Reactions of bis(silyl)palladium(II) complexes with allyl halides. Synthesis of mono(silyl)palladium(II) halides and X-ray structure of trans-PdCl(SiF2Ph)(PMe2Ph)2

Article abstract of DOI:10.1016/S0020-1693(99)00298-4

Reactions of trans-Pd(SiF₂Ph)₂L₂ (L = PMe₃ (1a), PMe₂Ph (1b), PMePh₂ (1c)) with allyl bromide readily proceeded in CH₂Cl₂ at - 20°C to form CH₂=CHCH₂

Full text of DOI:10.1016/S0020-1693(99)00298-4

www.elsevier.nl/locate/ica
Inorganica Chimica Acta 296 (1999) 19–25
Reactions of bis(silyl)palladium(II) complexes with allyl halides.
Synthesis of mono(silyl)palladium(II) halides and X-ray structure
of trans-PdCl(SiF2Ph)(PMe2Ph)2
Fumiyuki Ozawa a,*, Mitsuru Sugawara b, Koh Hasebe a, Tamio Hayashi c
a Department of Applied Chemistry, Faculty of Engineering, Osaka City Uni6ersity, Sumiyoshi-ku, Osaka 558-8585, Japan
b Graduate School of Pharmaceutical Sciences, Hokkaido Uni6ersity, Kita-ku, Sapporo 060-0812, Japan
c Department of Chemistry, Faculty of Science, Kyoto Uni6ersity, Sakyo-ku, Kyoto 606-8502, Japan
Received 2 February 1999; accepted 27 May 1999
Abstract
Reactions of trans-Pd(SiF2Ph)2L2 (L=PMe3 (1a), PMe2Ph (1b), PMePh2 (1c)) with allyl bromide readily proceeded in CH2Cl2
at −20°C to form CH2ꢀCHCH2SiF2Ph and the corresponding bromo(silyl)palladium complexes, trans-PdBr(SiF2Ph)L2 (2a–2c)
in high selectivities. Treatment of 1a–1c with dry HCl in CH2Cl2 at −20°C gave silyl chloride complexes, trans-PdCl(SiF2Ph)L2
(3a–3c), respectively. Complexes 2a–2c and 3a–3c were isolated and characterized by NMR spectroscopy and/or elemental
analysis. One of the complexes, trans-PdCl(SiF2Ph)(PMe2Ph)2 (3b), was identified also by X-ray diffraction study. Relevance of
bis-silyl complexes to catalytic silylation of allylic compounds with disilanes is discussed. © 1999 Elsevier Science S.A. All rights
reserved.
Keywords: Crystal structures; Palladium complexes; Silyl complexes; Allylsilanes
1. Introduction
sidered to proceed via the catalytic cycle depicted in
Scheme 1.
Palladium complex-catalyzed silylation of allylic
compounds such as allylic carboxylates and halides
with disilanes have provided a useful means of synthe-
sizing allylic silanes which are versatile intermediates in
organic synthesis [1–4]. The early examples, however,
suffered from the lack of general applicability mainly
due to the high reaction temperatures (120–170°C)
[1,2]. Recently, reactivity of the catalysis was improved
to a great extent by two groups. Hayashi and co-work-
ers [3] demonstrated that the disilanes which are un-
symmetrically substituted with chlorine or fluorine
(PhY2SiSiMe3; Y=Cl or F) react with various allylic
chlorides under mild conditions (25–60°C) to give
allylic silanes in high yields. On the other hand, Tsuji
et al. [4] reported the catalytic silylation of allylic
trifluoroacetates with Me3SiSiMe3, which proceeds
at room temperature (r.t.). These catalyses are con-
Oxidative addition of allylic substrate to a palla-
dium(0) species forms a (p-allyl)palladium complex,
which successively undergoes the reaction with disilane
to give a (p-allyl)(silyl)palladium intermediate. Reduc-
tive elimination of the p-allyl and silyl ligands affords
allylic silane. This catalytic cycle seems reasonable in
* Corresponding author. Tel.: +81-6-6605 2884; fax: +81-6-6605
2978.
Scheme 1.
0020-1693/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0020-1693(99)00298-4

20
F. Ozawa et al. / Inorganica Chimica Acta 296 (1999) 19–25
The reactions of PMe3- and PMe2Ph-coordinated
complexes 1a (l −28.2) and 1b (l −17.0) were com-
plete for 3 and 1 h, respectively, giving the correspond-
ing mono-silyl complexes 2a (l −13.5) and 2b (l
−4.5), exclusively. Also formed in the reaction systems
was CH2ꢀCHCH2SiF2Ph in quantitative yields as confi-
rmed by GLC analysis using methyl phenyl ether as an
internal standard. Complex 1c bearing PMePh2 ligands
(l −1.9) similarly reacted with allyl bromide in
CD2Cl2 at −20°C for 5 h to provide the corresponding
mono-silyl complex 2c (l 11.0) and allylsilane in 92%
selectivity, along with the by-production (8%) of [Pd(p-
allyl)(PMePh2)2]Br (l 7.0).
Scheme 2.
In contrast to allyl bromide, allyl chloride and ac-
etate exhibited much lower reactivity and selectivity.
Thus, the reaction of 1b with allyl chloride in CD2Cl2 at
−20°C took 72 h for the completion, giving a 7:1:2
mixture of trans-PdCl(SiF2Ph)(PMe2Ph)2 (3b) (l −3.1),
[Pd(p-allyl)(PMe2Ph)2]Cl (l −7.2), and Pd(p-al-
lyl)Cl(PMe2Ph) (l −2.7). The reaction with allyl ac-
etate proceeded only in 36% conversion after 14 days at
−20°C. In this reaction, [Pd(p-allyl)(PMe2Ph)2]OAc (l
−7.7) was exclusively produced without formation of
mono-silyl complex.
view of the versatility of (p-allyl)palladium intermedi-
ates in catalytic reactions as well as the observations
that isolated (p-allyl)palladium complexes can react
with disilanes to give allylic silanes [4,5]. However, since
palladium-catalyzed silylation of organic substrates of-
ten involves a bis(silyl)palladium intermediate [6,7] and
such a complex has been shown to be readily produced
by oxidative addition of disilane to a palladium(0)
species [8,9], it seems also possible that the catalytic
silylation of allylic compounds proceeds partly or pre-
dominantly via an alternative catalytic cycle given in
Scheme 2, where allylic silane is formed by the reaction
of a bis(silyl)palladium intermediate with allylic halide
or carboxylate.
2.2. Isolation and characterization of
mono(silyl)palladium complexes
Therefore, we examined in this study the reactions of
symmetrical and unsymmetrical bis(silyl)palladium com-
plexes, trans-Pd(SiF2Ph)2L2 (L=PMe3 (1a), PMe2Ph
(1b), PMePh2 (1c)) and trans-Pd(SiMe3)(SiF2Ph)-
(PMe2Ph)2 (1d) [9], with allyl halides and acetate. The
symmetrical bis-silyl complexes 1a–1c have been found
to react readily with allyl bromide to give allylsilane
and mono(silyl)palladium complexes in high yields.
The bromide complexes 2a, 2b, and 2c were synthe-
sized by the reactions in Eq. (1) and isolated as pale
yellow crystalline solids in 81, 89, and 55% yields,
respectively. On the other hand, since the selectivity for
chloride complex 3b in the reaction of 1b with allyl
chloride was low, this complex was prepared by an-
other method (Eq. (2)). Treatment of 1b with dry-HCl
in CH2Cl2 at −20°C selectively provided the desired
complex 3b, which was isolated as white crystals in 88%
yield. The reaction was carried out with an excess
amount of HCl (3 equiv./1b) to complete the reaction,
but no formation of palladium dichloride was detected
by 31P{1H} NMR analysis of the reaction solution.
Similarly, mono(silyl) complexes having PMe3 and
PMePh2 (3a and 3c) were synthesized in 75 and 35%
isolated yields, respectively. The PMe3 and PMe2Ph
complexes (2a, 2b, 3a, and 3b) were stable in the solid,
but gradually decomposed in solution at r.t. to give a
mixture of unidentified palladium species. The PMePh2
complexes (2c and 3c) were unstable in the solid as well
as in solution at r.t.
2. Results and discussion
2.1. Reactions of trans-Pd(SiF2Ph)2L2 (1a–1c) with
allyl halides
The symmetrical bis-silyl complexes having three
kinds of phosphine ligands, 1a–1c, were treated with
allyl bromide (3 equiv.) in CD2Cl2 at −20°C, and the
reactions were followed by 31P{1H} NMR spectroscopy
(Eq. (1)).
(2)
(1)

F. Ozawa et al. / Inorganica Chimica Acta 296 (1999) 19–25
21
Table 1
Characteristic NMR data of complexes 2a–2c and 3a–3c a
Complex
1H NMR (PCH3) b
19F NMR c
31P{1H} NMR
l
2JPꢁH
l
3JPꢁF
l
3JPꢁF
2a
2b
2c
3a
3b
3c
1.48 (vt)
1.80 (vt)
2.12 (vt)
1.44 (vt)
1.75 (vt)
2.05 (vt)
3.6
3.3
3.3
3.6
3.4
3.3
−29.9 (t)
−29.1 (t)
−28.0 (t)
−30.0 (t)
−29.2 (t)
−28.1 (t)
23
23
24
22
23
24
−13.5 (t)
−4.5 (t)
11.0 (t)
−11.9 (t)
−3.1 (t)
11.0 (t)
23
23
24
22
23
24
a All measurements were carried out in CD2Cl2 at −20°C. Coupling constants are in Hz.
b vt, virtual triplet. The coupling constants listed are apparent values for the virtual couplings.
c Referenced to 100% CF3CO2H as an external standard.
Complexes 2a, 2b, 3a, and 3b were identified by
NMR spectroscopy and elemental analysis. On the
other hand, since elemental analysis of the PMePh2-
coordinated complexes 2c and 3c was unfeasible due to
thermal instability, they were characterized by NMR
spectroscopy. Table 1 lists the characteristic NMR
data. The PCH3 protons were observed as a virtual
triplet with a small coupling to the 19F nuclei (B1 Hz),
indicating the square planar geometry having two phos-
phine ligands in mutually trans positions [10]. The
fluorine nuclei on the silicon were observed as a triplet
due to the coupling with two phosphorus nuclei. Con-
versely, the signal of phosphorus nuclei split into a
yields (Eq. (1)). As described in Section 1, this type of
reaction is possibly operative in the catalytic silylation
of allylic halides with disilanes. In order to test this
possibility, we next examined the reactions of unsym-
metrical bis-silyl complex trans-Pd(SiMe3)(SiF2Ph)-
(PMe2Ph)2 (1d) with allyl bromide and chloride. This
investigation is based on the previous finding that the
palladium-catalyzed silylation of allylic halides with
unsymmetrical disilanes such as PhCl2SiSiMe3 and
PhF2SiSiMe3 provides allylic silanes bearing electron-
withdrawing silyl groups (i.e. PhCl2Si and PhF2Si)
in high selectivity [3]. Thus, if the same selectivity
is observed in the stoichiometric systems, the
3
triplet with the JPꢁF value of ca. 23 Hz. These spectro-
scopic features are also consistent with the trans geome-
try in solution. The chemical shifts of fluorine nuclei in
the series of bromide complexes 2a–2c tended to shift
to lower magnetic field as the phosphine ligand became
less basic. A similar tendency was observed for the
chloride complexes 3a–3c, reflecting the difference in
the electron-donating ability of the phosphine ligands
in the order PMe3\PMe2Ph\PMePh2.
Fig. 1 shows the X-ray structure of 3b. The palla-
dium atom is in an almost perfect square planar envi-
ronment with two PMe2Ph ligands in mutually trans
positions, consistent with the NMR observations. The
ClꢁPdꢁP(1) and ClꢁPdꢁP(2) angles (91.77(2) and
91.16(2)°) are slightly wider than the P(1)ꢁPdꢁSi and
P(2)ꢁPdꢁSi angles (87.77(2) and 89.06(2)°), reflecting
bulkiness of the SiF2Ph ligand compared with the chlo-
ride ligand. Owing to the low trans-influence of the
,
chloride ligand, the PdꢁSi bond distance (2.2680(6) A)
is among the shortest range of silylpalladium complexes
,
so far identified by X-ray analysis (2.336–2.375 A) [8].
Fig. 1. Molecular structure of trans-PdCl(SiF2Ph)(PMe2Ph)2 (3b).
,
Selected bond distances (A) and angles (°): PdꢁCl=2.4280(6),
PdꢁP(1)=2.3202(6),
SiꢁF(1)=1.604(2),
ClꢁPdꢁSi=176.09(2), ClꢁPdꢁP(1)=91.77(2), ClꢁPdꢁP(2)=91.16(2),
P(1)ꢁPdꢁP(2)=175.29(2), P(1)ꢁPdꢁSi=87.77(2), P(2)ꢁPdꢁSi=
89.06(2), PdꢁSiꢁF(1)=115.08(6), PdꢁSiꢁF(2)=113.06(6),
PdꢁSiꢁC(1)=117.22(7), F(1)ꢁSiꢁF(2)=99.01(9), F(1)ꢁSiꢁC(1)=
104.9(1), F(2)ꢁSiꢁC(1)=105.60(9).
PdꢁP(2)=2.3304(6),
SiꢁF(2)=1.605(2),
PdꢁSi=2.2680(6),
SiꢁC(1)=1.867(2),
2.3. Reactions of trans-Pd(SiMe3)(SiF2Ph)(PMe2Ph)2
(1d) with allyl halides
It has been found that the symmetrical bis-silyl com-
plexes react with allyl bromide to give allylsilane in high

22
F. Ozawa et al. / Inorganica Chimica Acta 296 (1999) 19–25
result may be taken as an indication for bis-
(silyl)palladium intermediates. On the contrary, if the
opposite selectivity is found, one may exclude the possi-
bility for the catalytic cycle involving a bis-silyl
intermediate.
the reactions of bis-silyl complexes with allyl bromide
provided a highly selective way to mono(silyl)palladium
complexes, which have been assumed in some catalytic
silylation reactions [11], but well-defined examples of
such complexes have been extremely rare. The platinum
analogs have been reported in Ref. [12].
The results of stoichiometric reactions are given in
Eqs. (3) and (4). Treatment of 1d with allyl bromide (3
equiv.) in CD2Cl2 at −20°C rapidly afforded
CH2ꢀCHCH2SiMe3 and CH2ꢀCHCH2SiF2Ph in a 7:3
ratio, as confirmed by GLC. Also observed in the
reaction solution by 31P{1H} NMR spectroscopy was
the formation of 2b, [Pd(p-allyl)(PMe2Ph)2]Br, and
Pd(p-allyl)Br(PMe2Ph) in a 6:1:2 ratio. In the reaction
of 1d with allyl chloride under similar reaction condi-
tions, CH2ꢀCHCH2SiMe3 and CH2ꢀCHCH2SiF2Ph
were detected in a 9:1 ratio, along with the formation of
3b and [Pd(p-allyl)(PMe2Ph)2]Cl in a 9:1 ratio. Thus,
both results indicated that the bis-silyl complexes are
unlikely intermediates in the catalytic reactions.
3. Experimental
All manipulations were carried out under a nitrogen
atmosphere using conventional Schlenk techniques. Ni-
trogen gas was dried by passage through P2O5 (Merck,
Sicapent). NMR spectra were recorded on Jeol JNM-
EX270 and JNM-A400 spectrometers. Chemical shifts
are reported in l (ppm) referred to an internal SiMe4
standard for 1H NMR, to an external 85% H3PO4
standard for 31P NMR, and to an external 100%
CF3COOH standard for 19F NMR. Elemental analyses
were performed by the Hokkaido University Analytical
Center and by the Analytical Laboratory of the Depart-
ment of Applied Chemistry, Osaka City University.
GLC analysis was carried out on a Shimadzu GC-3BT
instrument, equipped with a TCD detector and a 1 m
glass-made column of 5% Silicone OV-1. Toluene,
THF, Et2O, hexane, and pentane were dried over
sodium benzophenone ketyl, distilled, and stored under
a nitrogen atmosphere. Dichloromethane was dried
over CaH2, distilled, and stored under a nitrogen atmo-
sphere. The complexes trans-Pd(SiF2Ph)L2 (L=PMe3
(1a), PMe2Ph (1b), PMePh2 (1c)) and trans-
Pd(SiMe3)(SiF2Ph)(PMe2Ph)2 (1d) were prepared as
previously reported [9]. All other compounds were ob-
tained from commercial sources and used without fur-
ther purification.
(3)
(4)
3.1. Reactions of bis-silyl complexes with allyl halides
A typical example is as follows. The complex trans-
Pd(SiF2Ph)(PMe3)2 (1a) (8.2 mg, 0.015 mmol) was
placed in an NMR sample tube equipped with a rubber
septum cap and the system was replaced with nitrogen
gas. The sample was cooled at −50°C, and CD2Cl2
(0.5 ml) and allyl bromide (3.9 ml, 0.045 mmol) were
added. The sample tube was placed in an NMR sample
probe controlled at −20°C, and the reaction system
was examined by 31P{1H} NMR spectroscopy. The
2.4. Conclusion
We have examined in this study intermediacy of
bis(silyl)palladium complexes in catalytic silylation of
allyl halides with disilanes. The symmetrical bis(silyl)-
palladium complexes bearing SiF2Ph groups (1a–1c)
reacted with allyl bromide and chloride under mild
conditions to give allylsilane (CH2ꢀCHCH2SiF2Ph) and
mono(silyl)palladium complexes. However, reactions of
unsymmetrical trans-Pd(SiMe3)(SiF2Ph)(PMe2Ph)2 (1d)
3
quintet signal of the starting 1a (l 28.2, JPꢁF=33 Hz)
gradually decreased to be replaced with a triplet at l
−13.5 (3JPꢁF=23 Hz) which is assignable to trans-
PdBr(SiF2Ph)(PMe3)2 (2a). The spectroscopic change
was complete for 2.7 h. GLC analysis of the reaction
solution using methyl phenyl ether as an internal stan-
dard revealed the quantitative formation of
CH2ꢀCHCH2SiF2Ph within an experimental error
(98%).
with
allyl
halides
predominantly
gave
CH2ꢀCHCH2SiMe3, and this selectivity of silyl group
was opposite to the previous observations for the cata-
lytic silylation of allylic halides with PhF2SiSiMe3 [3].
Apart from the relevance to the catalytic mechanism,

F. Ozawa et al. / Inorganica Chimica Acta 296 (1999) 19–25
23
The allylsilane produced was identified with an au-
thentic sample, prepared by the following method. Al-
lyltrichlorosilane [13] (10.8 g, 61.5 mmol) was dissolved
in Et2O (30 ml) and treated with PhMgCl (2 M, 62
mmol) at r.t. for 2 h. The resulting mixture was quickly
passed though a glass-wool filter to remove a white
precipitate of MgCl2. The filtrate was concentrated and
distilled under reduced pressure to give CH2ꢀCH-
CH2SiCl2Ph (b.p. 101–105°C at 8 mmHg) (9.8 g, 73%).
A part of the product (2.06 g, 9.5 mmol) was added in
one portion to a suspension of CuF2·2H2O (1.3 g, 9.4
mmol) in Et2O (15 ml) at 0°C, and stirred overnight at
r.t. The initial blue color of the mixture quickly turned
to brown and then gradually to green. The heteroge-
neous mixture was filtered through a cannula tipped
with a filter-paper, and the residue was extracted with
Et2O (3×5 ml). Distillation of the combined filtrates
gave CH2ꢀCHCH2SiF2Ph (b.p. 97°C at 54 mmHg)
C12H23BrF2P2PdSi: C, 29.92; H, 4.81; Br, 16.59. Found:
C, 30.12; H, 4.85; Br, 16.36%.
Similarly
prepared
were
trans-PdBr(SiF2Ph)-
(PMe2Ph) (2b) (89% yield, colorless crystals) and trans-
PdBr(SiF2Ph)(PMePh2)2 (2c) (55% yield, white needles).
trans-PdBr(SiF2Ph)(PMe2Ph)2 (2b). 1H NMR
(CD2Cl2, −20°C): l 1.80 (virtual triplet, J=3.3 Hz,
12H, PMe), 7.25–7.48 (m, 9H, Ph), 7.48–7.74 (m, 6H,
Ph). 31P{1H} NMR (CD2Cl2, −20°C): l −4.5 (t,
3JPꢁF=23 Hz). 19F NMR (CD2Cl2, −20°C): l −29.1
(t, 3JPꢁF=23 Hz, 1JFꢁSi=355 Hz). Anal. Calc. for
C22H27BrF2P2PdSi: C, 43.62; H, 4.49; Br, 13.19. Found:
C, 43.57; H, 4.55; Br, 13.31%.
trans-PdBr(SiF2Ph)(PMePh2)2 (2c). 1H NMR
(CD2Cl2, −20°C): l 2.12 (virtual triplet, J=3.3 Hz,
6H, PMe), 7.14–7.29 (m, 4H, Ph), 7.29–7.47 (m, 13H,
Ph), 7.47–7.61 (m, 8H, Ph). 31P{1H} NMR (CD2Cl2,
3
−20°C): l 11.0 (t, JPꢁF=24 Hz). 19F NMR (CD2Cl2,
1
3
(1.17 g, 67%). H NMR (CDCl3): l 2.08 (dtt, JHꢁH
=
3
1
3
4
−20°C): l −28.0 (t, JPꢁF=24, JFꢁSi=357 Hz). Ele-
mental analysis of this complex was unfeasible due to
decomposition.
7.9, JHꢁF=4.6, JHꢁH=1.3 Hz, 2H, SiCH2), 5.04 (dq,
3JHꢁH=9.9, 2JHꢁH=4JHꢁH=1.3 Hz, 1H, ꢀC(H)H), 5.09
(dq, 3JHꢁH=17.2, 2JHꢁH=4JHꢁH=1.3 Hz, 1H,
3
ꢀC(H)H), 5.82 (ddt, JHꢁH=17.2, 9.9 and 7.9 Hz, 1H,
3.3. Preparation of trans-PdCl(SiF2Ph)L2 complexes
ꢀCHCH2), 7.44 (m, 2H, SiPh), 7.52 (m, 1H, SiPh), 7.65
(m, 2H, SiPh). 19F NMR (CDCl3): l 64.2 (t, 3JHꢁF=4.6
Hz).
Synthesis of the PMe3 complex 3a represents a typi-
cal procedure. To a CH2Cl2 solution (2 ml) of trans-
Pd(SiF2Ph)2(PMe3)2 (1a) (211 mg, 0.386 mmol) was
added a CH2Cl2 solution of dry HCl (0.175 M, 7.5 ml,
1.31 mmol) at −20°C. The solution was stirred at the
same temperature for 0.6 h, and then concentrated to
ca. 1.5 ml under reduced pressure. Et2O (5 ml) was
carefully layered on the solution and the solvent layers
were allowed to stand at −70°C overnight to give
The other reactions of bis-silyl complexes with allyl
halides and acetate were similarly examined. p-Allyl
complexes formed in the reaction systems were iden-
tified by comparison of the chemical shifts in 31P{1H}
NMR spectra with those of authentic samples. The
[Pd(p-allyl)L2]X complexes were synthesized by oxida-
tive addition of CH2ꢀCHCH2X to Pd(styrene)L2 com-
plexes [14]. The Pd(p-allyl)X(L) complexes were
prepared by the treatment of [Pd(p-allyl)X]2 with corre-
sponding phosphines (1 equiv./Pd).
1
colorless crystals of 3a (126 mg, 75% yield). H NMR
(CD2Cl2, −20°C): l 1.44 (virtual triplet, J=3.6 Hz,
18H, PMe), 7.34–7.49 (m, 3H, Ph), 7.61–7.72 (m, 2H,
Ph). 31P{1H} NMR (CD2Cl2, −20°C): l −11.9 (t,
3JPꢁF=22 Hz). 19F NMR (CD2Cl2, −20°C): l −30.0
(t, 3JPꢁF=22, 1JFꢁSi=353 Hz). Anal. Calc. for
C12H23ClF2P2PdSi: C, 32.97; H, 5.30; Cl, 8.11. Found:
C, 32.93; H, 5.29; Cl, 8.28%.
3.2. Preparation of trans-PdBr(SiF2Ph)L2 complexes
The PMe3 complex 2a was prepared as follows. To a
CH2Cl2 solution (4 ml) of trans-Pd(SiF2Ph)2(PMe3)2
(1a) (201 mg, 0.368 mmol) was added allyl bromide
(100 ml, 1.15 mmol) at −20°C. The solution was stirred
at the same temperature for 2.2 h and then at r.t. for
0.3 h. The solution was concentrated to dryness under
reduced pressure, and the resultant solid was dissolved
in CH2Cl2 and filtered through a short Celite column to
remove a small amount of insoluble material. The
filtrate was concentrated to ca. 1.5 ml and carefully
layered Et2O, and then cooled at −70°C overnight to
give slightly yellow crystals of 2a (143 mg, 81% yield).
1H NMR (CD2Cl2, −20°C): l 1.48 (virtual triplet,
J=3.6 Hz, 18H, PMe), 7.34–7.52 (m, 3H, Ph), 7.60–
7.76 (m, 2H, Ph). 31P{1H} NMR (CD2Cl2, −20°C): l
Similarly
prepared
were
trans-PdCl(SiF2Ph)-
(PMe2Ph) (3b) (88% yield, colorless crystals) and trans-
PdCl(SiF2Ph)(PMePh2)2 (3c) (35% yield, white needles).
trans-PdCl(SiF2Ph)(PMe2Ph)2 (3b). 1H NMR
(CD2Cl2, −20°C): l 1.75 (virtual triplet, J=3.4 Hz,
12H, PMe), 7.25–7.48 (m, 9H, Ph), 7.48–7.57 (m, 2H,
Ph), 7.57–7.72 (m, 4H, Ph). 31P{1H} NMR (CD2Cl2,
−20°C): l −3.05 (t, 3JPꢁF=23 Hz). 19F NMR
3
1
(CD2Cl2, −20°C): l −29.2 (t, JPꢁF=23, JFꢁSi=355
Hz). Anal. Calc. for C22H27ClF2P2PdSi: C, 47.07; H,
4.85; Cl, 6.32. Found: C, 46.91; H, 4.80; Cl, 6.02%.
trans-PdCl(SiF2Ph)(PMePh2)2 (3c). 1H NMR
(CD2Cl2, −20°C): l 2.05 (virtual triplet, J=3.3 Hz,
3
−13.5 (t, JPꢁF=23 Hz). 19F NMR (CD2Cl2, −20°C):
3
1
l −29.9 (t, JPꢁF=23, JFꢁSi=355 Hz). Anal. Calc. for

24
F. Ozawa et al. / Inorganica Chimica Acta 296 (1999) 19–25
reflections measured, 4957 were classed as observed
(I\3|(I)) and these were used for the solution and
refinement of the structure.
Table 2
Crystal data and details of structure refinement for 3b
Formula
C22H27ClF2P2PdSi
All calculations were performed with the TEXSAN
Crystal Structure Analysis Package provided by Rigaku
Corporation, Tokyo, Japan [15]. The scattering factors
were taken from International Tables for X-ray Crys-
tallography [16]. The structure was solved by heavy
atom Patterson methods (PATTY) and expanded using
Fourier techniques (DIRDIF-92). The structure was
refined by full-matrix least-squares with anisotropic
thermal parameters for all non-hydrogen atoms. In the
final cycles of refinement, hydrogen atoms with
FW
Crystal system
Space group
561.34
triclinic
(
P1 (no. 2)
,
a (A)
9.694(1)
14.405(2)
9.430(1)
94.20(1)
105.076(9)
101.444(9)
1235.3(3)
2
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
V (A )
Z
3
,
Dcalc (g cm−3
F(000)
)
1.509
568
isotropic temperature factors (Biso=1.20Bbonded
)
atom
,
were located at idealized positions (d(CꢁH)=0.95 A)
and were included in calculation without refinement of
their parameters. The function minimized in least-
squares was Sw(ꢀFoꢀ−ꢀFcꢀ)2 (w=1/[|2(Fo)]). The final
R index was 0.028 (Rw=0.043, S=1.10). R=SꢀꢀFoꢀ−
ꢀFcꢀꢀ/SꢀFoꢀ and Rw=[Sw(ꢀFoꢀ−ꢀFcꢀ)2/SwꢀFoꢀ2]1/2. S=
[Sw(ꢀFoꢀ−ꢀFcꢀ)2/(No−Np)]1/2, where No is the number
of observed data and Np is the number of parameters
varied. Crystal data and details of data collection and
refinement are summarized in Table 2. Further infor-
mation including the positional parameters, anisotropic
thermal parameters, and full bond distances and angles
is available as supplementary material (see Section 4).
Crystal size (mm)
0.45×0.35×0.25
10.59
Mo Ka, 0.71069
+h, 9k, 9l
ꢀ–2q
1.10+0.30 tan q
55.0
4, fixed
v (Mo Ka) (cm−1
)
,
Radiation, u (A)
Data collected
Scan type
Scan range
2q Max. (°)
Scan speed (° min−1
)
No. of reflections measured
No. of unique reflections
No. of reflections used
No. of variables
R
5993
5660 (Rint=0.013)
4957 [I]3|(I)]
262
0.028
0.043
1.10
0.00
0.73 and −0.29
Rw
Goodness-of-fit
Max. shift/error
Max. and min. peak (e A
−3
,
)
4. Supplementary material
Crystallographic data (excluding structure factors)
for the structure of 3b have been deposited with the
Cambridge Crystallographic Data Centre (CCDC
121667). Copies of the data can be obtained, free of
charge, on application to CCDC (fax: +44-1223-336-
033 or e-mail: deposit@ccdc.cam.ac.uk).
6H, PMe), 7.13–7.27 (m, 4H, Ph), 7.27–7.46 (m, 13H,
Ph), 7.50–7.62 (m, 8H, Ph). 31P{1H} NMR (CD2Cl2,
3
−20°C): l 12.4 (t, JPꢁF=23 Hz). 19F NMR (CD2Cl2,
3
1
−20°C): l −28.1 (t, JPꢁF=23, JFꢁSi=355 Hz). Ele-
mental analysis was unfeasible due to decomposition.
3.4. X-ray diffraction of 3b
Acknowledgements
A single crystal of dimensions ca. 0.45×0.35×0.25
mm, which was grown from a mixture of CH2Cl2 and
Et2O, was sealed in a glass capillary tube. Intensity data
were collected on a Rigaku AFC5R four-circle diffrac-
tometer. Unit cell dimensions were obtained from a
least-squares treatment of the setting angles of 25 reflec-
tions in the range 25.55B2qB29.96°. The cell dimen-
sions suggested a triclinic cell and a statistical analysis
This work was supported by a Grant-in-Aid for
Scientific Research on Priority Area ‘The Chemistry of
Inter-element Linkage’ (No. 09239105) from the Min-
istry of Education, Science, Sports and Culture, Japan.
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