Reaction of η2-enone and enal-platinum(0) complexes with Lewis acidic compounds

Article abstract of DOI:10.1016/j.jorganchem.2003.12.018

Reaction of η²-enone and enal-platinum(0) complexes Pt(CH₂=CHCOR)(PPh₃)₂ (R=H, Me) with Lewis acidic compounds BX₃ (X=F, C₆F₅) afforded adducts formed by coordination of boron to

Full text of DOI:10.1016/j.jorganchem.2003.12.018

Journal of Organometallic Chemistry 689 (2004) 894–898
www.elsevier.com/locate/jorganchem
Reaction of g2-enone and enal-platinum(0) complexes
with Lewis acidic compounds q
Masaki Morita, Katsuharu Inoue, Tomohiro Yoshida,
*
*
Sensuke Ogoshi , Hideo Kurosawa
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Yamadaoka 2-1, Suita, Osaka 565-0871, Japan
Received 13 October 2003; accepted 11 December 2003
Abstract
Reaction of g2-enone and enal-platinum(0) complexes Pt(CH2@CHCOR)(PPh3)2 (R ¼ H, Me) with Lewis acidic compounds
BX3 (X ¼ F, C6F5) afforded adducts formed by coordination of boron to oxygen of the carbonyl group. The X-ray structure de-
termination of the adduct formed from B(C6F5)3 and g2-methylvinylketone complex showed no strong interaction between Pt and
carbonyl carbon. In contrast to the inability of the palladium(0) g2-enone complexes to form any Me3Al adduct, g2-cyclohexe-
noneplatinum(0) complex formed an isolable adduct with Me3Al, the structure of which was also confirmed by X-ray analysis. The
NMR spectral parameters (Pt–C, Pt–P and P–P coupling constants) of these adducts were compared with those of the original
g2-enone or enal-platinum(0) complexes as well as the ordinary g3-allylplatinum cation [Pt(PPh3)2(MeCHCHCH2)]þ.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Platinum complex; g2-Enone complex; g2-Enal complex; Lewis acid
1. Introduction
higher stability compared to their palladium analogs and
to provide additional spectroscopic information due to
the presence of the NMR-active 195Pt nucleus. Here, we
report on the preparation and spectroscopic properties
of the platinum complexes by the reaction of g2-enone
and enal complexes with Lewis acids.
The transition metal-catalyzed conjugate addition of
various organometallic reagents, e.g., AlR3, ZnR2,
Cp2ZrRCl, InR3, and BR3, to a; b-unsaturated carbonyl
compounds is one of the most useful reactions in organic
synthesis and yet one of the least understood reactions
[1,2]. Recently, we reported [3] that the coordination of
Lewis acid, such as BR3 and AlR3, to g2-enone and enal
complexes of palladium led to continuous structure
variation from acid-coordinated g2-olefin type to zwit-
terionic g3-allyl type (Scheme 1). These Lewis acid ad-
ducts could be model complexes as intermediates in
transition metal-catalyzed conjugate addition of alkyl-
metals to a; b-unsaturated carbonyl compounds. Anal-
ogous platinum complexes can be expected to have a
2. Results and discussion
The reaction of the enone complex Pt(CH2@
CHCOCH3)(PPh3)2 with BF3 ꢀ OEt2 or B(C6F5)3 gave
platinum complexes (1a, 1b) quantitatively, having the
expected composition in the elemental analysis (Eq. 1).
LA
-
LA
O
O
+
q Supplementary data associated with this article can be found, in the
online version, at doi:10.1016/j.jorganchem.2003.12.018.
* Corresponding authors. Tel.: +81-6-6879-7393; fax: +81-6-6879-
7394.
Pd
Pd
R3P
PR3
LA = BX3, AlX3
R3P
PR3
E-mail addresses: morita@chem.eng.osaka-u.ac.jp (M. Morita),
kurosawa@chem.eng.osaka-u.ac.jp (H. Kurosawa).
Scheme 1. Resonance forms of Lewis acid adducts.
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2003.12.018

M. Morita et al. / Journal of Organometallic Chemistry 689 (2004) 894–898
895
The X-ray structure analysis of 1b shows B(C6F5)3-
coordinated g2-enoneplatinum structure (Fig. 1), in
ꢀ
ꢀ
which the Pt–C(carbonyl) distance (2.97(1) A) is very
close to the corresponding distance (2.91(2) A) in the
acid-free g2-enone complex Pt(PhCH@CHCOCH3)
(PPh3)2 [4]. The overall structural features of 1b are
similar to those of the palladium analog Pd(PhCH@
CHCCH3(OB(C6F5)3))(PPh3)2 already reported [3]. The
reaction of the enal complex Pt(CH2@CHCHO)(PPh3)2
with BF3 ꢀ OEt2 led to isolation of the complex 2, which
existed as a mixture of two isomers (anti and syn; see Eq.
2) in solution. The anti form is the major isomer in solu-
tion, as confirmed by NOE measurements.
BX3
O
O
CH3
CH3
BX3
(1)
Pt
Pt
quant
Ph3P
PPh3
Ph3P
PPh3
Fig. 1. ORTEP drawing of 1b. Thermal ellipsoids are drawn at the 50%
probability level. All H atoms, phenyl groups and C6F5 groups
ꢀ
are omitted for clarity. Selected bond lengths (A) and angles (deg):
1a X = F, 1b X = C6F5
Pt–P1 ¼ 2.262(4), Pt–P2 ¼ 2.302(4), Pt–C1 ¼ 2.16(2), Pt–C2 ¼ 2.20(1),
Pt–C3 ¼ 2.97(1), C1–C2 ¼ 1.47(2), C2–C3 ¼ 1.37(2), C3–O ¼ 1.29(2),
O–B ¼ 1.51(2), P1–Pt–P2 ¼ 106.4(1).
BF3
O
H
O
H
H
O
BF3
BF3
+
Pt
Pt
Pt
(2)
quant
Ph3P
PPh3
Ph3P
PPh3
Ph3P
PPh3
squares plane determined by C1–C2–C3–O, where alu-
minum is positioned away from platinum. The Al–O–
C3–C2 torsion angle is )136°. The X-ray structure re-
ports on adducts between trialkyl or triarylaluminum
and carbonyl compounds have been rare, because it is
difficult to isolate these in the pure state due to the oc-
anti
2
syn
2'
O
O
AlMe3
AlMe3
quant
(3)
Pt
Pt
Ph3P
PPh3
Ph3P
PPh3
3
In the previous study on a series of palladium(0)-
Lewis acid adducts, any adduct was not isolated by
using Me3Al, the acidity of which is considerably weaker
than other acids employed [3]. Reaction of platinum(0)
g2-cyclohexenone complex with Me3Al afforded an
isolable adduct 3 (Eq. 3). The isolation of 3 would have
been attained by the higher Lewis basicity of the car-
bonyl oxygen of the coordinated enone ligand in the
platinum than in the palladium complexes. The plati-
num(0)-olefin bond is expected to contain the greater p
back bond component than the palladium(0)-olefin
bond [5], suggesting the higher electron density accu-
mulated on the olefinic part as well as on the carbonyl
substituent in platinum than in palladium complexes [6].
The X-ray structure analysis of 3, though not accurate
enough for detailed discussion of bond length, showed
occurrence of expected Al–O interaction (Fig. 2). The
Fig. 2. ORTEP drawing of 3. Thermal ellipsoids are drawn at the 50%
probability level. All H atoms and phenyl groups are omitted for
ꢀ
clarity. Selected bond lengths (A) and angles (deg): Pt–P1 ¼ 2.251(9),
ꢀ
Pt–C(carbonyl) distance (3.04(5) A) is too long to sug-
Pt–P2 ¼ 2.321(9), Pt–C1 ¼ 2.11(3), Pt–C2 ¼ 2.23(4), Pt–C3 ¼ 3.04(5),
C1–C2 ¼ 1.45(5), C2–C3 ¼ 1.30(6), C3–O ¼ 1.19(5), O–Al ¼ 1.80(3),
P1–Pt–P2 ¼ 110.3(3).
gest the g3-allyl electronic structure. There is a signifi-
cant deviation of the aluminum atom from the least

896
M. Morita et al. / Journal of Organometallic Chemistry 689 (2004) 894–898
currence of the fast transfer of the organic group from
aluminum to the coordinated carbonyl substrate [7].
The degree of the contribution of the g3-coordination
mode to the structure of the Lewis acid adducts with
enone or enal complexes in solution could be evaluated
from 13C and 31P NMR data. In the previous study on
the palladium analogs, the chemical shift of the carbonyl
carbon was used as a criterion for estimating the degree
of contribution of the g3-allyl structure to the overall
structure of the Lewis acid adducts [3]. The higher
chemical shift of the carbonyl carbon resonance was
correlated with the greater g3-allyl contribution. The
chemical shift of the carbonyl carbon in 1 (192.3 in 1a;
204.3 in 1b) is much the same as that (202.2) in the
original acid-free enone complex Pt(CH2@CHC-
OCH3)(PPh3)2, while the corresponding resonance in 2
(162.2) is considerably upfield shifted from the original
platinum(0)-enal complex Pt(CH2@CHCHO)(PPh3)2
(193.1). Also, in the palladium series, there is another
empirical rule; the P–P coupling increased from the
smallest values for acid-free Pd(0) enone complexes, e.g.
Pd(CH2@CHCOCH3)(PPh3)2 (12.2 Hz) [8] through
Lewis acid adducts (13.5–37.4 Hz) [3] to the largest
values for ordinary g3-allylpalladium(II) complexes, e.g.
[Pd(g3-PhCHCHCH2)(PPh3)2]þ (46.5 Hz) [3]. A varia-
tion of the P–P coupling according to the type of the
complex was also observed in the platinum series, al-
though the order of the amount of P–P coupling con-
stant is completely reversed compared to the palladium
series. Thus, the P–P couplings of 1 (17.1 Hz in 1a; 18.9
Hz in 1b) are smaller than that (37.8 Hz) of
Pt(CH2@CHCOCH3)(PPh3)2, but larger than that (9.0
Hz) of the g3-allylplatinum cation [Pt(g3-MeCH-
CHCH2)(PPh3)2]þ [9]. The P–P coupling constant of 2
(5.8 Hz), which is far from that of the acid-free enal
complex (37.8 Hz), is closer to that of the g3-allylplati-
num cation than those of 1 are. These trends in the
carbonyl carbon shifts and P–P coupling constants ap-
pear to suggest the greater contribution of the g3-allyl
structure in 2 than in 1. That the enal-acid adduct
contains the greater g3-allyl character than the enone-
acid adduct was also noted in the analogous palladium
series [3].
It should be pointed out, however, that the P–P
coupling constant may be affected by some unspecified
factors. For instance, it would be affected by the P–M–P
angle, which in turn is influenced by the steric bulk of
the other ligand groups. Note that the P–P coupling
constant of 2 is 5.8 Hz, while that of 20 is 15.6 Hz (see
Section 3). Before the factors responsible for the varia-
tion of the P–P coupling are elucidated, there remains
ambiguity in relying on this parameter for assessing the
degree of contribution, perhaps very small in nature, of
the g3-allyl structure to Lewis acid adducts of M(0)-
enone or enal complexes.
Comparison of the Pt–C and Pt–P coupling constants
between 1a or
2
and their parent complexes
Pt(CH2@CHCOR)(PPh3)2 shown in Scheme 2 seems
also interesting. Upon complexation of BF3 to the car-
bonyl oxygen, the Pt–C couplings for the olefinic car-
bons become smaller, with the particular attention being
paid to the Pt–C coupling for the inner olefin-carbon
that is remarkably smaller than that of the acid-free
complex. Moreover, the Pt–P coupling for the phos-
phorus nucleus located trans to the inner olefin-carbon
becomes considerably larger upon BF3 complexation.
Apparently the interaction between Pt and the inner
olefin-carbon becomes much weaker upon the Lewis
acid adduct formation [10].
There is another puzzling aspect in Pt–C coupling.
Any spin–spin coupling larger than 15 Hz (the full width
at half maximum) could not be observed between Pt and
the carbonyl carbon of 2, where the corresponding Pt–C
coupling in the acid-free enal complex is larger (46 Hz).
These observations are somewhat in contradiction to an
idea suggested by the trend in the carbonyl carbon
chemical shift that the carbonyl carbon interacts with Pt
to some extent in the Lewis acid adduct 2 (see above). The
decrease of Pt–C(carbonyl) coupling, though smaller in
difference, is also observed upon formation of 1a from
Pt(CH2@CHCOCH3)(PPh3)2. The Pt–C couplings of the
type shown in the Scheme 2 would be functions of several
factors, and more extensive work is clearly necessary for a
better understanding of the correlation between elec-
tronic structure and spectroscopic features of adducts
from M(0)-enone or enal complex and Lewis acids.
BF3
O
BF3
O
≤15
O
29
CH3
O
46
H
48
CH3
H
179
4590
198
4708
218
4213
208
4113
ca. 20
3657
51
3588
PPh3
150
162
3571
PPh3
Pt
2
Pt
Pt
Pt
3588
Ph3P
Ph3P
PPh3
Ph3P
Ph3P
PPh3
1a
Scheme 2. Comaparison of J(Pt–C) and J(Pt–P).

M. Morita et al. / Journal of Organometallic Chemistry 689 (2004) 894–898
897
3. Experimental
with hexane and recrystallized from TFH/hexane solu-
1
tion to give 195.1 mg of 1b in 54% isolated yield. H
General. All manipulations were conducted under a
nitrogen atmosphere using standard Schlenck or drybox
techniques. 1H, 31P and 13C nuclear magnetic resonance
spectra were recorded on JEOL GSX-270S and JEOL
AL-400 spectrometers. The chemical shifts in the 1H
nuclear magnetic resonance spectra were recorded rela-
tive to Me4Si, or C6D6 (d 7.16). The chemical shifts in
the 13C spectra were recorded relative to Me4Si, C6D6 (d
128) or CD2Cl2 (d 53.8). The chemical shifts in the 31P
spectra were recorded using 85% H3PO4 as an external
standard. Elemental analyses were performed at the
Instrumental Analysis Center, Faculty of Engineering,
Osaka University. X-ray crystal data were collected by a
Rigaku RAXIS-RAPID Imaging Plate diffractometer.
Materials. Unless indicated otherwise, all solvents
used in this work were distilled prior to use. THF,
hexane and C6D6 were distilled from sodium benzo-
phenone ketyl, CD2Cl2 from CaH2. All commercially
available reagents were distilled and degassed prior to
use. B(C6F5)3 (3.9 wt% PF-3/Isoper E solution) was
donated by Asahi Glass Co.
NMR (C6D6): d 1.07 (d, JHP ¼ 7:2 Hz, 3H), 1.99 (ddd,
JHH ¼ 1:7; 16:0 Hz, JHP ¼ 6:9 Hz, 1H), 2.85 (dddd,
JHH ¼ 1:7; 7:8 Hz, JHP ¼ 4:0; 11:7 Hz, 1H), 3.79
(ddd, JHH ¼ 7:8; 16:0 Hz, JHP ¼ 7:9 Hz, 1H), 6.74–6.91
(m, 24H), 7.19–7.23 (m, 6H). 31P NMR (C6D6): d 27.22
(d, JPP ¼ 18:9 Hz, JPPt ¼ 4762 Hz), 28.65 (d, JPP ¼ 18:9
Hz, JPPt ¼ 3566 Hz). 13C NMR (C6D6): d 24.1 (s), 38.7
(d, JCP ¼ 37:5 Hz, JCPt ¼ 192:1 Hz), 64.3 (dd,
JCP ¼ 8:7; 5:1 Hz, JCPt ¼ 67:0 Hz), 127.6–150.2 (m),
204.3 (br, JCPt ¼ 30:2 Hz). Anal. Calc. for C58H36
BF15OP2Pt: C, 53.52; H, 2.79. Found: C, 53.20; H, 3.15.
3.3. Synthesis of (CH2CHCH(OBF3))Pt(PPh3)2
(2=20 ¼ 88=12)
To a solution of Pt(CH2@CH2)(PPh3)2 (144.1 mg,
0.193 mmol) in 4 ml of THF was added 15.0 ll of
CH2@CHCHO (12.6 mg, 0.225 mmol) and 26.0 ll of
BF3 ꢀ OEt2 (29.2 mg, 0.205 mmol) at room temperature.
The reaction mixture was concentrated in vacuo to give
yellow solids quantitatively. The solids were washed
with hexane to give 140.0 mg of 2/20 in 88% isolated
yield. An analytical sample was prepared by recrystal-
lization from THF/hexane solution. 2. 1H NMR (C6D6):
d 2.19 (ddd, JHH ¼ 3:6; 12:8 Hz, JHP ¼ 7:3 Hz, 1H), 2.72
(ddd, JHH ¼ 4:3; 8:1; 12:8 Hz, 1H), 3.73 (dd,
JHH ¼ 3:6; 8:1 Hz, 1H), 6.83–7.12 (m, 18H), 7.30–7.48
(m, 12H). 31P NMR (C6D6): d 20.86 (d, JPP ¼ 5:8 Hz,
JPPt ¼ 3657 Hz), 26.94 (d, JPP ¼ 5:8 Hz, JPPt ¼ 4590
Hz). 13C NMR (C6D6): d 40.0 (d, JCP ¼ 36:5 Hz,
JCPt ¼ 179:2 Hz), 71.4 (br, JCPt ¼ ca. 20 Hz), 127.6–135.0
(m), 162.2 (br). 20. 1H NMR (C6D6): d 1.70(m, 1H), 2.46
(m, 1H), 3.32 (m, 1H). The other resonances are hidden
by those of the major isomer. 31P NMR (C6D6): d 27.11
(d, JPP ¼ 15:6 Hz, JPPt ¼ 4884 Hz), 30.25 (d, JPP ¼ 15:6
Hz, JPPt ¼ 3497 Hz). Anal. Calc. for C39H34BF3OP2Pt:
C, 55.53; H, 4.06. Found; C, 55.24; H, 3.89.
3.1. Synthesis of (CH2CHCCH3(OBF3))Pt(PPh3)2 (1a)
To a solution of Pt(CH2@CH2)(PPh3)2 (201.4 mg,
0.269 mmol) in 10 ml of THF was added 44.5 ll of
CH2@CHCOCH3 (37.5 mg, 0.535 mmol) and 33.7 ll of
BF3 ꢀ OEt2 (37.7 mg, 0.266 mmol) at room temperature.
The reaction mixture was concentrated in vacuo to give
yellow solids quantitatively. The solids were washed
with hexane to give 218.8 mg of 1a in 95% isolated yield
and recrystallized from THF/hexane solution to give
1
yellow solids (111.6 mg, 48%). H NMR (C6D6): d 1.68
(d, JHP ¼ 7:3 Hz, 3H), 1.94 (ddd, JHH ¼ 6:9; 10:5 Hz,
JHP ¼ 6:5 Hz, 1H), 2.89 (ddd, JHH ¼ 8:6; 10:5 Hz,
JHP ¼ 4:5 Hz, 1H), 3.60 (dd, JHH ¼ 6:9; 8:6 Hz, 1H),
6.83–7.04 (m, 24H), 7.33–7.43 (m, 6H). 31P NMR
(C6D6): d 26.36 (d, JPP ¼ 17:1 Hz, JPPt ¼ 3588 Hz),
28.51 (d, JPP ¼ 17:1 Hz, JPPt ¼ 4708 Hz). 13C NMR
(CHCHC(OAlMe )CH CH CH )
3.4. Synthesis of
(PPh3)2 (3)
Pt
2
3
2
2
(CD2Cl2):
d
22.5 (s), 38.8 (d, JCP ¼ 37:9 Hz,
JCPt ¼ 198:3 Hz), 68.4 (t, JCP ¼ 6:4, JCPt ¼ 50:7 Hz),
128.7–134.6 (m), 192.3 (br, JCPt ¼ 29:3 Hz). Anal. Calc.
for C40H36BF3OP2Pt: C; 56.02, H; 4.23. Found: C,
55.72; H, 4.39.
To a solution of Pt(CH2@CH2)(PPh3)2 (105.3 mg,
0.141 mmol) in 5 ml of THF was added 13.7 ll of cy-
clohexenone (13.6 mg, 0.141 mmol) and 0.14 ml (1.00
M) of a solution of AlMe3 in hexane at room temper-
ature. The reaction mixture was concentrated in vacuo
to give yellow solids quantitatively. The solids were
washed with hexane and recrystallized from THF/hex-
3.2. Synthesis
Pt(PPh3)2 (1b)
of
(CH2CHCCH3(OB(C6F5)3))
1
To a solution of Pt(CH2@CH2)(PPh3)2 (206.5 mg,
0.276 mmol) in 8 ml of THF was added 46.1 ll of
CH2@CHCOCH3 (38.8 mg, 0.554 mmol) and 5.0 ml of
B(C6F5)3 (142.0 mg, 0.277 mmol) at room temperature.
The reaction mixture was concentrated in vacuo to give
yellow solids quantitatively. The solids were washed
ane solution to give yellow crystals (71.6 mg, 57%). H
NMR (C6D6): d )0.30 (s, 9H), 0.86 (m 1H), 1.23 (m,
1H), 1.75 (m, 1H), 1.89 (m, 1H), 2.32 (m, 1H), 2.42 (m,
1H), 3.05 (m, 1H), 4.30 (t, JHP ¼ 6:8 Hz, J ¼ 29:4 Hz,
1H), 6.82–7.03 (m, 18H), 7.31–7.33(m, 12H). 31P NMR
(C6D6): d 22.44 (d, JPP ¼ 33:0 Hz, JPPt ¼ 4741 Hz),

898
M. Morita et al. / Journal of Organometallic Chemistry 689 (2004) 894–898
31.34 (d, JPP ¼ 33:0 Hz, JPPt ¼ 3289 Hz). For this
compound, accurate elemental analyses were precluded
by extremely air sensitivity and/or systematic problems
with elemental analysis of organometallic compounds
[11].
Acknowledgements
This work was supported by Grant-in-Aid for Sci-
entific Research on Priority Areas (Reaction Control
of Dynamic Complexes) from Ministry of Education,
Science, Sports, and Culture, Japan.
3.5. X-ray structure determination
Summary of crystal data, data collection, and struc-
ture refinement parameters for complex 1b and 3 is listed
in Table 1 and Table 2, respectively.
References
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Table 1
X-ray data for complex 1b
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Empirical formula
Formula weight
Crystal dimensions
Crystal system
2h range
C58H36F15OBP2Pt
1301.75
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0.25 ꢁ 0.25 ꢁ 0.25 mm
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ꢀ
ꢀ
Lattice parameters
a ¼ 11:1845ð2Þ A
b ¼ 14:7241ð2Þ A
(g) K. Soai, T. Hayasaka, S. Ugajin Soc, J. Chem. Chem.
Commun. (1989) 516;
ꢀ
c ¼ 17:4782ð6Þ A
a ¼ 65:804ð1Þ°
b ¼ 84:084ð1Þ°
c ¼ 82:8979ð9Þ°
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ꢁ
(i) I. Perez, J.P. Sestelo, M.A. Maestro, L.A. Sarandeses, J. Org.
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3
ꢀ
V ¼ 2601:0ð1Þ A
P-1 (No. 2)
2
Space group
Z value
Dcalcd
F000
Radiation
(j) C.S. Cho, S.-I. Motofusa, K. Ohe, S. Uemura, J. Org. Chem.
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1.662 g/cm3,
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1280.00
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Mo Ka (k ¼ 0:71069 A)
(l) Y. Takaya, M. Ogasawara, T. Hayashi, M. Sakai, N. Miyaura,
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Temperature
No. of reflections measured
0.0 °C
Total: 24868
Unique: 11767
0.076; 0.088
1.99
(m) T. Nishikata, Y. Yamamoto, N. Miyaura, Angew. Chem.,
Int. Ed. 42 (2003) 2768.
Residuals: R; Rw
Goodness-of-fit indicator
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5052.
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Table 2
X-ray data for complex 3
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Empirical formula
Formula weight
Crystal dimensions
Crystal system
2h range
C45H47AlOP2Pt
887.88
[5] F. Nunzi, A. Sgamellotti, N. Re, C. Floriani, J. Chem. Soc.,
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0.50 ꢁ 0.25 ꢁ 0.25 mm
monoclinic
[6] In fact, the resonances of olefinic carbons in Pt(CH2@CHC-
OCH3)(PPh3)2 (d 38.4, 60.3) were observed at the higher magnetic
field than those in the palladium analog (d 52.4, 72.8).
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Chem. Cryst. 29 (1999) 993;
3.9–55.0°
ꢀ
Lattice parameters
a ¼ 17:210ð3Þ A
ꢀ
b ¼ 14:000ð3Þ A
ꢀ
c ¼ 18:476ð4Þ A
b ¼ 116:768ð9Þ°
(c) M.R.P. van Vliet, G. van Koten, M.A. Rottenveel, M. Schrap,
K. Vrieze, B. Kojic-Prodic, A.L. Spek, A.J.M. Dulsenberg,
Organometallics 5 (1986) 1389.
3
ꢀ
V ¼ 3974ð1Þ A
P21/a (No. 14)
4
Space group
Z value
Dcalcd
F000
Radiation
[8] S. Ogoshi, M. Morita, H. Kurosawa, J. Am. Chem. Soc. 125
(2003) 9020.
1.484 g/cm3,
1784.00
[9] B. Crociani, F. Benetollo, R. Bertani, G. Bombieri, F. Meneghetti,
L. Zanotto, J. Organomet. Chem. 605 (2000) 28.
[10] The Pt–C coupling for the allyl center carbon in [Pt(g3-MeCH-
CHCH2)(PPh3)2]þ is small (24 Hz) compared to those for the allyl
terminal carbon (108 Hz) [8].
ꢀ
Mo Ka (k ¼ 0:71069 A)
Temperature
No. of reflections Measured
23.0 °C
Total: 26417
Unique: 8890
0.070; 0.089
3.91
Residuals: R; Rw
Goodness-of-fit indicator
[11] See the Supporting Information in the following: M.J. Carney,
P.J. Walsh, R.G. Bergman, J. Am. Chem. Soc. 112 (1990) 6426.