Revising the [PdCl2(1,2-(PPh2)2-1,2-C2B 10H10)] synthesis and comparison of its behavior with [PdCl2(1,2-(PiPr2)2-1,2-C 2B10H10)]. Crystal structure of [PdCl2(1,2-(PPh2)2-1,2-C2B 10H10)]

Article abstract of DOI:10.1016/S0022-328X(00)00356-9

Two methods for the revised synthesis of [PdCl₂(1,2-(PPh₂)₂-1,2-C₂B ₁₀H₁₀)] are described. They differ on the reagent complex, to say 1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane was mixed with [PdCl₂(cod)] or [PdCl₂(PhCN)] in non-nucleophilic solvents. The structure of [PdCl₂(1,2-(PPh₂)₂-1,2-C2B₁₀H ₁₀)] was determined by single-crystal X-ray study. The carborane cage is coordinated bidentately through the P atoms to the Pd(II) ion, the remaining two positions are occupied by two chloride ions which are mutually cis. Overall, the coordination about the metal can be described as a slightly distorted square-planar. The reaction of 1,2-bis(diisopropylphosphino)-1,2-dicarba-closo-dodecaborane in dichloromethane produced mostly a compound with similar formula, however some deboronation took place and [Pd₂(μ-Cl)₂{7,8-(PⁱPr₂) ₂-7,8-C₂B₉H₁₀}₂] was also produced. Larger amounts of this dinuclear complex were obtained when the closo species was refluxed for few minutes in a mild nucleophilic solvent.

Full text of DOI:10.1016/S0022-328X(00)00356-9

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 606 (2000) 183–187
Revising the [PdCl2(1,2-(PPh2)2-1,2-C2B10H10)] synthesis and
comparison of its behavior with [PdCl2(1,2-(PiPr2)2-1,2-C2B10H10)].
Crystal structure of [PdCl2(1,2-(PPh2)2-1,2-C2B10H10)]
Sari Paavola a, Raikko Kiveka¨s a,*1, Francesc Teixidor b, Clara Vin˜as b,*2
a Department of Chemistry, P.O. Box 55, FIN-00014 Uni6ersity of Helsinki, Finland
b Institut de Cie`ncia de Materials de Barcelona, CSIC, Campus UAB, 08193 Bellaterra, Spain
Received 18 April 2000; received in revised form 30 May 2000
Abstract
Two methods for the revised synthesis of [PdCl2(1,2-(PPh2)2-1,2-C2B10H10)] are described. They differ on the reagent complex,
to say 1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane was mixed with [PdCl2(cod)] or [PdCl2(PhCN)] in non-nucle-
ophilic solvents. The structure of [PdCl2(1,2-(PPh2)2-1,2-C2B10H10)] was determined by single-crystal X-ray study. The carborane
cage is coordinated bidentately through the P atoms to the Pd(II) ion, the remaining two positions are occupied by two chloride
ions which are mutually cis. Overall, the coordination about the metal can be described as a slightly distorted square-planar. The
reaction of 1,2-bis(diisopropylphosphino)-1,2-dicarba-closo-dodecaborane in dichloromethane produced mostly a compound with
similar formula, however some deboronation took place and [Pd2(m-Cl)2{7,8-(PiPr2)2-7,8-C2B9H10}2] was also produced. Larger
amounts of this dinuclear complex were obtained when the closo species was refluxed for few minutes in a mild nucleophilic
solvent. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Carboranes; Palladium; Deboronation; Cluster
substituents on the carbon atoms contain lone pairs,
strategies have been studied to preserve the closo nature
of the cluster through the reaction.
1. Introduction
Over the last 15 years enormous progress has been
made in the development and design of single-site cata-
lysts for the polymerization of a-olefins [1]. Two of the
fundamentals for these catalysts are that two cis posi-
tions of the metal center are available to perform the
reaction, and that the catalyst is cationic before inser-
tion of the alkene. Diphosphines have already been
demonstrated to be very convenient for this sort of
catalysis [2]. Taking into account that o-carbo-
ranyldiphosphines fall into this category, and consider-
ing the importance of Pd as a metal in catalysts, we
have reinvestigated the synthesis of [PdCl2(1,2-(PPh2)2-
1,2-C2B10H10)] in an effort to determine its crystal
structure. Also, considering the easy deboronation that
has been demonstrated to occur in the cluster when
2. Results and discussion
As we have demonstrated in a series of papers [3], the
reaction of o-carboranyldiphosphines with transition
metal complexes in methanol, or ethanol, leads to
deboronation of the closo carboranyl cluster to produce
11 vertex monoanionic nido species. This is shown in
Scheme 1.
1 *Corresponding author. E-mail: raikko.kivekas@helsinki.fi
(R.Kivekas).
2 *Corresponding author. Tel.: +358-9-19140198; e-mail:
sari.paavola@helsinki.fi
Scheme 1. Deboronation of the closo cluster by metal coordination in
nucleophilic solvents.
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00356-9

184
S. Paa6ola et al. / Journal of Organometallic Chemistry 606 (2000) 183–187
Thus, care should be taken in attempting the synthesis
of transition metal complexes incorporating the 1,2-
C2B10H10 fragment, as [PdCl2(1,2-(PPh2)2-1,2-
C2B10H10)], since deboronation seems to be the favored
process if a nucleophile is present. Based on the experi-
ence gained dealing with o-carboranyldiphosphines [3],
we attempted the synthesis of [PdCl2(1,2-(PPh2)2-1,2-
C2B10H10)], avoiding the use of nucleophilic solvents.
This led to a full characterization. Two methods, A and
B, were used which produce a suitable and pure solid.
Following our criteria to avoid nucleophiles we have
used dichloromethane and toluene. Furthermore, we
even considered that nucleophilic agents had to be kept
away in the separation process. This will be shown in
the synthesis of [PdCl2(1,2-(PiPr2)2-1,2-C2B10H10)]. Fol-
lowing these restrictions the yields produced are satis-
factory specially the one with [PdCl2(cod)], method A,
that produces [PdCl2(1,2-(PPh2)2-1,2-C2B10H10)] in 96%
yield. The w(BꢀH) in the IR of this compound at 2580
and 2545 cm−1 is in agreement with a closo structure of
the o-carboranyl fragment as is the 11B-NMR, which
display a pattern of intensity resonances of 2:3:5 in the
range −3/−10 ppm in agreement with a C26 symme-
try. This implies that one of the aromatic rings of each
phosphorus is above the mirror plane defined by the
two phosphorus and the two cluster carbon atoms
while the second is below. This plane also does contain
the PdCl2 fragment. To unambiguously proof the struc-
ture of this compound, a single crystal X-ray study was
performed.
Fig. 1. Perspective view of complex unit of [PdCl2(1,2-(PPh2)2-1,2-
C2B10H10)]·CH2Cl2. Thermal displacement ellipsoids are drawn at
20% probability level.
Table 1
,
Selected bond lengths (A) and angles (°) for [PdCl2(1,2-(PPh2)2-1,2-
C2B10H10)]·CH2Cl2
Bond lengths
PdꢀP1
PdꢀP2
2.2325(13)
2.2284(14)
2.3453(14)
2.3423(13)
1.876(4)
1.818(4)
1.807(4)
1.870(4)
1.809(4)
PdꢀCl1
PdꢀCl2
P1ꢀC1
P1ꢀC13
P1ꢀC19
P2ꢀC2
P2ꢀC25
P2ꢀC31
C1ꢀC2
1.814(4)
1.695(5)
The carborane cage in [PdCl2(1,2-(PPh2)2-1,2-
C2B10H10)]·CH2Cl2 is coordinated bidentately through
P atoms to the Pd(II) ion. Two chloride ions at cis
positions fulfil the slightly distorted square-planar coor-
dination around the metal. A perspective view of the
complex unit is given in Fig. 1 and selected bond
lengths and angles are listed in Table 1. PdꢀCl distances
Bond angles
P2ꢀPdꢀP1
P2ꢀPdꢀCl2
P1ꢀPdꢀCl2
P2ꢀPdꢀCl1
P1ꢀPdꢀCl1
Cl2ꢀPdꢀCl1
C2ꢀC1ꢀP1
B4ꢀC1ꢀP1
B5ꢀC1ꢀP1
B3ꢀC1ꢀP1
B6ꢀC1ꢀP1
C1ꢀC2ꢀP2
B7ꢀC2ꢀP2
B11ꢀC2ꢀP2
B3ꢀC2ꢀP2
B6ꢀC2ꢀP2
92.44(5)
87.24(5)
175.64(4)
173.65(4)
86.97(5)
93.82(5)
113.4(3)
125.6(3)
124.3(3)
115.8(3)
114.6(3)
114.6(2)
125.1(3)
124.2(3)
115.8(3)
115.4(3)
,
(2.3453(14) and 2.3423(13) A) are equal within experi-
mental errors, as well as PdꢀP distances (2.2325(13) and
,
2.2284(14) A). Angles around Pd do not deviate much
from values for a regular square-planar coordination
geometry.
The bond lengths in the coordination sphere of
[PdCl2(1,2-(PPh2)2-1,2-C2B10H10)]·CH2Cl2 agree well
with the corresponding values in [PdCl2(dppe)]·CH2Cl2
[4]; the PdꢀP bonds are equal within experimental
errors and the PdꢀCl distances are only slightly longer
in the compared compound. The difference in the
PdꢀCl distances probably originates from different
trans influence of the P atoms. Also, as a matter of
comparison, PdꢀP and PdꢀCl distances in [PdCl2(1,2-
(PPhCl)2-1,2-C2B10H10)]·2THF are both slightly shorter
than in [PdCl2(1,2-(PPh2)2-1,2-C2B10H10)]·CH2Cl2 [5].
The difference can be explained by the electron-
A nucleophilic attack by ethanol to the more positive
boron atoms, either B3 or B6, takes place producing a
mononegative chelating ligand. This and the chloride
compensate the Pd positive charge producing a neutral
Pd complex. Besides alcohols, other nucleophilic sol-
vents may also produce the deboronation reaction.

S. Paa6ola et al. / Journal of Organometallic Chemistry 606 (2000) 183–187
185
withdrawing capacity of Cl atoms bonded to P in the
former complex.
1H-NMR spectra indicates that in [PdCl2(1,2-(PiPr2)2-
1,2-C2B10H10)] two methyl groups in each isopropyl
group are not equivalent (Fig. 2). Two methyl groups
appear at the same chemical shift but the coupling
constants 3J(H,H) and 3J(P,H) are different. Their
values are 6.9 and 24.1 Hz for one methyl group, and
11.7 and 7.1 Hz for the other one. The 13C{1H} spec-
trum shows two different resonances at 21.29 and 20.00
ppm, which agree and support two different methyl
groups in each isopropyl group. Contrarily to the syn-
thesis of [PdCl2(1,2-(PPh2)2-1,2-C2B10H10)], a minor
quantity of the deboronated species [Pd2(m-Cl)2{7,8-
(PiPr2)2-7,8-C2B9H10}2] was obtained. Precise confirma-
tion of the nature of [Pd2(m-Cl)2-{7,8-(PiPr2)2-
7,8-C2B9H10}2] was obtained by comparing the cell
dimensions of obtained crystals with this of a pure
sample [3c].
To know what effect a ‘mild’ nucleophile could pro-
duce in a hypothetical separation process, [PdCl2(1,2-
(PiPr2)2-1,2-C2B10H10)] was refluxed for 5–10 min in
acetonitrile. In this case [PdCl2(1,2-(PiPr2)2-1,2-
C2B10H10)] and [Pd2(m-Cl)2{7,8-(PiPr2)2-7,8-C2B9H10}2]
were obtained in comparable quantities, largely depend-
ing on the refluxing time. No attempt was made to
separate this mixture as [Pd2(m-Cl)2{7,8-(PiPr2)2-7,8-
C2B9H10}2] can be easily produced from 1,2-(PiPr2)2-
1,2-C2B10H10 and [PdCl2(PhCN)2] in deoxygenated
ethanol, as was earlier reported [3c].
Comparison of configuration of the carborane ligand
in [PdCl2(1,2-(PPh2)2-1,2-C2B10H10)]·CH2Cl2 and this in
the free 1,2-(PPh2)2-1,2-C2B10H10 ligand reveals notice-
able differences. In the free ligand the P1ꢀC1ꢀC2ꢀP2
torsion angle is −10.9(3)° [6]. Moreover, the mutual
orientations of the phenyl groups compared to the
carborane cage are quite different, and thus, symmetry
deviates markedly from C26. Coordination of the ligand
to Pd(II) changes orientation of the phenyl groups
considerably. Symmetry of the ligand in the complex,
as well as that of the complex unit, in [PdCl2(1,2-
(PPh2)2-1,2-C2B10H10)]·CH2Cl2 is approximately C26
and the P1–C1–C2–P2 torsion angle is 0.4(3)°. In
addition, due to coordination, the C1–C2 distance
,
shortens from 1.722(4) A in the free ligand to 1.695(5)
,
A in the complex.
It seems clear that avoiding nucleophilic agents the
closo nature of the cage can be preserved. To proof so,
we have used ‘the safe’ CH2Cl2 to synthesize [PdCl2(1,2-
(PiPr2)2-1,2-C2B10H10)]. We had chosen the ꢀPiPr2 frag-
ment to produce a more nucleophilic o-carboranyl-
phosphine than 1,2-(PPh2)2-1,2-C2B10H10, and see if this
had some effect on the deboronation of the complex.
The reaction of 1,2-(PiPr2)2-1,2-C2B10H10 with
[PdCl2(cod)] was performed in CH2Cl2 as for
[PdCl2(1,2-(PPh2)2-1,2-C2B10H10)]. As the 11B-NMR
demonstrated, the closo nature of the carborane cluster
was preserved, and 11B-NMR resonances in the range
0/−10 ppm were found. Thus, a structure similar to
that of [PdCl2(1,2-(PPh2)2-1,2-C2B10H10)] is expected.
As a conclusion, we believe it is of outmost impor-
tance for producing pure samples of these C-substituted
closo carboranyl compounds, to use dry non-nucle-
ophilic solvents to perform the reaction, even avoiding
Fig. 2. Methyl signal region in the 1H-NMR spectra of [PdCl2(1,2-(PiPr2)2-1,2-C2B10H10)].

186
S. Paa6ola et al. / Journal of Organometallic Chemistry 606 (2000) 183–187
the eventual use of alcohols or nucleophilic agents in
purification, which in more or less extent will produce
deboronation of the cluster in the complex. We would
also extend these precautions to the syntheses of other
complexes already reported with transition metals other
than Pd as it is most possible that the same problem
occurs [7].
4.38. Found: C, 45.22; H, 4.30. IR: w (cm−1)=3061
(CarylꢀH), 2615, 2624, 2545, 2580 (BꢀH), 1437, 1096,
1
1075, 686, 506 (phosphines). H-NMR (CD2Cl2, 25°C):
l=8.26 (m, Haryl, 8H), 7.72–7.68 (m, Haryl, 4H), 7.63–
7.58 (m, Haryl, 8H), 3.25–1.17 (br, BꢀH). 1H{11B}-
NMR (CD2Cl2, 25°C): l=8.26 (m, Haryl
, 8H),
7.72–7.68 (m, Haryl, 4H), 7.63–7.58 (m, Haryl, 8H), 2.62
(br s, BꢀH, 2H), 2.44 (br s, BꢀH, 2H), 2.24 (br s, BꢀH,
2H), 2.08 (br s, BꢀH, 4H). 13C{1H}-NMR (CD2Cl2,
25°C): l=136.06 (m, o-Caryl), 133.67 (s, p-Caryl), 128.74
(m, m-Caryl), 125.85 (d, 1J(C,P)=4.1, ipso-Caryl), 125.05
3. Experimental
1
1
3.1. Instrumentation
(d, J(C,P)=2.8, ipso-Caryl), 87.31 (t(1:1:1), J(C,P)=
13.8, Ccluster). 11B-NMR (CD2Cl2, 25°C): l= −3.0 (d,
2B, 1J(B,H)=144), −3.5 (d, 3B, 1J(B,H)=160),
−10.03 (5B). 31P{1H}-NMR (CD2Cl2, 25°C): l=78.30
(s, PPh2).
Elemental analyses were performed using a Carlo
Erba EA1108 microanalyser. IR spectra were recorded
with KBr pellets on a Shimadzu FTIR-8300 spec-
1
1
trophotometer. H- and H{11B}-NMR (300.13 MHz),
13C{1H}-NMR (75.47 MHz), 31P{1H}-NMR (121.48
MHz) and 11B-NMR (96.29 MHz) spectra were
recorded with a Bruker ARX 300 instrument equipped
with the appropriate decoupling accessories. Chemical
shift values for 11B-NMR spectra were referenced to
external BF3·OEt2 and those for 1H-, 1H{11B}- and
13C{1H}-NMR spectra were referenced to SiMe4.
Chemical shift values for 31P{1H}-NMR spectra were
referenced to external 85% H3PO4. Chemical shifts are
reported in units of parts per million downfield from
tetramethylsilane, and all coupling constants are re-
ported in Hz.
3.4. Synthesis of [PdCl2(1,2-(PPh2)2-1,2-C2B10H10)]
(method B)
A mixture of 1,2-(PPh2)2-1,2-C2B10H10 (0.10 g, 0.20
mmol) and [PdCl2(PhCN)2] (0.077 g, 0.20 mmol) in
toluene (10 ml) was refluxed for 24 h. After filtration
the solid was washed with dichloromethane until the
washing solution was colourless. Clear solution was
obtained by filtration through Celite. The filtrate was
concentrated in vacuo. Layering with petroleum ether
precipitated solid product (0.09 g, 64%). Characteriza-
tion was as for method A.
3.2. Materials
3.5. Synthesis of [PdCl2(1,2-(PiPr2)2-1,2-C2B10H10)]
Unless otherwise noted, all manipulations were car-
ried out under a dinitrogen or argon atmosphere using
standard vacuum line techniques. Diethyl ether and
toluene were distilled from sodium benzophenone prior
to use. Dichloromethane was dried over molecular
sieves and deoxygenated prior to use, and the rest of
the solvents were of reagent grade quality and were
used without further purification. [PdCl2(cod)] [8] and
[PdCl2(PhCN)] [9] were prepared according to the liter-
ature methods. 1,2-(PPh2)2-1,2-C2B10H10 [10] and 1,2-
(PiPr2)2-1,2-C2B10H10 [11] were synthesised by
previously published methods.
1,2-(PiPr2)2-1,2-C2B10H10 (0.10 g, 0.27 mmol) and
[PdCl2(cod)] (0.077 g, 0.27 mmol) were dissolved in
dichloromethane (12 ml). The mixture was refluxed for
24 h. The solvent was evaporated and the obtained
solid was washed with diethyl ether and dried in vacuo
(0.42 g, 96%). Anal. Calc. for C14H38B10Cl2P2Pd: C,
30.36; H, 6.92. Found: C, 30.88; H, 6.88. IR (KBr): w
(cm−1)=2993, 2931, 2875 (CꢀH (PiPr)), 2636, 2576
(BꢀH), 1455, 1386, 1249, 1074, 1040, 877, 657, 638, 505
(phosphine). 1H-NMR (CD2Cl2, 25°C): l=1.70 (dd,
3J(H,H)=6.9, 3J(P,H)=24.1, 12H), 1.70 (dd,
3J(H,H)=11.7, 3J(P,H)=7.1, 12H), 2.10–2.08 (m,
4H). 13C{1H}-NMR (CD2Cl2, 25°C): l=86.58 (Ccluster),
1
1
3.3. Synthesis of [PdCl2(1,2-(PPh2)2-1,2-C2B10H10)]
(method A)
31.86 (d, J(C,P)=9.7, PꢀCH), 31.72 (d, J(C,P)=9.7,
PꢀCH), 21.29 (s, CH3), 20.00 (s, CH3). 11B{1H}-NMR
1
(CD2Cl2, 25°C): l= −0.4 (d, J(B,H)=83, 2B), −3.4
1
1
A mixture of 1,2-(PPh2)2-1,2-C2B10H10 (0.20 g, 0.39
mmol) and [PdCl2(cod)] (0.11 g, 0.39 mmol) in
dichloromethane (24 ml) was stirred at room tempera-
ture for 20 min prior refluxing for 24 h. The reaction
mixture was cooled and filtered through Celite. The
filtrate was dried in vacuo. The obtained solid was
washed with diethyl ether and dried in vacuo (0.26 g,
96%). Anal. Calc. for C26H30B10Cl2P2Pd: C, 45.26; H,
(d, J(B,H)=153, 2B), −9.9 (d, J(B,H)=153, 6B).
31P{1H}-NMR (CD2Cl2, 25°C): l=69.10 (s, PiPr2).
3.6. Synthesis of
[Pd2(v-Cl)2{7,8-(PiPr2)2-7,8-C2B9H10}2]
[PdCl2(1,2-(PiPr2)2-1,2-C2B10H10)] produced as above
was refluxed in acetonitrile for 5–10 min. The mixture

S. Paa6ola et al. / Journal of Organometallic Chemistry 606 (2000) 183–187
187
Table 2
hydrogen atoms were included in the calculations at
fixed distances from their host atoms and treated as
riding atoms using the SHELX-97 default parameters.
Experimental parameters are listed in Table 2.
Crystallographic data for [PdCl2(1,2-(PPh2)2-1,2-C2B10H10)]·CH2Cl2
Empirical formula
Formula weight
C27H32B10Cl4P2Pd
774.77
,
Wavelength (A)
0.71069
Triclinic
Crystal system
Space group
(
P1 (no. 2)
4. Supplementary material
Unit cell dimensions
,
a (A)
12.312(4)
13.797(4)
10.999(5)
110.58(2)
99.45(3)
86.36(3)
1725.4(11)
2
1.491
9.61
6239
397
,
b (A)
Crystallographic data (excluding structure factors)
for the structure reported in this paper have been
deposited with the Cambridge Crystallographic Data
Centre, CCDC no. 139282. Copies of this information
may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(Fax: +44-1223-336033; e-mail: deposit@ccdc.cam.ac.
uk or www:http://www.ccdc.cam.ac.uk).
,
c (A)
h (°)
i (°)
k (°)
V (A )
3
,
Z
Dcalc (g cm−3
)
v (cm−1
)
Number of unique reflections
Number of parameters
Goodness-of-fit on F2
R1(Fo) a [I\2|(I)]
1.061
0.0478
Acknowledgements
wR2(F2o) b [I\2|(I)]
0.1290
−3
1.63 and −1.68 c
,
Largest differential peak and hole (e A
)
This work was supported by Academy of Finland
(project 41519, SP and RK) and project MAT98-0921
(CV and FT).
a R1=SꢀꢀFoꢀ−ꢀFcꢀꢀ/SꢀFoꢀ.
b wR2=[Sw(ꢀFo2ꢀ−ꢀFc2ꢀ)2/SwꢀF2oꢀ2]1/2
.
c
,
Peak coordinates x=0.3896; y=0.1762; z=0.1825 (1.02 A from
,
Pd); hole coordinates x=0.3808; y=0.2091; z=0.1446 (0.95 A from
Pd).
References
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was filtered and the filtrate was dried in vacuo giving a
yellow–brown solid. Crystals were obtained from
CHCl3–CH2Cl2 (layering). Anal. Calc. for C14H38-
B9ClP2Pd: C, 33.13; H, 7.54. Found: C, 33.16; H, 7.29.
All other characterization was in agreement with litera-
ture data [3c].
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3.7. X-ray crystallographic study
[6] S. Paavola, R. Kiveka¨s, C. Vin˜as (unpublished results).
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Nauk. SSSR Ser. Khim. (1965) 932; Chem. Abst. 63 (1965)
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G. Allender, H.D. Smith Jr., Inorg. Chim. Acta 26 (1978) L38.
(e) W.E. Hill, B.G. Rackley, L.M. Silva-Trivino, Inorg. Chim.
Acta 75 (1983) 51. (f) J.G. Contreras, L.M. Silva-Trivin˜o, M.E.
Solis, Inorg. Chim. Acta 114 (1986) 51. (g) M. Kumada, K.
Sumitani, Y. Kiso, K. Tamao, J. Organomet. Chem. 50 (1973)
319. (h) M.E. Solis, M.S. Trivino, J.G. Contreras, Bol. Soc. Chil.
Quim. 27 (1982) 88; Chem. Abst. 97 (1982) 103204b.
[8] D. Drew, J.R. Doyle, Inorg. Synth. 28 (1990) 346.
[9] J.R. Doyle, P.E. Slade, H.B. Jonassen, Inorg. Synth. 6 (1960)
216.
Yellow crystals of [PdCl2(1,2-(PPh2)2-1,2-C2B10H10)]·
CH2Cl2 were grown from dichloromethane–n-hexane.
Single-crystal data collection was performed at −80°C
on a Rigaku AFC7S diffractometer using graphite
monochromatized Mo–Ka radiation. The unit cell
parameters were determined by least-squares refinement
of 25 carefully centred reflections. A total of 6552
reflections, giving 6239 independent reflections (Rint
0.0273) were collected by ꢀ/2q scan mode (2qmax
=
=
50.5o). The data obtained were corrected for Lorentz
and polarization effects. Correction for empirical ab-
sorption („ scan) was also applied. The structure was
solved by direct methods and refined by full-matrix
least squares on F2 techniques using the SHELX-97
program package [12]. Non-hydrogen atoms were
refined with anisotropic displacement parameters, and
[10] R.P. Alexander, H. Schroeder, Inorg. Chem. 2 (1963) 1107.
[11] F. Teixidor, C. Vin˜as, M.M. Abad, R. Nun˜ez, R. Kiveka¨s, R.
Sillanpa¨a¨, J. Organomet. Chem. 503 (1995) 193.
[12] G.M. Scheldrick, SHELX-97, Universita¨t Go¨ttingen, Go¨ttingen,
Germany, 1997.
.