), 134.9
(m, N ϭ 26.9 Hz, i-Cdppe), 145.1 (s, i-CPh) ppm. 31P NMR
(81 MHz, [D8]THF): δ ϭ 43.6 (s) ppm.
Compound 2b (R ؍ CH2CH2CH2Ph): 13C NMR (100 MHz, [D14]n-
1
1
hexane): δ ϭ 10.1 (br., t, JC,H ഠ 94 Hz, LiCH2), 31.0 (t, JC,H
ϭ
121.8 Hz, LiCH2CH2), 44.2 (t, 1JC,H ϭ 126.6 Hz, LiCH2CH2CH2),
1
2
1
125.7 (dt, JC,H ϭ 159.9, JC,H ϭ 7.4 Hz, p-C), 128.3 (dd, JC,H
ϭ
ϭ
6. [PdMe2(dppe)] (4): In a modified synthesis to that described in
ref.[33], a solution of MeLi (6.25 mmol) in diethyl ether (24 mL)
was added to [PdCl2(dppe)] (2.00 g, 3.47 mmol) at Ϫ78 °C. The
reaction mixture was slowly warmed to Ϫ30 °C, stirred overnight
and filtered. At Ϫ30 °C the solvent was distilled off in vacuo and
toluene (20 mL) was added to the residue. The precipitated LiCl
was filtered off and the solution was concentrated to about 5 mL
in vacuo at Ϫ30 °C. At Ϫ78 °C the addition of n-pentane (ca. 30
mL) resulted in the formation of 4 as a colourless precipitate that
was filtered off, washed with n-pentane (2 ϫ 10 mL) and dried in
vacuo at Ϫ30 °C. Yield: 0.95 g (51%). 1H NMR (400 MHz,
CDCl3): δ ϭ 0.41 (m, N ϭ 0.8 Hz, NЈ ϭ 14.1 Hz, 6 H, PdCH3; NЈ:
distance of the two outer lines lower in intensity), 2.22 (m, N ϭ
18.2 Hz, 4 H, PCH2), 7.32Ϫ7.42 (m, 12 H, Ph), 7.57Ϫ7.83 (m, 8 H,
Ph) ppm. 13C NMR (100 MHz, [D8]THF), for analysis PERCH[22]
program package was used: δ ϭ 1.95 (m, trans-2JP,C ϭ 107.3 Hz,
2
1
2
158.9, JC,H ϭ 7.6 Hz, o-C), 128.7 (dt, JC,H ϭ 156.3, JC,H
5.9 Hz, m-C), 142.6 (s, i-C). Couplings refer to H-coupled spec-
trum.
4. [PdR2(dppe)] (R ؍ CH2CH2Ph, 3a; CH2CHMePh, 3c): At Ϫ78
°C, 1.9 equiv. of LiCH2CH2Ph (2a) or LiCH2CHMePh (2c) in tolu-
ene (20Ϫ25 mL) was added to [PdCl2(dppe)] (ca. 3 mmol). The
reaction mixture was slowly warmed to Ϫ30 °C and stirred over-
night. The filtered solution was concentrated to about 5 mL in
vacuo at Ϫ30 °C. Cooling to Ϫ78 °C and addition of n-pentane
(ca. 25 mL) resulted in precipitation of 3a or 3c, respectively, that
were filtered off, washed with n-pentane (2 ϫ 5 mL) and dried in
vacuo at Ϫ30 °C.
Complex 3a (R ؍ CH2CH2Ph): Colorless microcrystalline powder.
Yield: 68%. 1H NMR (400 MHz, [D8]THF): δ ϭ 1.62 (m, 4 H,
PdCH2), 2.25 (m, N ϭ 17.8 Hz, 4 H, PCH2), 2.65 (m, 4 H,
PdCH2CH2), 6.87 (m, 6 H, Ph), 7.01 (m, 4 H, Ph), 7.43 (m, 12 H,
Ph), 7.65 (m, 8 H, Ph) ppm. 13C NMR (125 MHz, Ϫ30 °C,
[D8]THF): 27.9 (‘t’, N ϭ 21.2 Hz, PCH2), 28.6 (‘dd’, N ϭ 101.4/
9.3 Hz, PdCH2), 39.7 (s, PdCH2CH2), 124.7 (s, p-CPh), 128.4/128.6
(s/s, o-CPh/m-CPh), 129.5 (m, N ϭ 8.7 Hz, m-Cdppe), 130.9 (s, p-
Cdppe), 134.3 (m, N ϭ 12.6 Hz, o-Cdppe), 134.4 (m, superposed, N ϭ
29.4 Hz, i-Cdppe), 150.3 (m, N ϭ 10.7 Hz, i-CPh) ppm. 31P NMR
(202 MHz, Ϫ30 °C, [D8]THF): δ ϭ 40.3 (s) ppm.
1ϩ4
2ϩ3
cis-2JP,C ϭ 10.1 Hz, PdCH3), 28.5 (m,
J
P,C
/
J
P,C
ϭ 19.7/
21.9 Hz, PCH2; with opposite signs, assignment tentative), 129.5
3
5
(m, JP,C ϭ 8.6, JP,C ϭ 0.5 Hz, m-C), 130.9 (s, p-C), 134.2 (m,
2JP,C ϭ 13.6, JP,C ϭ Ϫ1.1 Hz, o-C), 135.0 (m, JP,C ϭ 28.8 Hz,
4
1
3ϩ4
J
ϭ 1.9 Hz, i-C) ppm. 31P NMR (81 MHz, [D8]THF): δ ϭ
P,C
45.6 (s) ppm.
7. [Pd(CH2CH2Ph)(SPh)(dppe)] (5a): At Ϫ78 °C, PhSH (77 mg,
0.70 mmol) in THF (15 mL) was added to
a solution of
[Pd(CH2CH2Ph)2(dppe)] (3a) (500 mg, 0.70 mmol) in THF (15
mL). After warming to Ϫ30 °C, the reaction mixture was stirred
overnight. At Ϫ30 °C, the precipitate formed was filtered off,
washed with pentane (2 ϫ 10 mL) and dried in vacuo. Yield:
251 mg (50%). 1H NMR (200 MHz, CDCl3): δ ϭ 1.53 (m, 2 H,
PdCH2), 2.00Ϫ2.48 (m, 4 H, PCH2), 2.22 (m, 2 H, PdCH2CH2),
6.0Ϫ6.2, 6.8Ϫ7.0, 7.2Ϫ7.8 (m, 30 H, Ph) ppm. 13C NMR
Complex 3c (R ؍ CH2CHMePh; 1:1 Mixture of Two Diastereo-
mers): Yellow microcrystalline powder. Yield: 69%. 1H NMR
(200 MHz, CDCl3): δ ϭ 0.92/0.99 (m/m, N/N ϭ 6.8/6.8 Hz, 6/6 H,
CHCH3), 1.22Ϫ2.49 (m, 2 ϫ 8 H, PCH2 ϩ PdCH2), 3.05 (m, 2 ϫ
2 H, CHMe), 6.9Ϫ7.2, 7.3Ϫ7.7 (m, 2 ϫ 30 H, Ph) ppm. 13C NMR
(125 MHz, CDCl3): δ ϭ 25.9/26.6 (s/s, CHCH3), 26.9/26.9 (‘t’, N ϭ
20.9 Hz, PCH2), 33.5/33.6 (‘dd’/‘dd’, N ϭ 99.7/9.0 Hz/100.8/8.9 Hz,
PdCH2), 42.4/42.5 (s/s, PdCH2CH), 124.1/124.2 (s/s, p-C), 126.5/
126.6/127.6/127.7 (s/s/s/s, o-C, m-C), 128.4/128.5/128.6/128.7 (m/m/
m/m, N ϭ 9.0/9.0/9.0/9.0 Hz, m-Cdppe), 129.5/2 ϫ 129.9/130.4 (s/s/
s, p-Cdppe), 132.5/133.3/133.5/134.3 (m/m/m/m, N ϭ 10.9/11.9/13.9/
13.9 Hz, o-Cdppe), 132.7/133.9 (m, N ϭ 29.0/30.0 Hz, i-Cdppe, 2 ϫ
i-Cdppe not found due to superposition), 154.0/154.2 (m/m, N ϭ
8.0/9.0 Hz, i-C) ppm. 31P NMR (81 MHz, CDCl3): δ ϭ 38.6/39.7
(s/s) ppm.
1ϩ4
2ϩ3
(100 MHz, CDCl3): δ ϭ 26.1 (dd,
J
P,C
ϭ 24.7 Hz,
J
ϭ
P,C
1ϩ4
2ϩ3
14.7 Hz, PCH2), 29.4 (dd,
J
P,C
ϭ 28.2 Hz,
J
P,C
ϭ 22.0 Hz,
2
3
PCH2), 30.1 (d, JPtrans,C ϭ 91.6 Hz, PdCH2), 37.0 (d, JPtrans,C
ϭ
4.2 Hz, PdCH2CH2), 122.9 (s, p-CSPh), 124.2 (s, p-CPh), 127.3/127.4/
3
128.0 (s/s/s, o-CPh, m-CPh, m-CSPh), 128.8 (d, JP,C ϭ 9.6 Hz, m-
3
1
Cdppe), 129.0 (d, JP,C ϭ 10.4 Hz, m-Cdppe), 130.3 (d, JP,C
ϭ
4
43.1 Hz, i-Cdppe), 130.4 (d, JP,C ϭ 2.5 Hz, p-Cdppe), 131.0 (d,
4JP,C ϭ 2.5 Hz, p-Cdppe), 132.1 (d, JP,C ϭ 28.6 Hz, i-Cdppe), 133.3
1
2
2
(d, JP,C ϭ 12.5 Hz, o-Cdppe), 133.7 (d, JP,C ϭ 12.0 Hz, o-Cdppe),
4
135.7 (d, JPtrans,C ϭ 1.6 Hz, o-CSPh), 144.5 (m, i-CPh), 147.0 (dd,
5. [Pd(CH2CH2CH2Ph)2(dppe)] (3b): At Ϫ78 °C, a solution of
LiCH2CH2CH2Ph (2b) (34.2 mmol) in toluene (50 mL) was added
to [PdCl2(dppe)] (3.30 g, 5.73 mmol). The reaction mixture was
slowly warmed to Ϫ30 °C and stirred overnight. The colorless pre-
cipitate was filtered off and washed at room temperature with n-
pentane as long as the filtrate remained colorless (ca. 20 mL). The
precipitate was dissolved in toluene (100 mL) at room temperature
and immediately filtered. At Ϫ30 °C, the solution was concentrated
in vacuo to about 10 mL. Cooling to Ϫ78 °C and addition of n-
3JPtrans,C ϭ 13.1, JPcis,C ϭ 3.1 Hz, i-CSPh) ppm. 31P NMR
3
2ϩ3
(81 MHz, CDCl3): δ ϭ 34.5 (d,
CH2CH2Ph), 53.2 (d,
J
P,P
ϭ 26.9 Hz, Ptrans to
ϭ 26.9 Hz, Ptrans to SPh) ppm.
2ϩ3
J
P,P
8. [Pd(CH2CH2CH2Ph)(SPh)(dppe)] (5b): At Ϫ78 °C, PhSH
(244 mg, 2.21 mmol) in THF (90 mL) was slowly added to a solu-
tion of [Pd(CH2CH2CH2Ph)2(dppe)] (3b) (1.644 g, 2.21 mmol) in
THF (90 mL). After warming to Ϫ30 °C, the reaction mixture was
stirred overnight. At Ϫ30 °C the solution was concentrated in va-
pentane (ca. 50 mL) resulted in the formation of 3b as a colorless cuo to 5 mL and at Ϫ78 °C pentane (25 mL) was added. At Ϫ30
2874 Eur. J. Inorg. Chem. 2002, 2868Ϫ2877

(Phenylalkyl)palladium Complexes Containing β-Hydrogen Atoms
FULL PAPER
2ϩ3
2
°C the pale pink precipitate that formed was filtered off, washed 25.6 Hz,
J
ϭ 11.9 Hz, PCH2), 29.0 (d, JPtrans,C ϭ 100.4 Hz,
P,C
1ϩ4
2ϩ3
with pentane (2 ϫ 10 mL) and dried in vacuo. Yield: 1.54 g (95%).
1H NMR (200 MHz, CDCl3): δ ϭ 1.12 (m, 2 H, PdCH2), 1.37 (m, 34.6 (s, PdCH2CH2), 42.4 (d, 4JPtrans,C
2 H, PdCH2CH2), 1.71 (m, 2 H, PdCH2CH2CH2), 1.94Ϫ2.43 (m, PdCH2CH2CH2), 125.5 (s, p-CPh), 128.5/129.0 (s/s, o-CPh, m-CPh),
4 H, PCH2), 6.6Ϫ6.7, 6.9Ϫ7.2, 7.4Ϫ7.8 (m, 30 H, Ph) ppm. 13C 129.3 (d, JP,C ϭ 9.7 Hz, m-Cdppe), 129.8 (d, JP,C ϭ 9.7 Hz, m-
PdCH2), 30.4 (dd,
J
P,C
ϭ 31.3 Hz,
J
P,C
ϭ 24.1 Hz, PCH2),
ϭ
15.3 Hz,
3
3
1ϩ4
1
NMR (125 MHz, CDCl3): δ ϭ 25.9 (dd,
J
P,C
ϭ 25.0 Hz,
Cdppe), 130.6 (d, JP,C ϭ 49.0 Hz, i-Cdppe), 131.0 (s, p-Cdppe), 132.0
2ϩ3
1ϩ4
2ϩ3
1
2
J
P,C
ϭ 15.0 Hz, PCH2), 28.9 (dd,
J
P,C
ϭ 27.9 Hz,
J ϭ
P,C
(s, p-Cdppe), 134.0 (d, JP,C ϭ 27.3 Hz, i-Cdppe), 134.5 (d, JP,C ϭ
22.0 Hz, PCH2), 29.0 (d, JPtrans,C ϭ 90.8 Hz, PdCH2), 33.3 (d, 9.7 Hz, o-Cdppe), 144.1 (s, i-CPh) ppm. 31P NMR (202 MHz, Ϫ30
2
4
2ϩ3
3JPtrans,C ϭ 4.0 Hz, PdCH2CH2), 41.3 (dd, JPtrans,C ϭ 14.9,
°C, [D8]THF):
CH2CH2CH2Ph), 59.5 (d,
δ
ϭ
28.9 (d,
J
ϭ
29.5 Hz, Ptrans to
P,P
4JPcis,C ϭ 3.0 Hz, PdCH2CH2CH2), 122.6 (s, p-CSPh), 124.5 (s, p-
CPh), 126.8 (s, m-CSPh), 127.5/128.2 (s/s, o-CPh, m-CPh), 128.5 (d,
3JP,C ϭ 9.0 Hz, m-Cdppe), 128.7 (d, 3JP,C ϭ 11.0 Hz, m-Cdppe), 130.1
J
P,P
ϭ 29.5 Hz, Ptrans to Br) ppm.
2ϩ3
Complex 10c (X ؍ Cl): Pale yellow solid. Yield: 420 mg (94%). 13C
1ϩ4
NMR (125 MHz, Ϫ30 °C, [D8]THF): δ ϭ 23.2 (dd,
J
ϭ
1
P,C
(s, p-Cdppe), 130.3 (d, JP,C ϭ 42.9 Hz, i-Cdppe), 130.7 (s, p-Cdppe),
2ϩ3
1ϩ4
26.3 Hz,
J
ϭ 11.0 Hz, PCH2), 30.3 (dd,
J
P,C
ϭ 32.7 Hz,
1
2
P,C
132.0 (d, JP,C ϭ 27.9 Hz, i-Cdppe), 133.1 (d, JP,C ϭ 12.0 Hz, o-
2ϩ3
2
J
P,C
ϭ 23.9 Hz, PCH2), 31.0 (d, JPtrans,C ϭ 101.2 Hz, PdCH2),
2
C
dppe), 133.3 (d, JP,C ϭ 12.1 Hz, o-Cdppe), 135.4 (s, o-CSPh), 143.2
3
4
34.0 (d, JP,C ϭ 4.5 Hz, PdCH2CH2), 42.2 (dd, JPtrans,C ϭ 15.3,
(s, i-CPh), 144.6 (d, JPtrans,C ϭ 9.9 Hz, i-CSPh) ppm. 31P NMR
3
4JPcis,C ϭ 3.2 Hz, PdCH2CH2CH2), 125.5 (s, p-CPh), 128.5/129.0 (s/
2ϩ3
(81 MHz, CDCl3): δ ϭ 34.0 (d,
J
P,P
ϭ 26.8 Hz, Ptrans to
ϭ 25.6 Hz, Ptrans to SPh) ppm.
3
s, o-CPh, m-CPh), 129.4 (d, JP,C ϭ 8.8 Hz, m-Cdppe), 129.7 (d,
2ϩ3
CH2CH2CH2Ph), 53.1 (d,
J
P,P
3JP,C ϭ 10.1 Hz, m-Cdppe), 130.7 (d, 1JP,C ϭ 49.0 Hz, i-Cdppe), 131.0
(s, p-Cdppe), 131.9 (s, p-Cdppe), 134.1 (one line of d, other one super-
9. [Pd(CH2CHMePh)(SPh)(dppe)] (5c)/[Pd(SPh)2(dppe)] (6a): At
Ϫ78 °C, PhSH (115 mg, 1.04 mmol) was added to a solution of
[Pd(CH2CHMePh)2(dppe)] (3c) (770 mg, 1.04 mmol) in THF (50
mL). After stirring overnight at Ϫ30 °C, the degree of conversion
was determined by 31P NMR spectroscopy. Then, PhSH was added
in a quantity that corresponded to the unchanged amount of 3c
and stirring (Ϫ30 °C) was continued. This procedure was repeated
until all of 3c had been consumed (final ratio 3c/PhSH ϭ 1:6). At
Ϫ30 °C, THF was removed in vacuo. The residue was taken up in
toluene (10 mL). Addition of pentane (50 mL) at Ϫ78 °C resulted
in the precipitation of a mixture of 5c/6a (74/26%) that was filtered,
washed with pentane and dried in vacuo at Ϫ30 °C.
2
posed, i-Cdppe), 134.3 (d, JP,C ϭ 11.3 Hz, o-Cdppe), 134.5 (d,
2JP,C ϭ 11.3 Hz, o-Cdppe), 144.2 (s, i-CPh) ppm. 31P NMR
2ϩ3
(202 MHz, Ϫ30 °C, [D8]THF): δ ϭ 27.7 (d,
J
P,P
ϭ 29.5 Hz,
2ϩ3
Ptrans to CH2CH2CH2Ph), 59.4 (d,
ppm.
J
ϭ 29.5 Hz, Ptrans to Cl)
P,P
11. Experiments Monitored by 31P NMR Spectroscopy: The corres-
ponding amounts of sulfur or selenium compounds were added
with a syringe to solutions of the palladium complex in THF/
[D8]THF (ca. 4:1). The reaction mixtures were transferred to NMR
tubes that were then sealed. The reactions were monitored by
31P{1H} NMR spectroscopy.
Complex 5c: 31P NMR (81 MHz, [D8]THF): δ ϭ 35.6 (d, 2ϩ3JP,P ϭ
[Pd(CH2CH2CH2Ph)(SPh)(dppe)] (5b) from 3b and PhSSPh: 31P
2ϩ3
25.7 Hz, Ptrans to CH2CHMePh), 51.3 (d,
to SPh) ppm.
J
P,P
ϭ 25.7 Hz, Ptrans
2ϩ3
NMR (81 MHz): δ ϭ 34.0 (d,
CH2CH2CH2Ph), 53.1 (d,
J
ϭ 25.6 Hz, Ptrans to
P,P
2ϩ3
J
P,P
ϭ 25.6 Hz, Ptrans to SPh) ppm.
Complex 6a: 31P NMR (81 MHz, CDCl3): δ ϭ 55.4 ppm.
[Pd(CH2CH2CH2Ph){S(iPr)}(dppe)] (5d) from 3b and iPrSH: 31P
2ϩ3
NMR (81 MHz): δ ϭ 40.7 (d,
J
ϭ 22.0 Hz, Ptrans to
P,P
10. [Pd(CH2CH2CH2Ph)X(dppe)] (X ؍ I, 10a; Br, 10b; Cl, 10c):
At Ϫ78 °C, MeI (290 mg, 2.04 mmol), H2CϭCHCH2Br (4.12 g,
34.1 mmol), or H2CϭCHCH2Cl (10 mL, without THF) was added
to [Pd(CH2CH2CH2Ph)(SPh)(dppe)] 5b (500 mg, 0.68 mmol) in
THF (10 mL). After stirring overnight at Ϫ30 °C, solvent and un-
changed RX compound were removed in vacuo. The residue was
taken up in toluene (10 mL) and cooled to Ϫ78 °C. Addition of
pentane (ca. 30 mL) resulted in precipitation of complexes 10 that
were filtered off, washed with pentane (2 ϫ 5 mL) and dried in
vacuo. All manipulations were performed at a maximum temper-
ature of Ϫ30 °C.
2ϩ3
CH2CH2CH2Ph), 55.9 [d,
J
P,P
ϭ 22.0 Hz, Ptrans to S(iPr)] ppm.
[Pd(CH2CH2CH2Ph){S(tBu)}(dppe)] (5e) from 3b and tBuSH: 31P
2ϩ3
NMR (81 MHz): δ ϭ 35.3 (d,
J
P,P
ϭ 23.2 Hz, Ptrans to
CH2CH2CH2Ph), 56.9 [d, 2ϩ3JP,P ϭ 22.0 Hz, Ptrans to S(tBu)] ppm.
[Pd(CH2CH2CH2Ph)(SBz)(dppe)] (5f) from 3b and BzSSBz: 31P
2ϩ3
NMR (81 MHz): δ ϭ 41.9 (d,
J
P,P
ϭ 23.2 Hz, Ptrans to
2ϩ3
CH2CH2CH2Ph), 56.6 (d,
J
P,P
ϭ 23.2 Hz, Ptrans to SBz) ppm.
[Pd(CH2CH2CH2Ph)(SMe)(dppe)] (5g) from 3b and MeSSMe: 31P
2ϩ3
NMR (81 MHz): δ ϭ 41.3 (d,
J
P,P
ϭ 23.2 Hz, Ptrans to
2ϩ3
Complex 10a (X ؍ I): Yellow solid. Yield: 500 mg (98%). 13C NMR
CH2CH2CH2Ph), 55.6 (d,
J
P,P
ϭ 23.2 Hz, Ptrans to SMe) ppm.
2
(125 MHz, Ϫ30 °C, [D8]THF): δ ϭ 24.3 (d, JPtrans,C ϭ 100.6 Hz,
[Pd(CH2CH2CH2Ph)(SeMe)(dppe)] (9a) from 3b and MeSeSeMe:
1ϩ4
2ϩ3
PdCH2), 30.2 (dd,
J
P,C
ϭ 30.0 Hz,
J
P,C
ϭ 22.6 Hz, PCH2;
2ϩ3
31P NMR (81 MHz): δ ϭ 46.1 (d,
J
P,P
ϭ 23.2 Hz, Ptrans to
other PCH2 not found, probably beneath solvent signal), 35.8 (s,
2ϩ3
CH2CH2CH2Ph), 52.4 (d,
J
P,P
ϭ 23.2 Hz, Ptrans to SeMe) ppm.
4
PdCH2CH2), 42.9 (d, JPtrans,C ϭ 13.9 Hz, PdCH2CH2CH2), 125.6
3
[PdMe(SePh)(dppe)] (9b) from
4
and PhSeSePh: 31P NMR
ϭ 23.2 Hz, Ptrans to Me), 56.8 (d,
(s, p-CPh), 128.5/128.9 (s/s, o-CPh, m-CPh), 129.2 (d, JP,C ϭ 9.2 Hz,
3
1
2ϩ3
m-Cdppe), 129.9 (d, JP,C ϭ 10.3 Hz, m-Cdppe), 130.2 (d, JP,C
ϭ
(81 MHz): δ ϭ 45.0 (d,
J
P,P
2ϩ3
47.4 Hz, i-Cdppe), 131.1 (s, p-Cdppe), 132.1 (s, p-Cdppe), 133.6 (d,
J
P,P
ϭ 23.2 Hz, Ptrans to SePh) ppm.
2
1JP,C ϭ 28.9 Hz, i-Cdppe), 134.5 (d, JP,C ϭ 11.8 Hz, o-Cdppe), 134.7
12. X-ray Structure of [Pd(CH2CH2Ph)2(dppe)] (3a): Single crystals
of complex 3a suitable for X-ray diffraction analysis were grown at
Ϫ30 °C by slow diffusion of n-pentane into a solution of 3a in
THF. Intensity data for complex 3a were collected at 200(2) K with
2
(d, JP,C ϭ 11.7 Hz, o-Cdppe), 143.8 (s, i-CPh) ppm. 31P NMR
2ϩ3
(202 MHz, Ϫ30 °C, [D8]THF): δ ϭ 30.2 (d,
J
ϭ 29.3 Hz,
P,P
2ϩ3
Ptrans to CH2CH2CH2Ph), 56.1 (d,
ppm.
J
P,P
ϭ 29.3 Hz, Ptrans to I)
˚
a Stoe STADI4 diffractometer with Mo-Kα radiation (0.71073 A,
Complex 10b (X ؍ Br): Pale yellow solid. Yield: 456 mg (95%). 13
C
ϭ
graphite monochromator). A summary of crystallographic data,
data collection parameters, and refinement parameters is given in
1ϩ4
NMR (125 MHz, Ϫ30 °C, [D8]THF): δ ϭ 24.0 (dd,
J
P,C
Eur. J. Inorg. Chem. 2002, 2868Ϫ2877
2875

T. Spaniel, H. Schmidt, C. Wagner, K. Merzweiler, D. Steinborn
FULL PAPER
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anisotropic displacement parameters. All hydrogen atoms were
found in the difference Fourier map and were refined isotropically.
CCDC-184402 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge
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Eur. J. Inorg. Chem. 2002, 2868Ϫ2877

(Phenylalkyl)palladium Complexes Containing β-Hydrogen Atoms
FULL PAPER
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Received April 24, 2002
[I02212]
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2877