Reaction of Palladium and Platinum Complexes Bearing α,/β-Unsaturated Carbonyl Compounds with Carbon Electrophiles: Control over Site of Electrophilic Attack, Oxygen or Metal

Article abstract of DOI:10.1021/om034122m

The reaction of (η²-CH₂=CHCHO)ML₂ (M = Pd, Pt; L = PPh₃, L₂ = DPPF) with methyl triflate gave η³-methoxyallyl complexes [(η³-CH ₃OCHCHCH₂)ML₂][OTf]. X-ray diffraction analysis on [(η³-CH₃OCHCHCH₂)M(dppf)] [OTf] (M = Pd, Pt) showed a distorted η³-allyl structure. The enone complexes (η²-CH₂=CHCOCH₃)M(PPh ₃)₂ also reacted with methyl triflate to give [(η ³-CH₃OC(CH₃)CHCH₂)M(PPh ₃)₂] [OTf]. It was proposed that these complexes were formed by the direct electrophilic attack of methyl triflate at the carbonyl oxygen of the enal or enone ligand on the palladium and platinum. In fact, no insertion of acrolein into the platinum-methyl bond of the separately isolated methylplatinum complex proceeded. On the other hand, methyl iodide underwent oxidative addition with zerovalent enal or enone complexes to give methylmetal complexes concomitant with dissociation of an enal or enone molecule.

Full text of DOI:10.1021/om034122m

5468
Organometallics 2003, 22, 5468-5472
Rea ction of P a lla d iu m a n d P la tin u m Com p lexes Bea r in g
r,â-Un sa tu r a ted Ca r bon yl Com p ou n d s w ith Ca r bon
Electr op h iles: Con tr ol over Site of Electr op h ilic Atta ck ,
Oxygen or Meta l
Masaki Morita, Katsuharu Inoue, Sensuke Ogoshi,* and Hideo Kurosawa*
Department of Applied Chemistry, Faculty of Engineering, Osaka University,
Yamadaoka 2-1, Suita, Osaka 565-0871, J apan
Received August 22, 2003
The reaction of (η2-CH2dCHCHO)ML2 (M ) Pd, Pt; L ) PPh3, L2 ) DPPF) with methyl
triflate gave η3-methoxyallyl complexes [(η3-CH3OCHCHCH2)ML2][OTf]. X-ray diffraction
analysis on [(η3-CH3OCHCHCH2)M(dppf)][OTf] (M ) Pd, Pt) showed a distorted η3-allyl
structure. The enone complexes (η2-CH2dCHCOCH3)M(PPh3)2 also reacted with methyl
triflate to give [(η3-CH3OC(CH3)CHCH2)M(PPh3)2][OTf]. It was proposed that these complexes
were formed by the direct electrophilic attack of methyl triflate at the carbonyl oxygen of
the enal or enone ligand on the palladium and platinum. In fact, no insertion of acrolein
into the platinum-methyl bond of the separately isolated methylplatinum complex proceeded.
On the other hand, methyl iodide underwent oxidative addition with zerovalent enal or enone
complexes to give methylmetal complexes concomitant with dissociation of an enal or enone
molecule.
In tr od u ction
reagents, e.g., AlR3, ZnR2, and R3SiSiR3, to R,â-unsatur-
ated carbonyl compounds.
Both nucleophilic and electrophilic addition reactions
of organic reagents to transition metal complexes are
among the most important transformations in organo-
metallic chemistry.1 There are two reaction sites, the
metal center and coordinated ligands, which receive
both nucleophilic and electrophilic attacks. In the elec-
trophilic addition the attack at metal converts the
electrophile into a new metal-bound ligand (e.g., H+ to
hydride), while that at an unsaturated ligand modifies
this into the other (e.g., acyl + Me+ to carbene).
Recently, we reported that the addition of several
metallic electrophiles, such as a Lewis acid or Me3SiOTf,
to the carbonyl oxygen of R,â-unsaturated carbonyl
compounds coordinated to zerovalent palladium led to
the formation of η3-allyl complexes bearing a metalloxy
or siloxy group at the allyl terminal.2,3 These new
compounds served as model intermediates in palladium-
catalyzed conjugate addition of various organometallic
We also reported the reaction of η2-enal and enone
complexes of palladium and platinum with Brønsted
acid to give η3-1-hydroxyallyl complexes.4 It is conceiv-
able that in the case of the reaction of Brønsted acid
there is a greater chance of the electrophilic addition
to the metal center than the case of Lewis acid or Me3-
SiOTf addition. Nevertheless we obtained evidence for
the exclusive occurrence of the attack of a proton at the
oxygen. This prompted us to use carbon electrophiles5
next as the reagent in the reaction with the coordinated
enal or enone. Here, we report the reaction of palladium
and platinum complexes bearing R,â-unsaturated car-
bonyl compounds with some methyl electrophiles which
results in the electrophilic attack at the carbonyl oxygen
or the metal center depending on the nature of the
leaving group of the methyl substrate.
Resu lts a n d Discu ssion
(1) (a) Kurosawa, H., Yamamoto, A., Eds. Fundamentals of Molec-
ular Catalysis; Elsevier: Amsterdam, 2003; Chapter 8. (b) Crabtree,
R. H. The Organometallic Chemistry of the Transition Metals, 3rd ed.;
Wiley-VCH: New York, 2001; Chapter 8. (c) Collman, J . P.; Hegedus,
L. S.; Norton, J . R.; Finke, R. G. Principles and Applications of
Organotransition Metal Chemistry; University Science Books; Mill
Valley, CA, 1987; Chapter 8.
(2) Lewis acid: (a) Ogoshi, S.; Yoshida, T.; Nishida, T.; Morita, M.;
Kurosawa, H. J . Am. Chem. Soc. 2001, 123, 1944-1950. Me3SiOTf:
(b) Ogoshi, S.; Tomiyasu, S.; Morita, M.; Kurosawa, H. J . Am. Chem.
Soc. 2002, 124, 11598-11599.
(3) R,â-Unsaturated carbonyl compounds have been used as precur-
sors to η3-1-siloxyallyl complexes of a number of metals. Ni: (a)
J ohnson, J . R.; Tully, P. S.; Mackenzie, P. B.; Sabat, M. J . Am. Chem.
Soc. 1991, 113, 6172-6177. (b) Grisso, B. A.; J ohnson, J . R.; Mackenzie,
P. B. J . Am. Chem. Soc. 1992, 114, 5160-5165. Co: (c) Chatani, N.;
Yamasaki, Y.; Murai, S.; Sonoda, N. Tetrahedron Lett. 1983, 24, 5649-
5652. Mo: (d) Ward, Y. D.; Villanueva, L. A.; Allred, G. D.; Liebeskind,
L. S. Organometallics 1996, 15, 4201-4210. (e) Moretto, A. F.;
Liebeskind, L. S. J . Org. Chem. 2000, 65, 7445-7455.
The reaction of η2-acroleinpalladium complexes with
MeOTf in toluene at room temperature quantitatively
gave palladium complexes having expected compositions
1
in elemental analysis (eq 1). The H, 31P, and 13C NMR
indicate that these complexes have an η3-methoxyallyl
structure. η3-1-Alkoxyallylpalladium complexes have
been proposed as an important intermediate in several
catalytic reactions, where they have a great tendency
to direct the nucleophilic attack of stabilized carbanions
(4) Brønsted acid: Ogoshi, S.; Morita, M.; Kurosawa, H. J . Am.
Chem. Soc. 2003, 125, 9020-9021.
(5) A similar reaction of C,O-η2-crotonaldehyde complex of osmium
with methyl triflate has been reported. Spera, M. L.; Chen, H.; Moody,
M. W.; Hill, M. M.; Harman, W. D. J . Am. Chem. Soc. 1997, 119,
12772-12778.
10.1021/om034122m CCC: $25.00 © 2003 American Chemical Society
Publication on Web 11/18/2003

Reaction of Palladium and Platinum Complexes
Organometallics, Vol. 22, No. 26, 2003 5469
reaction conditions, we set out to apply various meth-
ylating agents to the reaction with η2-acroleinpalladium
complex (eq 2). The reaction with MeOSO2F at room
temperature proceeded as readily as eq 1 to give a
similar complex 1c quantitatively. The corresponding
η3-1-methoxyallyl complex 1d was obtained by use of
MeOMs (10 equiv) in excellent yield (98%), but higher
temperature (60 °C in DCE-d4) and longer reaction time
(3 days) were required. The reaction with MeOSO2-
(C6H4-p-NO2) (10 equiv) at room temperature in 12 h
also led to the formation of the complex 1e in good yield
(85%). The lower reactivity of MeOMs and MeOSO2-
(C6H4-p-NO2) would be attributed to the lesser facility
of mesylate and p-nitrophenylsulfonate anion to leave
from the methyl cation than that of the triflate anion.9
Trimethyloxonium salt was also available for this reac-
tion to give the complex 1f quantitatively, although
somewhat longer time (3 h) was required because of its
insolubility. Of particular note is the reaction of MeI
with Pd(η2-CH2dCHCHO)(dppf), though very slow,
which gave the oxidative addition product PdMe(I)(dppf)
(3). The yield was 18%, as determined by NMR, in 1
day along with the release of acrolein even when 10
equiv of MeI was employed (eq 3).
F igu r e 1. ORTEP drawing of 1b‚3/2C6H6. Thermal el-
lipsoids are drawn at the 50% probability level. All H atoms
and the OTf anion are omitted for clarity. Selected bond
lengths (Å) and angles (deg): Pd-C1 ) 2.136(6); Pd-C2
) 2.214(7); Pd-C3 ) 2.373(7); C1-C2 ) 1.40(1); C2-C3
) 1.33(1); C3-O1 ) 1.387(8); O1-C4 ) 1.397(9); C2-C3-
O1-C4 ) 171.9(7).
at the 1-position of an allyl moiety bearing the alkoxy
group despite the steric disadvantage.6 However, there
are very few reports on their isolation, structure, and
reactivity.7 The present reaction represents a very
convenient route to prepare η3-1-alkoxyallyl complexes,
demonstrating the first preparation of the simplest η3-
1-alkoxyallyl complex of palladium. Similar treatment
of η2-acroleinplatinum complex with MeOTf also led to
quantitative formation of the corresponding platinum
analogues, 2a and 2b.
The structures of 1b and 2b, determined by X-ray
diffraction analysis, are consistent with the anticipated
structure. The structure of 1b is shown in Figure 1, and
that of 2b is very similar to this. The Pd-C3 bond
distance (2.373 Å) is somewhat longer than those in
usual η3-allylpalladium complexes, e.g., Pd-C1 ) 2.136
Å in 1b, and the C2-C3 bond distance (1.33 Å) is
shorter than the C1-C2 bond distance (1.40 Å). The two
atoms in the methoxy group are almost coplanar with
the three allyl carbons. This unsymmetrical coordina-
tion of an allyl moiety to palladium is similar to that in
the other distorted η3-allylpalladium8 and η3-1-meth-
oxyallylpalladium complexes.7b,c The unsymmetrical η3-
allyl coordination would control the position of the
nucleophilic attack.1a
We also examined the effect of the substituent in the
carbonyl compound. The reaction of η2-methylvinyl
ketone complexes of palladium and platinum with
MeOTf gave corresponding η3-methoxyallyl complexes,10
while M(Me)(I)(PPh3)2 (M ) Pd, Pt) were formed by the
reaction with MeI (eq 4). Oxidative addition of MeI to
the palladium complex proceeded faster than that to the
platinum complex (5 vs 47 h). This is a somewhat
unexpected order of reactivity, if the relative ease of the
reductive elimination of MMe2L2 (M ) Pd faster than
M ) Pt) is taken into account.11 The oxidative addition
(8) (a) van Haaren, R. J .; Goubitz, K.; Fraanje, J .; van Strijdonck,
G. P. F.; Oevering H.; Coussens, B.; Reek, J . N. H.; Kamer, P. C. J .;
van Leeuwen, P. W. N. M. Inorg. Chem. 2001, 40, 3363-3372. (b)
Togni, A.; Burckhardt, U.; Gramlich, V.; Pregosin, P. S.; Salzmann, R.
J . Am. Chem. Soc. 1996, 118, 1031-1037. (c) Burckhardt, U.; Gramlich,
V.; Hofmann, P.; Nesper, R.; Pregosin, P. S.; Salzmann, R.; Togni, A.
Organometallics 1996, 15, 3496-3503.
To evaluate the scope of carbon electrophiles to
generate η3-1-methoxyallyl complexes under similar
(6) (a) Chaptal, N.; Colovray-Gotteland, V.; Grandjean, C.; Cazes,
B.; Gore, J . Tetrahedron Lett. 1991, 32, 1795-1798. (b) Vicart, N.;
Cazes, B.; Gore, J . Tetrahedron Lett. 1995, 36, 535-538. (c) Trost, B.
M.; J a¨kel, C.; Plietker, B. J . Am. Chem. Soc. 2003, 125, 4438-4439.
(7) (a) Ogoshi, S.; Ohe, K.; Chatani, N.; Kurosawa, H.; Murai, S.
Organometallics 1991, 10, 3813-3818. (b) Vicente, J .; Abad, J . A.; Gil-
Rubio, J .; J ones, P. G. Inorg. Chim. Acta 1994, 222, 1-4. (c) Milani,
B.; Paronetto, F.; Zangrando, E. J . Chem. Soc., Dalton Trans. 2000,
3055-3057.
(9) Noyce, D. S.; Virgilio, J . A. J . Org. Chem. 1972, 37, 2643-2647.
(10) NMR studies revealed that the complexes 4 and 5 were formed
as a mixture of almost equal amounts of syn and anti isomers at the
early stage of the reaction. The isomerization between these two
isomers proceeded gradually to give a thermodynamic mixture (syn/
anti ) 98/2 for 4, 94/6 for 5, respectively).
(11) (a) Low, J . J .; Goddard, W. A., III. J . Am. Chem. Soc. 1986,
108, 6115-6128. (b) Low, J . J .; Goddard, W. A., III. Organometallics
1986, 5, 609-622.

5470 Organometallics, Vol. 22, No. 26, 2003
Morita et al.
were collected by a Rigaku RAXIS-RAPID imaging plate
diffractometer.
Ma ter ia ls. All solvents used in this work were distilled
prior to use. THF, hexane, benzene, and C6D6 were distilled
from sodium benzophenone ketyl; CD2Cl2 and CDCl3, from
CaH2. All commercially available reagents were distilled and
degassed prior to use.
[(CH2CHCH(OCH3))P d (P P h 3)2][CF 3SO3] (1a ). To a solu-
tion of Pd(CH2dCHCHO)(PPh3)2 (153.8 mg, 0.224 mmol) in 5
mL of toluene was added 26.0 µL of MeOTf (37.7 mg, 0.230
mmol) at room temperature. The reaction mixture was con-
centrated in vacuo to give brown solids quantitatively. The
solids were washed with hexane to give 181.6 mg of the
complex 1a in 95% isolated yield. An ti isom er (95%). 1H NMR
(CD2Cl2): δ 2.74 (t, J ) 12.4 Hz, 1H), 2.85 (s, 3H), 3.22 (dt,
J ) 3.0, 7.8 Hz, 1H), 5.30 (dt, J ) 1.6, 11.1 Hz, 1H), 6.63 (dd,
J ) 9.2, 10.8 Hz, 1H), 7.1-7.5 (m, 30H). 31P NMR (CD2Cl2): δ
23.27 (d, J PP ) 36.6 Hz), 27.11 (d, J PP ) 36.6 Hz). 13C NMR
(CD2Cl2): δ 60.3 (s), 60.4 (dd, J CP ) 2.9, 27.4 Hz), 96.4 (dd,
J CP ) 4.0, 6.1 Hz), 121.4 (q, J CF ) 319.9 Hz), 129-135 (m),
may proceed via an initial slow olefin dissociation step,12
which is particularly sluggish for the Pt(0) complex. In
contrast, the formation of [Pt(η3-CH3OCHCHCH2)(dppf)]-
[(C6H4-p-NO2)OSO2] involving the attack of MeOSO2-
(C6H4-p-NO2) at the coordinated enal of Pt(η2-CH2d
CHCHO)(dppf) required a reaction time (20 h) almost
similar to that for 1e. The reaction of (η2-CH2d
CHCOOCH3)Pt(PPh3)2 with MeOTf in C6D6 at room
temperature gave Pt(Me)(OTf)(PPh3)2 and [Pt(Me)-
(PPh3)3]+ by oxidative addition.13
1
142.0 (dd, J CP ) 1.7, 16.5 Hz, COMe). Syn isom er (5%). H
NMR (CD2Cl2): δ 3.17 (m, 1H), 3.63 (m, 1H), 5.01 (m, 1H),
6.48 (m, 1H). The other resonances are hidden by those of the
major isomer. 31P NMR (CD2Cl2): δ 21.52 (d, J PP ) 41.5 Hz),
28.60 (d, J PP ) 41.5 Hz). Anal. Calcd for C41H37F3O4P2SPd (a
mixture of anti and syn isomers): C, 57.85; H, 4.38. Found:
C, 58.11; H, 4.47.
Sch em e 1. P r op osed Mech a n ism for F or m a tion of
η3-1-Meth oxya llyl Com p lexes
[(CH2CHCH(OCH3))P d (d p p f)][CF 3SO3] (1b). To a solu-
tion of Pd(CH2dCHCHO)(dppf) (163.1 mg, 0.228 mmol) in 5
mL of toluene was added 30 µL of MeOTf (43.5 mg, 0.265
mmol) at room temperature. The reaction mixture was con-
centrated in vacuo to give yellow solids quantitatively. The
solids were washed with hexane to give 197.7 mg of the
complex 1b in 99% isolated yield. Syn isom er (85%). 1H NMR
(CD2Cl2): δ 2.58 (ddd, J ) 2.7, 10.3, 13.0 Hz, 1H), 2.89 (s, 3H),
3.27 (dt, J ) 3.0, 8.1 Hz, 1H), 4.0-4.6 (m, 8H), 5.32 (m, 1H),
6.70 (dd, J ) 9.2, 10.8 Hz, 1H), 7.2-7.8 (m, 20H). 31P NMR
(CD2Cl2): δ 20.12 (d, J PP ) 45.6 Hz), 25.69 (d, J PP ) 45.6 Hz).
13C NMR (CD2Cl2): δ 59.7 (dd, J CP ) 3.4, 29.3 Hz), 59.9 (s),
73-78 (m), 97.7 (dd, J CP ) 3.0, 6.3 Hz), 128-135 (m), 138.9
(dd, J CP ) 2.8, 19.1 Hz, COMe). An ti isom er (15%). 1H NMR
(CD2Cl2): δ 3.12 (s, 3H), 3.67 (t, J ) 7.8 Hz, 1H), 4.83 (m, 1H),
6.52 (m, 1H). The other resonances are hidden by those of the
major isomer. 31P NMR (CD2Cl2): δ 20.59 (d, J PP ) 47.7 Hz),
28.48 (d, J PP ) 47.7 Hz). Anal. Calcd for C39H35F3O4P2SFePd
(a mixture of syn and anti isomers): C, 53.17; H, 4.00. Found:
C, 53.25; H, 4.05. X-ray data for 1b‚3/2C6H6. M ) 998.12, red,
triclinic, P1h (No. 2), a ) 10.0513(5) Å, b ) 10.3216(4) Å, c )
22.1580(7) Å, R ) 98.078(2)°, â ) 102.590(1)°, γ ) 91.862(2)°,
V ) 2216.5(2) Å3, Z ) 2, Dcalcd ) 1.495 g/cm3, T ) -70.0 °C, R
(Rw) ) 0.056 (0.108).
For the purpose of understanding the course of the
reaction to form η3-methoxyallyl complexes, reaction of
Pt(Me)(OTf)(dppf) with acrolein was attempted. How-
ever, no insertion of acrolein into the Pt-Me bond
occurred at room temperature in CD2Cl2 after 48 h.
Therefore, the sequence of oxidative addition of MeOTf
to the Pt(0) complex followed by the insertion of acrolein
into the Pt-Me bond would be unlikely for eq 1. On the
basis of these results, we propose that the η3-1-meth-
oxyallyl complexes of palladium and platinum would be
formed by the nucleophilic substitution of MeOTf by the
carbonyl oxygen of the acrolein complex, described in
Scheme 1.
[(CH2CHCH(OCH3))P d (d p p f)][F SO3] (1c). To a solution
of Pd(CH2dCHCHO)(dppf) (10.8 mg, 0.015 mmol) in 0.5 mL
of CD2Cl2 was added 1.3 µL of MeOSO2F (1.9 mg, 0.016 mmol)
at room temperature. The complex 1c was formed quantita-
tively.
[(CH2CHCH(OCH3))P d (d p p f)][CH3SO3] (1d ). To a solu-
tion of Pd(CH2dCHCHO)(dppf) (10.8 mg, 0.015 mmol) in 0.5
mL of C2D4Cl2 was added 12.7 µL of MeOMs (16.5 mg, 0.150
mmol) at room temperature. The tube was heated to 60 °C,
and the reaction was monitored by NMR measurement. After
3 days the complex 1d was formed in 98% yield along with
PdCl2(dppf) in 2% yield.
[(CH2CHCH(OCH3))P d (d p p f)][p-NO2C6H4SO3] (1e). Pd-
(CH2dCHCHO)(dppf) (10.8 mg, 0.015 mmol) and MeOSO2C6H4-
p-NO2 (22.7 mg, 0.151 mmol) were charged in an NMR sample
tube, then CD2Cl2 was added at room temperature. After 12
h, the complex 1e was formed in 85% yield along with PdCl2-
(dppf) in 15% yield.
Exp er im en ta l Section
Gen er a l P r oced u r es. 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 J EOL GSX-270S and J EOL AL-400
1
spectrometers. The chemical shifts in the H nuclear magnetic
resonance spectra were recorded relative to Me4Si, CD2Cl2 (δ
5.32), C6D6 (δ 7.16), or CDCl3 (δ 7.26). The chemical shifts in
the 13C nuclear magnetic resonance spectra were recorded
relative to Me4Si, CD2Cl2 (δ 53.8) or CDCl3 (δ 77.0). The
chemical shifts in 31P nuclear magnetic resonance spectra were
recorded using 85% H3PO4 as an external standard. Elemental
analyses were preformed at the Instrumental Analysis Center,
Faculty of Engineering, Osaka University. X-ray crystal data
(12) Birk, J . P.; Halpern, J .; Pickard, A. L. J . Am. Chem. Soc. 1968,
90, 4491-4492.
(13) The reaction of Pt(CH2dCH2)(PPh3)2 with MeOTf under the
same conditions gave Pt(Me)(OTf)(PPh3)2 at first, which then decom-
posed gradually to [Pt(Me)(PPh3)3]+.
[(CH2CHCH(OCH3))P d (d p p f)][BF 4] (1f). Pd(CH2dCHC-
HO)(dppf) (10.8 mg, 0.015 mmol) and [(CH3)3O][BF4] (2.2 mg,

Reaction of Palladium and Platinum Complexes
Organometallics, Vol. 22, No. 26, 2003 5471
0.015 mmol) were charged in an NMR sample tube, and CD2-
Cl2 was added at room temperature. After 3 h, the complex 1f
was formed quantitatively.
Selected NMR data for 3. 1H NMR (CD2Cl2): δ 0.86 (t, J ) 7.6
Hz, 3H). 31P NMR (CD2Cl2): δ 12.24 (d, J PP ) 31.8 Hz), 33.88
(d, J PP ) 31.8 Hz).
[(CH2CHCH(OCH3))P t(P P h 3)2][CF 3SO3] (2a ). To a solu-
tion of Pt(CH2dCH2)(PPh3)2 (228.0 mg, 0.305 mmol) in 6 mL
of toluene was added 30.0 µL of CH2dCHCHO (25.2 mg, 0.449
mmol) and 37.0 µL of MeOTf (53.7 mg, 0.327 mmol) at room
temperature. The reaction mixture was concentrated in vacuo
to give white solids quantitatively. The solids were washed
with hexane to give 278.9 mg of the complex 2a in 97% isolated
yield. Syn isom er (75%). 1H NMR (CD2Cl2): δ 2.06 (t, J )
12.2 Hz, 1H), 2.81 (m, 1H), 2.84 (s, 3H), 4.90 (dtt, J ) 3.0, 8.1,
11.1 Hz, 1H), 6.30 (dd, J ) 9.5, 10.8 Hz, J HPt ) 48.6 Hz, 1H),
7.1-7.5 (m, 30H). 31P NMR (CD2Cl2): δ 19.08 (d, J PP ) 1.5
Hz, J PPt ) 4532 Hz), 22.52 (d, J PP ) 1.5 Hz, J PPt ) 3815 Hz).
13C NMR (CD2Cl2): δ 50.1 (d, J CP ) 30.6 Hz, J CPt ) 149.4 Hz),
59.9 (s), 93.3 (dd, J CP ) 1.6, 4.3 Hz, J CPt ) 23.0 Hz), 121.4 (q,
J CF ) 321.7 Hz), 128-135 (m). The resonance for the carbon-
bearing methoxy group was observed at 134.9 ppm by the C-H
[(CH2CHCCH3(OCH3))P d (P P h 3)2][CF 3SO3] (4). To a so-
lution of Pd(CH2dCHCOCH3)(PPh3)2 (194.7 mg, 0.278 mmol)
in 6 mL of toluene was added 32.0 µL of MeOTf (46.6 mg, 0.283
mmol) at room temperature. The reaction mixture was con-
centrated in vacuo to give brown solids quantitatively. The
solids were washed with hexane to give 198.3 mg of the
complex 4 in 83% isolated yield. Syn isom er (46%). 1H NMR
(CD2Cl2): δ 1.75 (dd, J ) 3.2, 4.9 Hz, 3H), 2.33 (ddt, J ) 2.2,
3.2, 8.6 Hz, 1H), 3.08 (s, 3H), 3.34 (dt, J ) 3.8, 7.8 Hz, 1H),
5.00 (tt, J ) 1.6, 10.5 Hz, 1H), 7.1-7.5 (m, 30H). 31P NMR
(CD2Cl2): δ 23.13 (d, J PP ) 33.3 Hz), 29.97 (d, J PP ) 33.3 Hz).
13C NMR (CD2Cl2): δ 23.0 (dd, J CP ) 1.0, 4.3 Hz, CH3), 54.8
(dd, J CP ) 2.8, 30.6 Hz), 57.4 (s), 82.9 (dd, J CP ) 2.9, 5.4 Hz),
128-135 (m), 163.9 (d, J CP ) 11.6 Hz, COMe). An ti isom er
1
(54%). H NMR (CD2Cl2): δ 1.38 (dd, J ) 4.6, 11.3 Hz, 3H),
2.94 (m, 2H), 3.49 (s, 3H), 4.61 (dd, J ) 8.1, 13.5 Hz, 1H). The
1
other resonances are hidden by those of the major isomer. 31
P
COSY measurement. An ti isom er (25%). H NMR (CD2Cl2):
δ 2.43 (m, 1H), 3.18 (s, 3H), 3.43 (m, 1H), 4.79 (m, 1H), 6.01
(d, J ) 4.6 Hz, 1H). The other resonances are hidden by those
of the major isomer. 31P NMR (CD2Cl2): δ 16.57 (d, J PP ) 7.6
Hz, J PPt ) 3901 Hz), 17.97 (d, J PP ) 7.6 Hz, J PPt ) 4154 Hz).
Anal. Calcd for C41H37F3O4P2SPt (a mixture of syn and anti
isomers): C, 52.40; H, 3.97. Found: C, 51.71; H, 3.81.
[(CH2CHCH(OCH3))P t(d p p f)][CF 3SO3] (2b). To a solu-
tion of Pt(CH2dCH2)(dppf) (161.0 mg, 0.207 mmol) in 6 mL of
benzene was added 16.0 µL of CH2dCHCHO (13.4 mg, 0.239
mmol) and 25.0 µL of MeOTf (36.3 mg, 0.221 mmol) at room
temperature. The reaction mixture was concentrated in vacuo
to give yellow solids quantitatively. The solids were washed
with hexane to give 194.8 mg of the complex 2b in 97% isolated
yield. An analytical sample was prepared by recrystallization
from THF/benzene/hexane solution. Syn isom er (80%). 1H
NMR (CD2Cl2): δ 1.95 (t, J ) 11.6 Hz, J HPt ) 61.6 Hz, 1H),
2.83 (m, 4H, allylic syn proton at the terminal carbon overlaps
with the methoxy proton), 3.9-4.6 (m, 8H), 4.89 (q, J ) 9.7
Hz, 1H), 6.16 (q, J ) 9.7 Hz, J HPt ) 41.6 Hz, 1H), 7.3-7.8 (m,
NMR (CD2Cl2): δ 22.93 (d, J PP ) 36.0 Hz), 33.71 (d, J PP
)
36.0 Hz). 13C NMR (CD2Cl2): δ 19.6 (dd, J CP ) 0.9, 4.9 Hz,
CH3), 52.6 (dd, J CP ) 3.4, 31.5 Hz), 86.3 (dd, J CP ) 3.8, 5.7
Hz), 167.2 (d, J CP ) 13.1 Hz). The other resonances are hidden
by those of the major isomer. Anal. Calcd for C42H39F3O4P2-
SPd (a mixture of anti and syn isomers): C, 58.31; H, 4.54.
Found: C, 58.41; H, 4.47.
[(CH2CHCCH3(OCH3))P t(P P h 3)2][CF 3SO3] (5). To a solu-
tion of Pt(CH2dCH2)(PPh3)2 (206.1 mg, 0.276 mmol) in 6 mL
of benzene was added 24.0 µL of CH2dCHCOCH3 (20.2 mg,
0.288 mmol) and 32.0 µL of MeOTf (46.4 mg, 0.283 mmol) at
room temperature. The reaction mixture was concentrated in
vacuo to give white solids quantitatively. The solids were
washed with hexane to give 240.5 mg of the complex 5 in 92%
1
isolated yield. Syn isom er (94%). H NMR (CD2Cl2): δ 1.59
(dddd, J ) 3.5, 4.9, 8.9, 14.6 Hz, 1H), 1.70 (d, J ) 3.0 Hz, 3H),
2.89 (q, J ) 7.6, Hz, 1H), 3.01 (s, 3H), 4.59 (ddd, J ) 4.1, 7.8,
11.6 Hz, J HPt ) 51.8 Hz, 1H), 7.0-7.5 (m, 30H). 31P NMR (CD2-
Cl2): δ 20.28 (d, J PP ) 2.2 Hz, J PPt ) 4640 Hz), 24.25 (d,
J PP ) 2.2 Hz, J PPt ) 3718 Hz). 13C NMR (CD2Cl2): δ 21.1 (dd,
J CP ) 1.0, 4.0 Hz, J CPt ) 19.8 Hz), 44.4 (d, J CP ) 34.8 Hz,
J CPt ) 179.7 Hz), 56.8 (s), 76.9 (d, J CP ) 4.3 Hz, J CPt ) 19.9
20H). 31P NMR (CD2Cl2): δ 18.96 (d, J PP ) 11.7 Hz, J PPt
)
4527 Hz), 21.03 (d, J PP ) 11.7 Hz, J PPt ) 3948 Hz). 13C NMR
(CD2Cl2): δ 50.1 (d, J CP ) 32.1 Hz, J CPt ) 144.5 Hz) 59.5 (s),
73-77 (m), 94.6 (dd, J CP ) 1.6, 4.0 Hz, J CPt ) 22.0 Hz), 121.4
(q, J CF ) 321.7 Hz), 128-138 (m). The resonance for the
carbon-bearing methoxy group was observed at 132.2 ppm by
Hz), 121.6 (q, J CF ) 322.1 Hz), 128-136 (m), 160.6 (dd, J CP
)
2.1, 11.6 Hz, COMe). An ti isom er (6%). 1H NMR (CD2Cl2): δ
1.47 (dd, J ) 2.4, 8.9 Hz, 3H), 2.19 (m, 1H), 2.60 (m, 1H), 3.50
(s, 3H), 4.33 (ddd, J ) 3.8, 7.8, 11.9 Hz, 1H). The other
resonances are hidden by those of the major isomer. 31P NMR
(CD2Cl2): δ 21.33 (s, J PPt ) 4711 Hz), 22.72 (s, J PPt ) 3652
Hz). Anal. Calcd for C42H39F3O4P2SPt (a mixture of syn and
anti isomers): C, 52.89; H, 4.12. Found: C, 52.59; H, 4.07.
1
the C-H COSY measurement. An ti isom er (20%). H NMR
(CD2Cl2): δ 2.42 (td, J ) 2.7, 11.8 Hz, J HPt ) 60.2 Hz, 1H),
3.08 (s, 3H), 3.43 (m, 1H), 6.04 (m, 1H). The other resonances
are hidden by the major isomer. 31P NMR (CD2Cl2): δ 16.65
(d, J PP ) 16.0 Hz, J PPt ) 3948 Hz), 18.90 (d, J PP ) 16.0 Hz,
J PPt ) 4243 Hz). Anal. Calcd for C45H41F3O4P2SFePt (a mixture
of syn and anti isomers): C, 51.59; H, 3.94. Found: C, 51.57;
H, 3.92. X-ray data for 2b‚3/2C6H6. M ) 1086.81, yellow,
triclinic, P1h (No. 2), a ) 9.9669(8) Å, b ) 10.3655(7) Å, c )
22.007(1) Å, R ) 98.413(1)°, â ) 102.4313(6)°, γ ) 91.7362-
(7)°, V ) 2191.9(3) Å3, Z ) 2, Dcalcd ) 1.647 g/cm3, T ) -60.0
°C, R ) 0.056.
Oxid a t ive Ad d it ion of CH3I t o P d (CH 2dCH CH O)-
(d p p f). To a solution of Pd(CH2dCHCHO)(dppf) (10.8 mg,
0.015 mmol) in 0.5 mL of CD2Cl2 was added 9.3 µL of MeI
(21.3 mg, 0.150 mmol) at room temperature. The tube was
heated to 40 °C, and the reaction was monitored by NMR
measurement. After 24 h the complex 3 was formed in 18%
yield with 82% of Pd(CH2dCHCHO)(dppf) remaining unre-
acted.
Oxid a tive Ad d ition of CH3I to P d (CH2dCHCOCH3)-
(P P h 3)2. To a solution of Pd(CH2dCHCOCH3)(PPh3)2 (8.0 mg,
0.011 mmol) in 0.5 mL of CD2Cl2 was added 7.1 µL of MeI
(16.2 mg, 0.114 mmol) at room temperature. The reaction was
monitored by NMR measurement. After 7 h trans-Pd(CH3)-
(I)(PPh3)2 was quantitatively formed.
Oxid a tive Ad d ition of CH3I to P t(CH2dCHCOCH3)-
(P P h 3)2. To a solution of Pt(CH2dCHCOCH3)(PPh3)2 (8.3 mg,
0.011 mmol) in 0.5 mL of CD2Cl2 was added 6.6 µL of MeI
(14.9 mg, 0.105 mmol) at room temperature. The reaction was
monitored by NMR measurement. After 47 h trans-Pt(CH3)-
15
(I)(PPh3)2 was quantitatively formed.
[(CH2CHCH(OCH3))P t(d p p f)][p-NO2C6H4SO3]. Pt(CH2d
CHCHO)(dppf) (12.1 mg, 0.015 mmol) and MeOSO2C6H4-p-
NO2 (32.6 mg, 0.150 mmol) were charged in an NMR sample
tube, then CD2Cl2 was added at room temperature. After
20 h, [(CH2CHCH(OCH3))Pt(dppf)][p-NO2C6H4SO3] was formed
quantitatively.
P d (CH3)(I)(d p p f) (3). An authentic sample of complex 3
was generated by the reaction of trans-Pd(Me)(I)(PPh3)214 (5.1
mg, 0.007 mmol) with DPPF (3.7 mg, 0.007 mmol) in CD2Cl2.
(14) Fitton, P.; J ohnson, M. P.; McKeon, J . E. J . Chem. Soc., Chem,
Commun. 1968, 6-7.
(15) Chat, J .; Shaw, B. L. J . Chem. Soc. 1959, 705-716.

5472 Organometallics, Vol. 22, No. 26, 2003
Morita et al.
Rea ction of P t(CH2dCHCOOCH3)(P P h 3)2 w ith MeOTf.
To a solution of Pt(CH2dCHCOOCH3)(PPh3)2 (12.1 mg, 0.015
mmol) in 0.5 mL of C6D6 was added 1.7 µL of MeOTf (2.5 mg,
0.015 mmol) at room temperature. After 48 h colorless solids
precipitated from the solution. In this solution, Pt(Me)(OTf)-
(PPh3)2 was formed in 39% yield. The solution was removed
by decantation, and the solids were resolved in CD2Cl2 with
toluene (5.0 µL, 0.047 mmol) as internal standard. [Pt(Me)-
(PPh3)3][OTf] was formed in 33% yield.
Ack n ow led gm en t. Partial support of this work
through Grants-in-Aid for scientific research from the
Ministry of Education, Science and Culture, J apan, and
the J SPS Research Fellowship for Young Scientists
(M.M.) is gratefully acknowledged.
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal
data and refinement parameters, bond lengths and angles, and
positional and thermal parameters for 1b and 2b. This
material is available free of charge via the Internet at
http://pubs.acs.org.
Attem p ted In ser tion of Acr olein in to th e P t-Me Bon d .
To a solution of cis-Pt(Me)(OTf)(dppf)16 (12.1 mg, 0.013 mmol)
in 0.5 mL of CD2Cl2 was added 0.9 µL of acrolein (0.8 mg, 0.013
mmol) at room temperature. After 48 h, no reaction occurred.
(16) Thorn, D. L.; Fultz, W. C. J . Phys. Chem. 1989, 93, 1234-1243.
OM034122M