Synthesis of heterodinuclear hydride complexes by oxidative addition of a transition-metal hydride to Pt(0) and Pd(0) complexes

Article abstract of DOI:10.1016/j.jorganchem.2015.04.048

Abstract Heterodinuclear hydridoplatinum and -palladium complexes, (dppe)HPt-ML_n (ML_n = MoCp(CO)₃ (3a), WCp(CO)₃ (3b)), (dppe)Pt(μ-H)(μ-CO)Mn(CO)₄ (3c), (dppe)Pt(μ-H)(μ-CO)FeCp(CO) (3d), cis-L′₂HPt-ML_n (5aa: LE' = PPh₃; ML_n = MoCp(CO)₃, 5ba: LE' = PPh₃; ML_n = WCp(CO)₃, 5ab: LE' = PMePh₂; ML_n = MoCp(CO)₃, 5ac: LE' = PMe₂Ph; ML_n = MoCp(CO)₃), (dppe)Pd(μ-H)(μ-CO)ML_n (ML_n = MoCp(CO)₂ (7a), WCp(CO)₂ (7b)), (dppe)Pd(μ-H)(μ-CO)Mn(CO)₄ (7c) are prepared by the oxidative addition of mononuclear transition-metal hydride complexes to zero-valent platinum or palladium complexes. The reactions of the heterodinuclear hydride complexes 3a, 3d and 7a with electron deficient alkenes and alkynes such as dimethyl fumarate or DMAD cause reductive elimination at the Pt or Pd center to give the Pt(alkene or alkyne)(dppe) and MHL_n,, suggesting reversibility of this process. The DFT calculations suggest that these reactions are controlled by the thermodynamic stability and the electron rich alkene complex of Pt(0) (or Pd(0)) are preferable to prepare these heterodinuclear hydride complexes by the oxidative addition.

Full text of DOI:10.1016/j.jorganchem.2015.04.048

Journal of Organometallic Chemistry 792 (2015) 194e205
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis of heterodinuclear hydride complexes by oxidative addition
of a transition-metal hydride to Pt(0) and Pd(0) complexes*
Nobuyuki Komine*, Ayako Kuramoto, Toshiyuki Yasuda, Tatsuya Kawabata,
,
1
Masafumi Hirano, Sanshiro Komiya*
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Nakacho, Koganei, Tokyo
184-8588, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Heterodinuclear hydridoplatinum and -palladium complexes, (dppe)HPteMLn (MLn ¼ MoCp(CO)3 (3a),
WCp(CO)3 (3b)), (dppe)Pt(
m
-H)(
MoCp(CO)3, 5ba: Lʹ
MLn ¼ MoCp(CO)3, 5ac: Lʹ ¼ PMe2Ph; MLn ¼ MoCp(CO)3), (dppe)Pd(
(7a), WCp(CO)2 (7b)), (dppe)Pd( -H)( -CO)Mn(CO)4 (7c) are prepared by the oxidative addition of
m
-CO)Mn(CO)4 (3c), (dppe)Pt(
m
-H)(
m
-CO)FeCp(CO) (3d), cis-L02HPteMLn
Received 30 December 2014
Received in revised form
24 April 2015
Accepted 26 April 2015
Available online 21 May 2015
(5aa: Lʹ
¼
PPh3; MLn
¼
¼
PPh3; MLn
¼
WCp(CO)3, 5ab: Lʹ
¼
PMePh2;
m
-H)(
m
-CO)MLn (MLn ¼ MoCp(CO)2
m
m
mononuclear transition-metal hydride complexes to zero-valent platinum or palladium complexes. The
reactions of the heterodinuclear hydride complexes 3a, 3d and 7a with electron deficient alkenes and
alkynes such as dimethyl fumarate or DMAD cause reductive elimination at the Pt or Pd center to give the
Pt(alkene or alkyne)(dppe) and MHLn,, suggesting reversibility of this process. The DFT calculations
suggest that these reactions are controlled by the thermodynamic stability and the electron rich alkene
complex of Pt(0) (or Pd(0)) are preferable to prepare these heterodinuclear hydride complexes by the
oxidative addition.
Keywords:
Heterodinuclear hydride complex
Oxidative addition
Reductive elimination
DFT calculation
© 2015 Elsevier B.V. All rights reserved.
Introduction
fundamental reactions such as hydrogenations, hydrosilylations,
isomerizations, polymerizations, etc. These backgrounds have
Cooperative effect among different transition-metal elements is
a well-known phenomenon both in homo- and heterogeneous
catalyses but the intrinsic insight into this nature is still one of the
most intriguing and interesting unsolved problems [1e10]. Never-
theless, the combination of two or more different metal elements is
widely used for industrially important catalysts such as PteRe in
naphtha reforming and CoeMo or NieMo in hydrodesulfurization
processes. One of the leading approaches for understanding of the
cooperative effect at the molecular level is the study of hetero-
dinuclear transition-metal complexes. Among these approaches,
studies of heterodinuclear hydrides promise to reveal the cooper-
ative effect on the reactivity of the metalꢀhydride bond. In fact, a
transition metalꢀhydride species closely engages in many
stimulated the studies on heterodinuclear hydrides. The synthetic
pathways for heterodinuclear hydride complexes are therefore of
great interest for these studies. One of the solid synthetic ap-
proaches is a metathetical reaction (Scheme 1).
Braunstein and coworkers have reported the synthesis of the
heterodinuclear hydridoplatinum complexes cis-(Ph3P)2HPt-
MCp(CO)3 (M ¼ Mo, W) and cis-(R3P)2Pt(
(R ¼ Ph, Et) by the metathetical reaction of trans-PtH(Cl)(PR3)2 with
the corresponding carbonylmetalates [11]. A -hydride elimination
m-H)(m-CO)Mn(CO)4
b
from heterodinuclear ethyl complex is also a great method to
prepare the hydride complex. We have documented the prepara-
tion of (dppe)HPteMoCp(CO)3 by
b-hydride elimination from
(dppe)EtPteMoCp(CO)3 [12]. The last but not least methodology
shown in Scheme 1 is the oxidative addition of mono-nuclear hy-
dride complex to a zero-valent metal compound [13]. We previ-
ously communicated the oxidative addition of MHCp(CO)3
(M ¼ Mo, W) to Pt(alkene)(dppe) (alkene ¼ styrene, ethyl acrylate)
giving the corresponding heterodinuclear platinum hydride com-
plex (dppe)HPteMCp(CO)3 (M ¼ Mo, W) [14]. At the same time,
*
This paper is dedicated to Prof. Mingos for his outstanding contribution to
organometallic chemistry.
* Corresponding authors. Tel./fax: þ81 42 388 7044.
E-mail addresses: komine@cc.tuat.ac.jp (N. Komine), komiya@cc.tuat.ac.jp
(S. Komiya).
Adams and coworkers also reported the preparation of (tBu3P)Pt(
m-
1
Present address: Gakushuin University.
http://dx.doi.org/10.1016/j.jorganchem.2015.04.048
0022-328X/© 2015 Elsevier B.V. All rights reserved.

N. Komine et al. / Journal of Organometallic Chemistry 792 (2015) 194e205
195
structure. The PteMo bond distance (2.786(1) Å) is significantly
shorter than those for (Ph3P)2HPteMoCp(CO)3 (2.839(1) Å) [11] and
(dppe)EtPteMoCp(CO)3 (2.912(3) and 2.934(3) Å) [14]. The IR
spectra of 3a and 3b showed absorption bands at 2042 cmꢀ1 and
2041 cmꢀ1, respectively, which were assigned to the
n(PteH) vi-
brations for terminal hydride ligands. The
n(CO) frequencies in KBr
pellets of 3a, at 1926 and 1819 cmꢀ1, and of 3b, at 1925 and
1828 cmꢀ1, correspond to a typical pattern for a MXCp(CO)3 “four-
legged piano-stool” structure [17]. The 1H and 31P{1H} NMR data for
3a and 3b are consistent with the structure drawing in Scheme 2.
Unlike the triethylphosphine derivatives, (Ph3P)2HPteMoCp(CO)3
(M ¼ Mo, W) [11], the NMR spectra of 3a and 3b do not show any
fluxional behavior below room temperature. It is worthwhile to
note that the 31P{1H} NMR in C6D6 showed two doublets with 195Pt
Scheme 1. Possible pathways for the preparation of heterodinuclear hydride
complexes.
2
1
satellites at
d
49.0 (d, JPP ¼ 3 Hz, JPtP ¼ 3312 Hz) and 50.8 (d,
2JPP ¼ 3 Hz, JPtP ¼ 2118 Hz) for 3a, and
d
51.3 (d, JPP ¼ 4 Hz,
1
2
1JPtP ¼ 3313 Hz) and 52.8 (d, JPP ¼ 4 Hz, 1JPtP ¼ 2093 Hz) for 3b.
Without 1H decoupling, a large PeH coupling (2JPH ¼ 194 Hz) for the
downfield resonance was observed in the 31P NMR of 3a, while
upfield resonance has no PeH coupling. Therefore, the downfield
resonance is assigned to the phosphorus nucleus trans to the hy-
2
H)(m-CO)Os(CO)3(SnPh3) by the oxidative addition of OsH(-
CO)4(SnPh3) to Pt(PBut3)2 [15]. Not only for the importance as a
synthetic method for the heterodinuclear hydrides, this reaction
potentially changes the nature and reactivity of the hydride ligand
because the hydride migrates between different metal elements. In
this paper, we report a full account for the synthesis of hetero-
dinuclear hydridoplatinum and -palladium complexes by the
oxidative addition of the corresponding mononuclear hydride
complexes with zero-valent platinum and palladium complexes.
The reactions of the heterodinuclear hydride complexes are also
described.
1
dride. In both cases, the upfield resonances have larger JPtP
coupling than the other. This perturbation comes from the smaller
trans influence of the MLn fragment than the hydride [18].
The reaction of 1 with hydridomanganese complex MnH(CO)5
(2c) is noteworthy. This reaction also proceeded in benzene at room
temperature but the product obtained was a
m-hydrido-m-carbonyl
platinumemanganese complex, (dppe)Pt( -H)(
m
m
-CO)Mn(CO)4 (3c)
Results and discussion
in 93% yield. Single crystals of 3c suitable for the X-ray analysis
involve two quite similar but crystallographically independent
molecules in a unit cell and one of them is depicted in Fig. 2. Unlike
the Mo analogs, 3c has a bridging carbonyl and hydride ligands
between the Pt and Mn atoms. The Pt geometry is regarded as a
square-planar by the bridging hydride and carbonyl carbon, and
two phosphorus atoms of dppe, whereas the Mn has a near-perfect
Preparations of heterodinuclear hydridoplatinum and -palladium
complexes by oxidative addition
Oxidative addition of transition-metal hydride to Pt(0) complex
having a dppe ligand
Oxidative addition of MoHCp(CO)3 (2a) to a zero-valent plat-
inum complex, Pt(CH2]CHPh)(dppe) (1) smoothly gave a hetero-
dinuclear hydridoplatinum complex, (dppe)HPteMoCp(CO)3 (3a)
at room temperature in 92% yield with liberation of styrene in 78%
yield (Scheme 2). Similar treatment of 1 with WHCp(CO)3 (2b) also
gave the corresponding heterodinuclear hydridoplatinum complex,
(dppe)HPteWCp(CO)3 (3b) in 88% with concomitant formation of
styrene in 75%. On the other hand, other transition-metal hydrides
having tertiary phosphine ligand(s) 2e-h did not react with 1 at all.
Notably, WHCp(CO)2(PPh3) (2f) did not react with 1 at all, while 2b
readily produced 3b in high yield, suggesting the importance of the
acidity of the hydride used [16]. In the case of ruthenium dihydrides
2i,j, 1 reacted with these dihydridoruthenium(II) to give a complex
mixture, which was difficult to be characterized. In these reactions
using dihydride complexes, a considerable amount of ethylbenzene
was formed (56% for 2i, 56% for 2j), suggesting styrene was hy-
drogenated during the reaction.
octahedral geometry generated from the
gands. The PteMn distance for 3c is 2.686(2) Å, which is shorter
than those for (Et3P)2Pt( -H)( -CO)Mn(CO)4 (2.730(2) Å) [11] and
(dppe)MePteMn(CO)5 (2.795(2) Å) [20]. The PteP1 and PteP2
distances are 2.292(1) and 2.230(2) Å, respectively. These distances
m-H and the five CO's li-
m
m
are slightly shorter than these in (Et3P)2Pt(m-H)(m-CO)Mn(CO)4
(2.353 (3), 2.283(3) Å). The bridging carbonyl C1eO1 is symmet-
rically bound to Pt and Mn with Pt(or Mn)eC1 distances of 2.03 and
2.02 Å, respectively. These values are close to 2.02(1) and 2.03(1) Å
found for (Et3P)2Pt(
dinuclear hydrideplatinumemanganese complex shows
bands for terminal carbonyl ligands at 1949, 1930 and 1836 cmꢀ1
and a typical lower band for a bridging carbonyl at 1707 cmꢀ1
Therefore, this intense and lower shifted band can be used as a
criterion for the presence of -carbonyl group [17].
m-H)(
m-CO)Mn(CO)4. The IR spectrum of the
n
(CO)
.
m
The NMR spectrum of 3c showed fluxional behavior, which is
described in the following section, but the fluxionality is almost
frozen at ꢀ80 ꢁC. The 1H NMR in CD2Cl2 at ꢀ80 ꢁC showed a double
These complexes 3a-b were characterized by 1H and 31P{1H}
NMR and IR spectroscopies, as well as by X-ray structure analysis of
3a. The single crystals of 3a suitable for the X-ray analysis were
obtained by recrystallization from a benzene and hexane mixed
solvent. Fig. 1 depicts an ORTEP drawing of 3a, showing the for-
mation of a PteMo single bond. Unfortunately, the hydride was not
clearly found in the differential Fourier map of 3a, but Pt, Mo, P1,
and P2 were placed in the same plane and their deviation from
their least-squares plane is within 0.17 Å. The P1ePteP2 and
P2ePteMo bond angles are 84.9(2)ꢁ and 112.0(1)ꢁ, respectively.
These data suggest the Pt having a distorted square-planar geom-
etry with a putative hydride ligand. On the other hand, the Mo
fragment can be regarded as a distorted four-legged piano-stool
2
1
doublet at
d
ꢀ4.39 (dd, JPH ¼ 99.8, 13.2 Hz, JPtH ¼ 547 Hz, 1H)
which is assigned as the hydride. The 1JPtH value for 3c in CD2Cl2 is
smaller than one for 3a. The 31P{1H} NMR spectrum at ꢀ80 ꢁC
showed an AB pattern with 195Pt satellites at
d
44.6
(1JPtP ¼ 2303 Hz) and 46.1 (1JPtP ¼ 4057 Hz). The doublet resonance
at
d
46.1 in the 31P{1H} NMR changed to a double doublet in non-
decoupling 31P NMR by a large coupling with the hydride
(2JPH ¼ 87 Hz). Therefore, this resonance was assigned to the
phosphorus trans to the hydride. The small 1JPtP coupling constant
(1JPtP ¼ 2303 Hz) at
d 44.6 arises from the stronger trans influence,
suggesting the presence of a carbon fragment, but it does not have a
Mn in the trans position. This fact is considered to have the bridged

196
N. Komine et al. / Journal of Organometallic Chemistry 792 (2015) 194e205
Scheme 2. Reactions of Pt(styrene)(dppe) (1) with transition-metal hydride complexes.
hydride and carbonyl structure, even in the CD2Cl2 solution. These
195PteP coupling constants in 3c reflect smaller trans influence
from the bridging hydride than carbonyl ligand. These NMR data in
CD2Cl2 are close to these of PPh3 derivative reported by Braunstein
and coworkers [11c]. These are consistent with the molecular
structure shown in Fig. 2. However, the NMR spectrum of 3c
measured in toluene-d8 was remarkably different from those in
CD2Cl2. Namely, the 31P{1H} NMR of 3c in toluene-d8 at ꢀ80 ꢁC
larger 1JPtH and smaller 1JPtP values indicate stronger bonding of the
hydride ligand with Pt in toluene-d8 solution.
Similarly, the treatment of FeHCp(CO)2 (2d) with 1 produced
(dppe)Pt(m-H)(m-CO)Fe(CO) (3d) in 52% yield. This compound was
also characterized by 1H and 31P{1H} NMR and IR spectroscopies. As
the most characteristic feature of 3d, the IR spectrum showed
intense
n
(CO) bands at 1950 cmꢀ1 and 1695 cmꢀ1. The latter
n
(CO)
band indicates the presence of a
m-carbonyl group in 3d. The NMR
showed two signals with 195Pt satellites at
d
49.7 (1JPtP ¼ 2803 Hz)
spectra suggest the involvement of some dynamic processes in a
solution of 3d (vide infra).
and 52.8 (1JPtP ¼ 2856 Hz). The hydride resonance appeared as a
double doublet at
d
ꢀ2.24 (2JPH ¼ 154, 6.6 Hz, 1JPtH ¼ 719 Hz). The
Fig. 2. An ORTEP drawing of one of the two crystallographically independent mole-
Fig. 1. ORTEP drawing of (dppe)HPteMoCp(CO)3 (3a) [19]. All hydrogen atoms and
incorporated solvent molecule are omitted for clarity. Ellipsoids represent 50%
probability.
cules of (dppe)Pt(m-H)(m-CO)Mn(CO)4 (3c) obtained from the benzene/hexane solution
[21]. All hydrogen atoms except the hydride and incorporated solvent molecule are
omitted for clarity. Ellipsoids represent 50% probability.

N. Komine et al. / Journal of Organometallic Chemistry 792 (2015) 194e205
197
Oxidative addition of transition-metal hydrides to Pt(0) complex
having monodentate phosphine ligands
A series of reactions of monodentate phosphine complex
Pt(alkene)L20 (4) with 2a or 2b were achieved to give corresponding
cis-dinuclear hydridoplatinum complex
5 (Table 1). Without
exception, these products have the cis geometry regardless of the
cone angle of phosphines used (
q
¼ 145ꢁ for PPh3, 136ꢁ for PMePh2,
122ꢁ for PMe2Ph) [22]. The molybdenum hydride 2a was found to
be more reactive than the tungsten hydride 2b (entries 4 and 5). No
reaction occurred when dimethyl fumarate (e value ¼ 1.490)
complex was used (entries 6 and 7), while the ethylene (e
value ¼ ꢀ0.200), (E)-stilbene (e value ¼ ꢀ0.080), and methyl
acrylate (e value ¼ 0.600) complexes readily reacted with 2a and 2b
(entries 1e5). The
p-acidic character of the coordinating alkene
seems to discourage the reaction. Probably this reaction may be
controlled by the electron density of the Pt center in the oxidative
addition reaction of MHLn or facile dissociation of the alkene ligand
in 4 to give a reactive coordinatively unsaturated species.
Oxidative addition of transition-metal hydride complexes to Pd(0)
ethyl acrylate complex
The same method can be applied to the Pd(0) complex. The
reaction of Pd(ethyl acrylate)(dppe) (6) [23] with 1 equiv of 2a in
C6D6 produced a heterodinuclear hydridopalladium complex 7a in
45% yield [Eq. (1)].
Fig. 3. Variable temperature 1H NMR spectra of (dppe)Pt(
toluene-d8.
m-H)(
m
-CO)Mn(CO)4 (3c) in
(1)
observed at 1710 and 1749 cmꢀ1, respectively, suggesting the
analogous bridging structure.
Complex 7a showed a fluxional behavior in solution, but this
behavior could be frozen below ꢀ80 ꢁC in toluene-d8. The IR
spectrum of 7a shows the stretching vibration assignable to the nCO
at 1936, 1852 and 1703 cmꢀ1. According to the IR spectrum,
compared with the Pt analog, the last band suggests the presence of
Dynamic behavior of heterodinuclear hydride complexes
a
m-carbonyl group. Thus, we tentatively assigned this compound as
As described above, all m-hydrido-m-carbonyl heterodinuclear
(dppe)Pd( -H)( -CO)MoCp(CO)2 (7a). Similarly, treatment of 6
with hydridotungsten 2b and -manganese complexes 2c in THF also
gave corresponding bridged heterodinuclear complexes, (dppe)
m
m
complexes showed fluxional behavior in a solution. Figs. 3 and 4
show variable-temperature 1H and 31P{1H} NMR spectra of (dppe)
Pt(m-H)(m
-CO)Mn(CO)4 (3c) in toluene-d8 [24]. In the 31P{1H} NMR,
Pd(m-H)(
m-CO)WCp(CO)2 (7b) and (dppe)Pd(
m-H)(
m-CO)Mn(CO)4
a couple of AB patterns at ꢀ80 ꢁC gradually broadened and
(7c). In the IR spectrum of 7b and 7c, bridging
n
CO bands were
collapsed, and a singlet is eventually appeared at 100 ꢁC. A double
Table 1
Reactions of Pt(alkene)L2 with transition-metal hydride complexes.a
0
Entry
Lʹ
Alkene
MHLn
Product
Yield/%
1
2
3
4
5
6
7
8
9
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PMePh2
PMe2Ph
(E)-stilbene
(E)-stilbene
Ethylene
Methyl acrylate
Methyl acrylate
Dimethyl fumarate
Dimethyl fumarate
Methyl acrylate
Methyl acrylate
2a
2b
2a
2a
2b
2a
2b
2a
2a
cis-(Ph3P)2HPteMoCp(CO)3 (5aa)
cis-(Ph3P)2HPteWCp(CO)3 (5ba)
cis-(Ph3P)2HPteMoCp(CO)3 (5aa)
cis-(Ph3P)2HPteMoCp(CO)3 (5aa)
cis-(Ph3P)2HPteWCp(CO)3 (5ba)
NRb
90
96
88
90
23
NRb
cis-(Ph2MeP)2HPteMoCp(CO)3 (5ab)
cis-(PhMe2P)2HPteMoCp(CO)3 (5ac)
92
95
a
Conditions: temp ¼ r.t., solvent ¼ C6D6 time ¼ 20 min.
NR ¼ no reaction.
b

198
N. Komine et al. / Journal of Organometallic Chemistry 792 (2015) 194e205
(process B). In this process, 3c converts into (dppe)PteMnH(CO)5
intermediate, where the -bonded HeMn(CO)5 fragment can freely
rotate, and get back to the -hydrido- -carbonyl species via non-
s
m
m
bridged structure, (dppe)HPteMn(CO)5. Although we do not have
conclusive data to differentiate the present mechanism, we believe
that process B seems to be likely because (i) the entropy of acti-
vation for the twist-rotation in cis-Pt(SnMe3)2(PMePh2)2 is quite
different from the present results, (ii) we have observed similar
non-dissociative
PteCo(CO)4 through the process alike process B [28], and (iii) the
activation parameters for the rotation of (dppe)[
h1 2-(E)-cin-
rotation
for
(dppe)[m- ,h
h1 2-(E)-cinnamyl]
m
- ,h
namyl]PteCo(CO)4 in toluene-d8
[
D
Hs
¼
46 kJ molꢀ1
,
DGs
¼ 57 kJ molꢀ1, and
D
Ss ¼ ꢀ37 J molꢀ1 Kꢀ1] are very close to
303
that for 3c. Braunstein and coworkers already suggested the same
intermolecular mechanism for the dynamic process in analogous
complexes with monodentate phosphine ligands [11c]. The NMR
spectra of the iron analog 3d suggest the involvement of similar
dynamic processes. The activation parameters for the dynamic
behavior of 3d are also estimated as follows:
D
Hs ¼ 25.7 kJ molꢀ1
,
DGs
¼ 58.5 kJ molꢀ1
,
D
Ss ¼ ꢀ109.8 J molꢀ1 Kꢀ1 in CD2Cl2. The
298
larger negative entropy of activation probably results from sterical
balkiness of the FeCp(CO)2 fragment.
Reaction of heterodinuclear hydridoplatinum and -palladium
complexes with unsaturated compounds
Reactions with alkenes
Of particular interest to hydride complexes is the reaction with
unsaturated compounds. Reactions of the heterodinuclear hydrido-
platinum complexes with alkenes were studied, and the results are
summarized in Table 2. When a hydridoplatinumemolybdenum
complex (dppe)HPtꢀMoCp(CO)3 (3a) was treated with dimethyl
fumarate at room temperature, the hydridomolybdenum complex 2a
and a zero-valent platinum complex Pt(dimethyl fumarate)(dppe)
were produced in 100% and 74% yields, respectively (entry 1). From
the platinum's point of view, this reaction is regarded as the reduc-
tive elimination between the MoCp(CO)3 and H ligands at the Pt
center. This is, therefore, the reverse reaction of the oxidative addi-
tion of 2a to the Pt(0) complex. Similar treatments of 3a with
dimethyl maleate, acrylonitrile, and ethyl acrylate gave 2a and cor-
responding Pt(alkene)(dppe) in low yields at small conversions
(entries 2e4). When ethylene was employed in this reaction, a het-
erodinuclear ethyl complexes (dppe)EtPtꢀMoCp(CO)3 was obtained
in 88% yield. Similar treatment of 3d with ethyl acrylate at room
temperature also resulted in the reductive elimination to give 2d and
Pt(ethyl acrylate)(dppe) in 80% and 100% yields, respectively [29].
Fig. 4. Variable temperature 31P{1H} NMR spectra of (dppe)Pt(
in toluene-d8.
m-H)(m-CO)Mn(CO)4 (3c)
doublet in 1H NMR, which is assigned to hydride ligand also
broadened simultaneously and finally gave a triplet. These spectral
changes are consistent with the exchange of two phosphorus nuclei
without dissociation (nor half-dissociation) of the phosphorus,
hydride and manganese fragments [25]. It is interesting to note that
only the outer two signals of the double doublet in 1H NMR was
broadened and coalesced, but the inner two signals remained sharp
(separation ¼ {j2JP(1)Hjꢀj2JP(2)Hj)). The coalescence of the outer
resonance indicates the opposite sign of the two PeH coupling
constants in 3c. Similar dynamics is also observed in analogous
complexes such as cis-(R3P)2Pt(
m
-H)(
m
-CO)Mn(CO)4 (R ¼ Ph, Et)
[11].
The activation parameters for these dynamic processes of the 1H
Reactions of the palladium derivative (dppe)Pd(m-H)(m-CO)
MoCp(CO)2 (7a) with alkenes were also studied, and the results are
summarized in Table 3.
NMR are estimated by gNMR simulation [26]:
D
Hs ¼ 37.2 kJ molꢀ1
,
DGs
¼ 55.8 kJ molꢀ1, and
D
Ss ¼ ꢀ62.5 J molꢀ1 Kꢀ1 in toluene-d6
298
D
and
Hs
¼
34.3 kJ molꢀ1
,
DGs
¼
56.8 kJ molꢀ1
,
Treatment of 7a with electron-deficient alkenes such as
dimethyl fumarate caused facile reductive elimination to give
MoHCp(CO)3 (2a) in 55% yield (entry 1). Similar treatment of 7a
with ethylene gave a new heterodinuclear ethyl complex (dppe)
EtPtꢀMoCp(CO)3 (entry 7). However, when terminal alkenes such
as methyl acrylate or acrylonitrile were employed, mononuclear
branched alkylmolybdenum complexes 10 were observed (entries
3 and 4). We consider that these branched alkylmolybdenum
complexes 10 are produced by a Markovnikov insertion of the
alkene into the PdeH bond in 7a followed by the subsequent
reductive elimination at Pd [14,30].
298
D
Ss ¼ ꢀ75.3 J molꢀ1 Kꢀ1 in CD2Cl2. The solvent did not significantly
affect these activation parameters, suggesting this dynamic process
to proceed in the same mechanism in toluene-d8 and CD2Cl2. The
large negative entropy of activation supports the non-dissociative
process. The following mechanisms shown in Scheme 3 are
consistent with all these experimental results. Process A is a twist-
rotation at Pt center via a pseudotetrahedral transition state. A
similar mechanism is suggested for fluxional behavior of cis-
bis(stannyl)- and bis(silyl)bis(phosphine)platinum and palladium
complexes [27]. The activation parameters for the twist-rotation at
Pt in cis-Pt(SnMe3)2(PMePh2)2 have been reported as
D
Hs ¼ 60 1 kJ molꢀ1 and
D
Ss ¼ 32 5 J molꢀ1
K
ꢀ1. The most
Reactions with alkynes
significant difference between the dynamic processes in 3c and cis-
Pt(SnMe3)2(PMePh2)2 is the
involves rotation of the
The reactions of (dppe)HPtꢀMoCp(CO)3 (3a) with electron-
deficient alkynes such as MeO2CC^CCO2Me, PhC^CPh,
HC^CCO2Me, and HC^CPh resulted in the facile reductive
D
s
Ss value. An alternative mechanism
-bonded HeMn(CO)5 intermediate

N. Komine et al. / Journal of Organometallic Chemistry 792 (2015) 194e205
199
Scheme 3. Possible mechanisms for the dynamic process of (dppe)Pt(m-H)(m-CO)Mn(CO)4 (3c).
elimination to give hydridomolybdenum complex, MoHCp(CO)3
(2a) and the corresponding zero-valent platinum(0) complexes,
Pt(alkyne)(dppe) (11) (Table 4, entries 1,2,4,6) [31].
respectively. A n
(CO) band at 1663 cmꢀ1 is assignable to the
methoxycarbonyl group. 31Pt{1H} NMR spectrum of 12a showed a
couple of doublets with 195Pt satellites at 2.54 and 3.24 ppm.
In contrast, 3a did not react with electron-rich alkyne such as
propyne. This is a similar to the reactivity of 3a for electron rich al-
kenes. It should also be noted that, in the reaction with terminal
alkynes having an electron-withdrawing group, further Markovni-
kov addition of MoHCp(CO)3 (2a) to the coordinating alkyne in
Pt(alkyne)(dppe) took place to give new heterodinuclear alkenyl
Similar to the platinum derivative, the reactions of (dppe)Pd(
m-
H)( -CO)MoCp(CO)2 (7a) with electron-deficient alkynes such as
m
MeO2CC^CCO2Me, PhC^CPh, and HC^CPh in C6D6 at room tem-
perature induced smooth hydride transfer from Pd to Mo to give
MoHCp(CO)3 (2a) and Pd(alkyne)(dppe) (Table 5, entries 1,3,5).
Further Markovnikov addition of resulting 2a to the coordinating
alkyne in Pd(alkyne)(dppe) took place to give new heterodinuclear
complexes (dppe)Pt(m-CR]CH2)(m-CO)MoCp(CO)2 (R
¼
CO2Me
(12a), Ph (12b), C6H4Me-p (12c)) in 48 h at room temperature (enties
5,7,8). These complexes 12a-c were characterized by 1H and 31P{1H}
NMR and IR spectroscopies, as well as by X-ray structure analysis of
12a. Single crystals of 12a suitable for the X-ray analysis were ob-
tained by recrystallization from THF with hexane. Fig. 5 shows an
ORTEP drawing of 12a. The geometry at Pt is essentially square
planar consisting of dppe, alkenyl and bridging carbonyl ligands. The
alkenyl complexes (dppe)Pd(
(14b), C6H4Me-p (14c)) in 24 h at room temperature. Contrary to
m
-CR]CH2)(
m
-CO)MoCp(CO) (R ¼ Ph
the platinum derivative, the corresponding alkenyl complexes
(dppe)Pd(
m
-CR]CHR)(
m
-CO)MoCp(CO) (R
¼
CO2Me (14d), Ph
(14e)) were formed even when 1,2-disubstituted electron deficient
alkynes were used in the reaction with 7a.
alkenyl C1]C2 moiety coordinates to Mo by an
of the carbonyl ligands is bridging between the Pt and Mo centers.
h
2 fashion, and one
DFT calculations of heterodinuclear hydridoplatinum complexes
The IR spectra of 12a showed n
(CO) bands at 1870 cmꢀ1 and
In order to understand the thermodynamic property and the
energy diagram of heterodinuclear hydridoplatinum complexes,
1731 cmꢀ1 assignable to a terminal and bridging carbonyl groups,
Table 2
Reaction of heterodinuclear hydrideplatinum complexes with alkenes.a
Entry
Complex
Alkene
Time/h
Conv./%
Yield/%
8
2
1
2
3
4
5
6
7b
8
9
3a
3a
3a
3a
3a
3a
3a
3d
3d
Dimethyl fumarate
Dimethyl maleate
Acrylonitrile
Ethyl acrylate
Styrene
1-Butene
Ethylene
Dimethyl fumarate
Ethyl acrylate
00.25
00.25
00.25
06
43
24
42
00.25
00.25
82
30
23
2
0
0
80
100
100
74
36
23
2
0
0
0
100
100
100
28
17
4
0
0
0
85
80
a
Conditions: [3] ¼ 0.02 M, [alkene] ¼ 0.03 M. temp ¼ 30 ꢁC, solvent ¼ C6D6.
Ethylene insertion product (dppe)EtPteMoCp(CO)3 was formed in 88%.
b

200
N. Komine et al. / Journal of Organometallic Chemistry 792 (2015) 194e205
Table 3
Reactions of (dppe)Pd(m-H)(m
-CO)MoCp(CO)2 (7a) with alkenes.a
Entry
Alkene
Time/h
Conv./%
Yield/%
9
2a
10
1
2
3
4
Dimethyl fumarate
Dimethyl maleate
Acrylonitrile
Ethyl acrylate
Styrene
00.5
00.1
00.1
00.5
43
100
100
100
80
0
92
NDd
NDd
NDd
NDd
0
55
60
33
35
0
0
0
19 (R ¼ CN)
12 (R ¼ CO2Me)
5
0
0
0
6b
7c
1-Butene
Ethylene
26
42
0
0
0
0
80
a
Conditions: [7a] ¼ 0.02 M, [alkene] ¼ 0.03 M. temp ¼ 30 ꢁC, solvent ¼ C6D6.
Isomerization of 1-butene to cis-2-butene and trans-2-butene (1:4) was observed.
Ethylene insertion product (dppe)EtPdꢀMoCp(CO)3 was formed in 88%.
Not determined.
b
c
d
the density functional theory (DFT) calculations were performed. In
these calculations, 1,2-bis(dihydrophoshino)ethane (dhpe) was
used instead of dppe, and the effect of solvent was not included.
Thermodynamic analyses for the oxidative addition of Pt(alke-
ne)(dhpe) with MoHCp(CO)3 (2a) and FeHCp(CO)2 (2d) were shown
in Scheme 4. In both cases, the oxidative addition of MHLn to
Pt(styrene)(dhpe) is an exothermic reaction and the reaction
spontaneously proceeds to the heterodinuclear hydridoplatinum
side. On the other hand, the oxidative addition of MoHCp(CO)3 to
Pt(methyl acrylate)(dhpe) is considered to be slightly more favor-
able process, but FeHCp(CO)2 is unlikely to add oxidatively to
Pt(methyl acrylate)(dhpe). This is consistent with the experimental
hand, only little energy difference between them was observed for
the PteMn and PteFe complexes. This is consistent with the fact
that the PteMo complex 3a has a robust non-bridged structure,
while facile interconversion between the bridged and non-bridged
structures is observed for the PteMn complex 3c and the PteFe
complex 3d.
Conclusion
A series of heterodinuclear hydridoplatinum and -palladium
complexes were synthesized by the oxidative addition of corre-
sponding mononuclear hydride complex with zero-valent plat-
inum and palladium complexes. The backward reductive
elimination of the metal fragment and hydride ligand at the Pt and
Pd center also proceeded smoothly, especially when electron
deficient alkenes were introduced. The trends are similar to the
reductive elimination of diorganotransition metal complexes. The
product ratios are controlled by the relative thermodynamic
results described above.
0
The relative free energies for (dhpe)Pt(
m-H)(
m-CO)MLn
0
(MLn ¼ MoCp(CO)2, Mn(CO)4, FeCp(CO)) compared to (dhpe)
HPteMLn (MLn ¼ MoCp(CO)3, Mn(CO)5, FeCp(CO)2) are summa-
rized in Scheme 5. The non-bridged structure is found to be more
stable than the bridged one for the PteMo complex. On the other
Table 4
Reactions of (dppe)HPtꢀMoCp(CO)3 (3a) with alkynes.a
Entry
Alkyne
Time/h
Conv./%
Yield/%
11
2a
12
1
2
3
4
5
6
7
8
DMAD
1
48
48
0.5
48
0.5
48
48
48
48
48
100
50
0
98
100
54
100
100
100
0
96
45
0
89
0
8
0
0
0
83
36
0
70
0
8
0
0
0
0
0
0
3
63
2
82
96
0
0
0
Diphenylacetylene
Phenylpropyne
Methyl 2-propynate
Phenylacetylene
4-ethynyltoluene
Propargyl alcohol
Propyne
9
10
11
0
0
0
0
Acetylene
100
a
Conditions: [3a] ¼ 0.02 M, [alkyne] ¼ 0.03 M. temp ¼ 30 ꢁC, solvent ¼ C6D6.

N. Komine et al. / Journal of Organometallic Chemistry 792 (2015) 194e205
201
Chemical shifts were reported in ppm downfield from TMS for 1H
and 13C and 85% H3PO4 in D2O for 31P. IR spectra were recorded on a
JASCO FT/IR-410 and JASCO FT/IR-4100 spectrometers using KBr
disks. Elemental analyses were carried out with a PerkineElmer
2400 series II CHN analyzer. PtI2(dppe) [33], MoHCp(CO)3 [34],
WHCp(CO)3 [35], MnH(CO)5 [36], and FeHCp(CO)2 [37] were pre-
pared according to literature procedures.
Synthesis of platinum(0) and palladium(0) complex having a dppe
ligand
Synthesis of Pt(styrene)(dppe) (1)
This new compound was prepared according to the modified
literature method [21]. To a solution of PtI2(dppe) (105.1 mg,
0.124 mmol) in THF (5 mL) was added a solution of NaBH4 (25.3 mg,
0.668 mmol) in EtOH (10 mL) and THF (3 mL) at ꢀ40 ꢁC and the
solution was stirred for 30 min at this temperature. Styrene (0.5 mL,
4.4 mmol) was added dropwise to this reaction solution
under ꢀ40 ꢁC. The mixture was warmed up to room temperature
gradually for 3 h. Then, the solution was concentrated under
reduced pressure, and excess MeOH was added to give analytically
pure pale yellow powder, which was filtered, washed with MeOH,
and dried under vacuum at room temperature. Yield 90% (77.7 mg,
Fig. 5. ORTEP drawing of (dppe)Pt{m-C(CO2Me)]CH2}(m-CO)MoCp(CO) (12a) [32]. All
hydrogen atoms and incorporated solvent molecule are omitted for clarity. Ellipsoids
represent 50% probability.
0.114 mmol). 31P{1H} NMR (C6D6, rt, 121.6 Hz):
d 51.3 (d,
stability of the starting compounds and products. Thus the Pt(0) or
Pd(0) complexes having an electron-rich alkene are favorable
starting complex for preparation of the heterodinuclear hydride
complexes by this oxidative addition method.
1
2
2JPP ¼ 81.8 Hz, JPtP ¼ 3305 Hz), 51.7 (d, JPP ¼ 81.8 Hz,
1JPtP ¼ 3320 Hz). 1H NMR (C6D6, rt, 300.4 Hz):
d 1.8e2.1 (m, 4H,
PCH2CH2P), 3.3 (m, 2H, CHH]CHPh), 4.56 (m, 1H, CHH]CHPh),
6.8e7.2 (m, 12H, m,p-Ph), 7.37 (d, 2H, 3JHH ¼ 7.5 Hz, Ph), 7.6e7.8 (m,
6H, o-Ph).
Experimental section
General procedures
Synthesis of Pd(ethyl acrylate)(dppe) (6)
This new compound was prepared according to the modified
literature method [21]. To a suspension of PdCl2(dppe) (241.0 mg,
0.418 mmol) in THF (8 mL) was added a solution of NaBH4 (77.7 mg,
2.05 mmol) in MeOH (5 mL) and THF (5 mL) at ꢀ70 ꢁC and this
reaction mixture was stirred until the color solution formed at this
temperature. Ethyl acrylate (2 mL,18 mmol) was added dropwise to
this reaction solution under ꢀ40 ꢁC. The mixture was warmed to
room temperature for 6 h. Then, the solution was concentrated
under reduced pressure, and excess MeOH was added to give
analytically pure white powder, which was filtered, washed with
MeOH, and dried under vacuum at room temperature. Yield 71%
All manipulations were carried out under a dry nitrogen or
argon atmosphere using standard Schlenk techniques. Solvents
were dried over and distilled from appropriate drying agents under
N2: hexane, benzene, toluene, diethyl ether and THF from Na/
benzophenone ketyl; CH2Cl2 from P2O5; acetone from Drierite;
MeOH from magnesium methoxide. The deuterated solvent for
NMR were commercially obtained and dried with appropriate
drying agents before use (C6D6 from Na; CD2Cl2 from P2O5;
acetone-d6 from Drierite). NMR spectra were recorded on a JEOL
LA-300 (300.4 MHz for 1H, 121.6 MHz for 31P, 75.3 Hz for 13C) and a
JEOL ECX400P (399.8 MHz for 1H, 161.8 MHz for 31P) spectrometers.
(179.0 mg, 0.2958 mol). 31P{1H} NMR (C6D6, rt, 121.6 Hz):
d
33.5 (d,
Table 5
Reactions of heterodinuclear hydridepalladium complexes with alkynes.a
Entry
Alkyne
Time/h
Yield/%
13
2a
14
1
2
3
4
5
6
7
DMAD
0.1
24
0.2
24
0.1
24
24
87
0
76
0
11
0
39
0
0
0
100
0
25
0
Diphenylacetylene
Phenylacetylene
4-ethynyltoluene
16
0
NDb
0
45
32
0
a
Conditions: [7a] ¼ 0.02 M, [alkyne] ¼ 0.03 M. temp ¼ 30 ꢁC, solvent ¼ C6D6.
b
Not determined.

202
N. Komine et al. / Journal of Organometallic Chemistry 792 (2015) 194e205
Scheme 4. DFT calculations for reaction of Pt(alkene)(dhpe) with MoHCp(CO)3 or FeHCp(CO)2.
2JPP ¼ 42.5 Hz), 39.9 (d, 2JPP ¼ 42.5 Hz). 1H NMR (C6D6, rt, 300.4 Hz):
(dppe)HPteWCp(CO)3 (3b)
d
1.0 (t, 3JHH ¼ 8 Hz, 1H, OCH2CH3), 1.9e2.1 (m, 4H, PCH2CH2P), 3.4
To a solution of Pt(styrene)(dppe) (1) (97.5 mg, 0.139 mmol) in
benzene (12 mL) was added a solution of WHCp(CO)3 (17.8 mg,
0.0723 mmol) in benzene (3 mL) at room temperature and the
solution was stirred for 30 min at this temperature. Then, the so-
lution was concentrated under reduced pressure, and excess hex-
ane was added to give an analytically pure pale yellow powder,
which was filtered, washed with hexane, and dried under vacuum
at room temperature (yield 84%, 99.7 mg, 0.118 mmol). Recrystal-
lization from benzene/hexane gave orange powder of 3b. Yield 45%
(br, 1H, cis-CH2]CHCO2Et), 4.0 (br, 1H, CH2]CHCO2Et), 4.2 (br, 2H,
OCH2CH3), 4.6 (1H, br, trans-CH2]CHCO2Et), 6.9e7.1 (m, 12H, m,p-
Ph), 7.5e7.8 (m, 8H, o-Ph).
Synthesis of heterodinucler hydrideplatinum and -palladium
complexes
(dppe)HPteMoCp(CO)3 (3a)
(52.4 mg, 0.0624 mmol). IR (KBr, cmꢀ1): 1817 (
nCO), 1925 (nCO),
To a solution of Pt(styrene)(dppe) (1) (97.5 mg, 0.139 mmol) in
benzene (12 mL) was added a solution of MoHCp(CO)3 (1a)
(17.8 mg, 0.0723 mmol) in benzene (3 mL) at room temperature and
the solution was stirred for 30 min at this temperature. Then, the
solution was concentrated under reduced pressure, and excess
hexane was added to give analytically pure pale yellow powder,
which was filtered, washed with hexane, and dried under vacuum
at room temperature (yield 84%, 99.7 mg, 0.118 mmol). Recrystal-
lization from benzene/hexane gave yellow cubes of 3a. Yield 45%
(52.4 mg, 0.0624 mmol). Mp 188 ꢁC (dec.). Anal. Found: C, 48.99; H,
3.67%. Calcd for C34H30O3P2MoPt: C, 48.64; H, 3.60%. IR (KBr, cmꢀ1):
2041 (
n
PtH). 31P{1H} NMR (C6D6, rt,121.6 Hz):
d
51.33 (d, 2JPP ¼ 4 Hz,
1JPtP ¼ 3313 Hz). 52.76 (d, JPP ¼ 4 Hz, JPtP ¼ 2093 Hz). 1H NMR
2
1
(C6D6, rt, 300.4 Hz):
1.8e2.1 (m, 4H, PCH2CH2P), 5.26 (s, 5H, Cp), 6.9e7.8 (m, 20H, Ph).
d
ꢀ2.92 (d, 2JPH ¼ 210 Hz, 1JPtH ¼ 970 Hz, PtH),
(dppe)Pt(m-H)(m-CO)Mn(CO)4 (3c)
To a solution of Pt(styrene)(dppe) (1) (143.8 mg, 0.2061 mmol)
in benzene (3 mL) was added a solution of MnH(CO)5 (2c) (90.4 mg,
0.461 mmol) in benzene (1.5 mL) at room temperature and the
solution was stirred for 30 min at this temperature. Then, the so-
lution was concentrated under reduced pressure, and excess hex-
ane was added to give analytically pure red powder, which was
filtered, washed with hexane, and dried under vacuum at room
temperature (yield 93%, 151.4 mg, 0.192 mmol). Recrystallization
from benzene/hexane gave red cubes of 3c. Yield 21% (77.0 mg,
1817 (
121.6 Hz):
nCO), 1925 (nCO), 2041 (n
PtH). 31P{1H} NMR (C6D6, rt,
d
49.0 (d, 2JPP ¼ 3 Hz, 1JPtP ¼ 3312 Hz 1P, trans to Mo), 50.8
(d, 2JPP ¼ 3 Hz, 2JPH ¼ 201 Hz, 1JPtP ¼ 2118 Hz, 1P, trans to H). 1H NMR
(C6D6, rt, 300.4 Hz): d d ꢀ2.39 (d, 2JPH ¼ 194 Hz, 1JPtH ¼ 869 Hz, PtH),
1.8e2.1 (m, 4H, PCH2CH2P), 5.25 (s, 5H, Cp), 6.9e7.8 (m, 20H, Ph).
0
Scheme 5. Relative free energies of (dhpe)Pt(
m
-H)(
m
-CO)MLn compared to (dhpe)HPteMLn.

N. Komine et al. / Journal of Organometallic Chemistry 792 (2015) 194e205
203
0.0975 mmol). Anal. Found: C, 48.55; H, 3.67%. Calcd for
31H25MnO5P2Pt: C, 47.16; H, 3.19%. IR (KBr, cmꢀ1): 1707 (
CO),1836
0.0772 mmol) at room temperature and the solution was stirred for
10 min at this temperature. After removal of the solvent, the residue
was washed with hexane and dried under vacuum. Recrystalliza-
tion from benzene and hexane gave yellow powder of 5ab in 59%
C
n
(nCO), 1930 (nCO), 1949 (nCO), 2045 (n
PtH). 31P{1H} NMR (toluene-
d8, ꢀ80 ꢁC, 161.8 Hz):
d
49.7 (d, 2JPP ¼ 13.2 Hz, 1JPtP ¼ 2803 Hz), 52.8
(m, 1JPtP ¼ 2856 Hz). 1H NMR (toluene-d8, ꢀ80 ꢁC, 399.8 Hz):
d
ꢀ2.15
(20.4 mg, 0.0284 mmol). IR (KBr, cmꢀ1): 1811 (
nCO), 1915 (nCO),
2
1
(d, JPH ¼ 158 Hz, JPtH ¼ 726 Hz, PtH), 1.68 (m, 4H, PCH2CH2P),
2110
(
¼
n
PtH). 31P{1H} NMR (C6D6, rt, 121.6 Hz):
d
¼
10.6 (d,
11.0 Hz,
ꢀ5.99 (d,
6.8e7.0 (m, 12H, m,p-Ph), 7.51 (m, 2H, o-Ph), 7.62 (m, 2H, o-Ph). 31
P
2JPP
11.0 Hz, JPtP
¼
3564 Hz), 13.8 (d, JPP
1
2
{1H} NMR (CD2Cl2, ꢀ80 ꢁC, 161.8 Hz):
d
44.6 (d, JPP ¼ 33 Hz,
1JPtP ¼ 2451 Hz). 1H NMR (C6D6, rt, 300.4 Hz):
d
2
1JPtP ¼ 2303 Hz), 46.1 (d, 2JPP ¼ 33 Hz, 2JPH ¼ 87 Hz, 1JPtP ¼ 4057 Hz).
2JPH ¼ 176 Hz, 1JPtH ¼ 714 Hz, 1H, PtH), 1.49 (m, 3H, PMe), 1.97 (m,
3H, PMe), 5.26 (s, 5H, Cp), 6.98e7.60 (m, 20H, Ph).
1H NMR (CD2Cl2, ꢀ80 ꢁC, 399.8 Hz):
d
ꢀ4.39 (dd, JPH ¼ 99.8,
2
13.2 Hz, 1JPtH ¼ 547 Hz, PtH), 2.43 (m, 4H, PCH2CH2P), 7.3e7.5 (m,
12H, m,p-Ph), 7.55 (m, o-Ph), 7.74 (m, o-Ph). 31P{1H} NMR (acetone-
(PhMe2P)2HPteMoCp(CO)3 (5ac)
d6, ꢀ80 ꢁC, 121.6 Hz):
d
46.6 (d, 2JPP ¼ 30.6 Hz, 1JPtP ¼ 3846 Hz), 47.1
To a solution of Pt(methyl acrylate)(PPhMe2)2 (0.0333 g,
2
1
(d, JPP ¼ 30.6 Hz, JPtP ¼ 2404 Hz). 1H NMR (acetone-d6, ꢀ80 ꢁC,
0.0597 mmol) in benzene was added MoHCp(CO)3 (0.0170 g,
0.0691 mmol) at room temperature and the solution was stirred for
15 min at this temperature. After removal of the solvent, the residue
was washed with hexane and dried under vacuum. Recrystalliza-
tion from benzene and hexane gave yellow powder of 5ac in 95%
399.8 Hz):
d
ꢀ4.13 (dd, 2JPH ¼ 104, 12.5 Hz, 1JPtH ¼ 555 Hz, PtH), 2.73
(m, 4H, PCH2CH2P), 7.4e7.6 (m, 12H, Ph). 7.70 (m, 4H, o-Ph), 7.92 (m,
4H, o-Ph).
(dppe)Pt(m-H)(
m-CO)FeCp(CO) (3d)
yield. IR (KBr, cmꢀ1): 1811 (
n
CO), 1915 (
n
CO), 2110 (
n
PtH). 31P{1H}
11.0 Hz,
2
To
a
solution of Pt(styrene)(dppe) (1) (100.27 mg,
NMR (C6D6, rt, 121.6 Hz):
d
ꢀ1.15 (d, JPP ¼
0.14372 mmol) in THF (3 mL) was added a THF solution of
FeHCp(CO)2 (2d) [35], prepared from NaFeCp(CO)2 and AcOH
at ꢀ30 ꢁC and the solution was stirred for 1 h at this temperature.
Then, the solution was concentrated under reduced pressure, and
excess hexane was added to give dark-purple powder, which was
filtered, washed with hexane, and dried under vacuum at room
temperature. Recrystallization from THF/hexane gave purple
powder of 3d. Yield 52% (57.9 mg, 0.0751 mmol). Anal. Found: C,
1JPtP ¼ 2260 Hz), ꢀ5.66 (s, 2JPP ¼ 36.0 Hz, 1JPtP ¼ 3531 Hz) 1H NMR
(C6D6, rt, 300.4 Hz):
d
ꢀ6.12 (dd, 2JPH ¼ 186, 6.3 Hz, 1JPtH ¼ 748 Hz,
2
3
1H, PtH), 1.18 (d, JPH ¼ 9.9 Hz, JPtH ¼ 42.0 Hz, 6H, Me), 1.50 (d,
2JPH ¼ 8.1 Hz, 6H, Me,), 5.32 (s, 5H, Cp), 6.96e7.52 (m, 10H, Ph).
(dppe)Pd(m-H)(
m-CO)MoCp(CO)2 (7a)
To
a
solution of Pd(ethyl acrylate)(dppe) (6) (38.5 mg,
0.0636 mmol) in THF (ca. 1 mL) was added MoHCp(CO)3 (17.8 mg,
0.0723 mmol) at ꢀ30 ꢁC and the solution was stirred for 30 min at
this temperature. Then hexane (ca. 20 mL) was added to precipitate
51.79; H, 4.07%. Calcd for C33H30FeO2P2Pt: C, 51.38; H, 3.92%. IR (KBr,
31
cmꢀ1): 1695 (
n
CO), 1904 (
n
CO). P{1H} NMR (toluene-d8, ꢀ80 ꢁC,
2
1
161.8 Hz):
d
44.2 (d, JPP ¼ 48 Hz, JPtP ¼ 2238 Hz), 45.7 (d,
analytically pure yellow powder of (dppe)Pd(m-H)(m-CO)
2JPP ¼ 48 Hz, JPtP ¼ 4245 Hz). 1H NMR (toluene-d8, ꢀ80 ꢁC,
MoCp(CO)2 (7a), which was filtered, washed with hexane, and
dried under vacuum at room temperature (yield 94%, 46.1 mg,
0.0601 mmol). Recrystallization from toluene gave orange powder
of 7a. Yield 45% (22.0 mg, 0.0286 mmol). Anal. Calcd for
1
399.8 Hz):
d
ꢀ7.27 (dd, 2JPH ¼ 83.9, 26.8 Hz, 1JPtH ¼ 564 Hz, PtH),1.83
(m, 4H, PCH2CH2P), 4.58 (s, 5H, Cp), 6.93 (m, 12H, m,p-Ph), 7.7 (m,
8H, o-Ph). 31P{1H} NMR (CD2Cl2, ꢀ80 ꢁC, 161.8 Hz):
d 44.3 (d,
2JPP ¼ 44 Hz, 1JPtP ¼ 2243 Hz), 48.0 (d, 2JPP ¼ 44 Hz, 1JPtP ¼ 4193 Hz).
C36H34MoO3.5P2Pd: C, 56.50; H, 4.86. Found: C, 55.77, H, 5.13. Mp
1H NMR (CD2Cl2, ꢀ80 ꢁC, 399.8 Hz):
d
ꢀ7.93 (dd, JPH ¼ 83.5,
125e128
ꢁC
(dec.).
Molar
electric
conductivity
L
2
23.7 Hz, 1JPtH ¼ 553 Hz, PtH), 2.43 (m, 4H, PCH2CH2P), 4.63 (s, 5H,
Cp), 7.41 (m, 12H, m,p-Ph), 7.56 (m, 4H, o-Ph), 7.73 (m, 4H, o-Ph).
(THF, ꢀ21 ꢁC) ¼ 0.49 S cm2 molꢀ1. IR (KBr, cmꢀ1): 1703 (
nCO), 1852
(
d
n
CO), 1936 (
n
CO). 31P{1H} NMR (toluene-d8, ꢀ80 ꢁC, 121.6 Hz):
25.1 (d, JPP ¼ 28 Hz), 26.5 (d, JPP ¼ 28 Hz). 1H NMR (toluene-
2
2
2
(Ph3P)2HPteMoCp(CO)3 (5aa)
d8, ꢀ80 ꢁC, 300.4 Hz):
d
ꢀ4.64 (dd, JPH ¼ 80.5, 9.0 Hz, 1H, PdH),
To
a
solution of Pt(trans-stilbene)(PPh3)2 (0.0690 g,
2.3e2.4 (m, 4H, PCH2CH2P), 5.25 (s, 5H, Cp), 7.40e7.65 (m, 12H, m,p-
Ph), 7.70e7.95 (m, 8H, o-Ph).
0.0621 mmol) in benzene was added MoHCp(CO)3 (0.0246 g
(0.100 mmol)) at room temperature and the solution was stirred for
20 min at this temperature. After removal of the solvent, the res-
idue was washed with hexane and dried under vacuum. Recrys-
tallization from benzene and hexane gave yellow powder of 5aa in
73% (22.0 mg, 0.0286 mmol). Spectroscopic data of the product was
compared with literature [11].
(dppe)Pd(m-H)(m-CO)WCp(CO)2 (7b)
To a solution of Pd(styrene)(dppe) (6) (73.4 mg, 0.121 mmol) in
THF (6 mL) was added WHCp(CO)3 (60.4 mg, 0.181 mmol) at ꢀ30 ꢁC
and the solution was stirred for 1 h at this temperature. Then, the
solution was concentrated under reduced pressure at ꢀ30 ꢁC, and
excess hexane was added to give analytically pure yellow powder of
(Ph3P)2HPteWCp(CO)3 (5ba)
7b. Yield 90% (95.6 mg, 0.109 mmol). IR (KBr, cmꢀ1): 1710 (
nCO),
To a solution of Pt(trans-stilbene)(PPh3)2 (0.0105 g, 0.012 mmol)
in benzene was added WHCp(CO)3 (0.0040 g, 0.012 mmol) at room
temperature and the solution was stirred for 30 min at this tem-
perature. After addition of hexane to the reaction mixture, this
solution was stored at ꢀ30 ꢁC overnight to give yellow needles. This
needles were dried under vacuum. Yield 91% (0.0118 g,
1851 (nCO), 1926 (nCO), 1731 (n
PdH). 31P{1H} NMR (toluene-
d8, ꢀ80 ꢁC, 121.6 Hz):
d
25.8 (br), 27.8 (br). 1H NMR (toluene-
2
d8, ꢀ80 ꢁC, 300.4 Hz):
d
ꢀ5.4 (d, JPH ¼ 63.4 Hz, 1H, PdH), 2.0e2.1
(m, 4H, PCH2CH2P), 4.7 (s, 5H, Cp), 6.7e7.1 (m, 12H, m,p-Ph), 7.4e7.6
(m, 8H, o-Ph).
0.011 mmol). 31P{1H} NMR (121.6 MHz, rt, toluene-d8):
d
27.6 (s,
(dppe)Pd(m-H)(m-CO)Mn(CO)4 (7c)
1JPtP ¼ 3615 Hz), 32.5 (s, 1JPtP ¼ 2625 Hz). 1H NMR (300.4 MHz, rt,
To a solution of Pd(styrene)(dppe) (6) (45.0 mg, 0.0739 mmol) in
THF (3 mL) was added MnH(CO)5 (42.2 mg, 0.215 mmol) at ꢀ30 ꢁC
and the solution was stirred for 1 h at this temperature. Then, the
solution was concentrated under reduced pressure at ꢀ30 ꢁC, and
excess hexane was added to give analytically pure orange powder
of 7c. Yield 90% (46.6 mg, 0.0665 mmol). Anal. Calcd for
toluene-d6):
d
ꢀ6.75 (d, 1H, 1JPH ¼ 166 Hz, 1JPtH ¼ 681 Hz, PtH), 5.18
(s, 5H, Cp), 6.88e7.65 (m, 30H, Ph).
(Ph2MeP)2HPteMoCp(CO)3 (5ab)
To
a solution of Pt(trans-stilbene)(PPh2Me)2 (0.0267 g,
0.0479 mmol) in benzene was added MoHCp(CO)3 (0.0190 g,
C31H25MnO5P2Pd: C, 53.13; H, 3.60. Found: C, 52.72, H, 3.75. IR (KBr,

204
N. Komine et al. / Journal of Organometallic Chemistry 792 (2015) 194e205
cmꢀ1): 1749 (
n
CO), 1919 (
n
CO), 1940 (
n
CO), 1956 (
n
CO), 2054 (
n
CO).
(dppe)Pd{
m
-(MeO2C)C]C(CO2Me)}(
m-CO)MoCp(CO) (14e)
31P{1H} NMR (toluene-d8, ꢀ80 ꢁC, 121.6 Hz):
d
25.1 (br). 1H NMR
Anal. Found: C, 54.39, H, 4.37%. Calcd for C39H36MoO6P2Pd: C,
(toluene-d8, ꢀ80 ꢁC, 300.4 Hz):
d
ꢀ6.05 (vt, 2JPH ¼ 23.7 Hz,1H, PdH),
54.15; H, 4.19%. IR (KBr, cmꢀ1): 1692 (
nCO), 1748 (nCO), 1905 (nCO).
1.68e1.72 (m, 4H, PCH2CH2P), 6.9e7.1 (m, 12H, m, p-Ph), 7.3e7.6 (br,
8H, o-Ph).
31P{1H} NMR (C6D6, rt,121.6 Hz):
d
38.17 (d, 2JPP ¼ 41.3 Hz), 45.79 (d,
2JPP ¼ 41.3 Hz). 1H NMR (C6D6, rt, 300.4 Hz):
d 1.71e1.78 (m, 4H,
PCH2CH2P), 3.06 (s, 3H, CO2Me), 3.51 (s, 3H, CO2Me), 3.40 (s, 1H, ]
CHCO2Me), 5.44 (s, 5H, Cp), 7.0e7.2 (m, 12H, m,p-Ph), 7.5e7.8 (m,
Reactions of heterodinucler hydrideplatinum and -palladium
complexes with alkynes and alkenes
8H, o-Ph). 31P{1H} NMR (CD2Cl2, rt, 121.6 Hz):
d 39.75 (d,
2JPP ¼ 42 Hz), 47.25 (d, 2JPP ¼ 42 Hz). 1H NMR (CD2Cl2, rt, 300.4 Hz):
d
2.06e2.41 (m, 4H, PCH2CH2P), 2.67 (d, JPH ¼ 7.8 Hz, 1H, ]
Reaction of heterodinucler hydrideplatinumemolybdenum complex
(3a) with methyl propiolate
A typical procedure for reaction of 3a with methyl propiolate is
given. (a) NMR reaction: C6D6 (0.5 mL) was vacuum-transferred to
an NMR tube (5 mmø ꢂ 180 mm) containing 3a (11.6 mg,
0.0138 mmol) and ferrocene. After addition of methyl propiolate
CHCO2Me), 2.88 (s, 3H, CO2Me), 3.45 (s, 3H, CO2Me), 5.19 (s, 5H, Cp),
7.3e7.5 (m, 12H, m,p-Ph), 7.6e7.7 (m, 8H, o-Ph).
Acknowledgments
We thank the Ministry of Education, Sports, Culture, Science,
and Technology (MEXT), Japan Society for the Promotion of Science
(JSPS) and Tokyo University of Agriculture and Technology for
financial support for this research. A part of this work was sup-
ported by Grant-in-Aids for Scientific Research on Priority Areas
“Chemistry of Concerto Catalysis” (No. 18065006) and Innovative
Areas “3D Active-Site Science” (No. 26105003) by MEXT and JSPS.
(17 mL, 0.014 mmol), the sample tube was placed in NMR probe, and
1H and 31P{1H} NMR spectra were periodically measured to follow
the reaction. (b) Reaction in Schlenk tube: To a solution of (dppe)
HPteMoCp(CO)3 (3a) (83.3 mg, 0.0992 mmol) in benzene (10 mL)
was added a solution of methyl propiolate (18.3 mL, 0.198 mmol) at
room temperature and the solution was stirred for 48 h at this
temperature. After removal of the solvent, recrystallization from
benzene/hexane gave orange crystal of (dppe)Pt{m-C(CO2Me)]
Appendix A. Supplementary data
CH2}(m-CO)MoCp(CO) (12a). Yield 69% (61.2 mg, 0.0683 mmol). Mp
246 ꢁC (dec.). Molar electric conductivity L (in THF at rt):
0.0110 S cm2 molꢀ1. Anal. Found: C, 50.90; H, 3.76%. Calcd for
CCDC No. 1041348 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/data_request/cif.
C
37H34MoO4P2Pt: C, 49.62; H, 3.83%. IR (KBr, cmꢀ1): 1663 (
n
CO),
1731 (nCO), 1870 (n d 46.54
CO). 31P{1H} NMR (CD2Cl2, rt, 121.6 Hz):
2
1
2
(d, JPP ¼ 36 Hz, JPtP ¼ 3258 Hz), 53.86 (d, JPP ¼ 3.6 Hz,
1JPtP ¼ 2772 Hz). 1H NMR (CDCl3, rt, 300.4 Hz):
d 2.2e2.5 (m, 4H,
Appendix B. Supplementary data
PCH2CH2P), 2.58 (d, 4JPH ¼ 6.0 Hz, 3JPtH ¼ 34 Hz, 1H, ]CH (Pt cis)),
3.03 (s, 3H, CH3), 3.29 (dd, 4JPH ¼ 10, 1.5 Hz, 3JPtH ¼ 116 Hz, 1H, ]CH
(Pt trans)), 5.04 (s, 5H, Cp), 7.3e7.8 (m, 20H, Ph). 13C{1H} NMR
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2015.04.048.
(CD2Cl2, rt, 75.3 Hz):
d
139.20 (d, JPC ¼ 80 Hz, C]CPt), 38.57 (s,
References
JPtC ¼ 16 Hz, C]CPt), 50.57 (s, CO2Me), 179.22 (s, CO2Me), 28.71 (d,
2
1
1JPC ¼ 35 Hz, JPC ¼ 13 Hz, PCH2CH2P), 31.39 (d, JPC ¼ 36,
2JPC ¼ 14 Hz, PCH2CH2P), 127e135 (m, Ph), 236.32 (m, CO(termi-
nal)), 245.88 (d, 2JPC ¼ 23 Hz, CO(bridging)).
[1] (a) P. Braunstein, L.A. Oro, P.R. Raith (Eds.), Metal Clusters in Chemistry,
WileyVCH, 1999 and references cited therein;
(b) D.F. Shriver, H.D. Kaesz, R.D. Adams, The Chemistry of Metal Cluster
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(dppe)Pt{
m
ꢀCPh]CH2}(
m-CO)MoCp(CO) (12b)
Yield 45%. Mp 234 ꢁC (dec.). Molar electric conductivity L (in
THF at rt): 0.0127 S cm2 molꢀ1. Anal. Found: C, 54.46; H, 4.03%.
Calcd for C41H36MoO2P2Pt: C, 53.89; H, 3.97%. IR (KBr, cmꢀ1): 1723
(nCO), 1858 (n d 49.78 (d,
CO). 31P{1H} NMR (C6D6, rt, 121.6 Hz):
2JPP ¼ 4 Hz, 1JPtP ¼ 3313 Hz), 51.60 (d, 2JPP ¼ 4 Hz, 1JPtP ¼ 2113 Hz). 1H
[3] (a) J.H. Jinfelt, in: J.R. Anderson, M. Boudard (Eds.), Catalysis-science and
Technology, Springer-Verlag, Berlin, 1981;
NMR (CDCl3, rt, 300.4 Hz):
d 2.1e2.4 (m, 4H, PCH2CH2P), 2.89 (d,
(b) J. Biswas, G.M. Bickle, P.G. Gray, D. Do, J. Barbier, J. Catal. Rev. Sci. Eng. 30
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(d) C. Kim, G.A. Somorjai, J. Catal. 134 (1992) 179.
4JPH ¼ 6.9 Hz, 3JPtH ¼ 25 Hz, 1H, ]CH (Pt cis)), 3.35 (d, 4JPH ¼ 13 Hz,
3JPtH ¼ 119 Hz,1H, ]CH (Pt trans)), 4.64 (s, 5H, Cp), 6.6e8.0 (m, 25H,
Ph).
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(dppe)Pt{
m-C(C6H4Me-p)]CH2}(m-CO)MoCp(CO) (12c)
IR (KBr, cmꢀ1): 1724 (
n
CO), 1858 (n
CO). 31P{1H} NMR (C6D6, rt,
121.6 Hz):
d
44.53 (s, 1JPtP ¼ 3256 Hz), 51.15 (s 1JPtP ¼ 2701 Hz). 1H
NMR (C6D6, rt, 300.4 Hz): d 1.8e2.1 (m, 4H, PCH2CH2P), 2.14 (s, 3H),
4
3
3.38 (d, JPH ¼ 6.3 Hz, JPtH ¼ 24 Hz, 1H, ]CH (Pt cis)), 3.60 (d,
4JPH ¼ 14 Hz, JPtH ¼ 119 Hz, 1H, ]CH (Pt trans)), 4.69 (s, 5H, Cp),
3
6.6e8.0 (m, 24H, Ph).
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was already described in the reference 11.
(dppe)Pd{m-CPh]CH2}(m-CO)MoCp(CO) (14b)
31P{1H} NMR (C6D6, rt, 121.6 Hz):
d
35.2 (d, 2JPP ¼ 29.8 Hz), 36.7
2
(d, JPP ¼ 29.8 Hz). 1H NMR (C6D6, rt, 300.4 Hz):
d 1.6e2.2 (m, 4H,
PCH2CH2P), 2.73 (dd, 4JPH ¼ 11.7 Hz, 2JHH ¼ 1.8 Hz, 1H, ]CHH), 3.12
(ddd, 4JPH ¼ 8.1 Hz,1.8 Hz, 2JHH ¼ 2.7 Hz,1H, ]CHH), 5.45 (s, 5H, Cp),
7.3e7.7 (m, 25H, Ph).

N. Komine et al. / Journal of Organometallic Chemistry 792 (2015) 194e205
205
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supporting information.
[25] These dynamic behaviors in both of the 1H and 31P{1H} NMR spectra indicate
the inequivalent two phosphorus nuclei becoming equivalent to each other
upon heating. Therefore, this dynamic process has no relation to the equi-
librium between the bridged and non-bridged complexes.
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the intrinsic thermodynamic stability of the hydridoiron(II) 2d because this is
a reversible reaction.
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square plane and octahedral geometries, respectively. This means the Pt
and Mn have the dsp2 and d2sp3 hybridizations. We, therefore, prefer not to
draw the Pt-Mn bond despite the close Pt-Mn distance.
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