Activation of Si-Si and Si-H Bonds at a Platinum Bis(diphenylphosphanyl)ferrocene (dppf) Complex: Key Steps for the Catalytic Hydrogenolysis of Disilanes

Article abstract of DOI:10.1002/ejic.201501210

Treatment of the platinum(0) complex [Pt(dppf)(nbe)] [1; dppf = 1,1′-bis(diphenylphosphanyl)ferrocene, nbe = norbornene] with the 1,2-dihydrodisilanes HPh₂SiSiPh₂H or HMe₂SiSiMe₂H gave [Pt(SiR₂H)₂(dppf)] (2, R = Ph; 4, R = Me) by oxidative addition of the Si-Si bond. The bis-silyl complexes 2 and 4 react with H₂ to give [Pt(H)(SiR₂H)(dppf)] (3, R = Ph; 5, R = Me) and H₂SiR₂. Adding HPh₂SiSiPh₂H to the hydrido silyl complex 3, which can also be prepared through Si-H activation of H₂SiPh₂ at 1, resulted in the regeneration of 2 as well as in the release of H₂SiPh₂. Treatment of HR₂SiSiR₂H with H₂ (1.7 bar) in the presence of 2 or 4 under moderate conditions led to the catalytic formation of H₂SiR₂ with TONs up to 25. The catalytic conversions are distinguished by a high selectivity for the hydrogenolysis of the 1,2-dihydrodisilanes, and no significant tendency for redistribution reactions at Si was observed.

Full text of DOI:10.1002/ejic.201501210

DOI: 10.1002/ejic.201501210
Full Paper
Disilanes
Activation of Si–Si and Si–H Bonds at a Platinum
Bis(diphenylphosphanyl)ferrocene (dppf) Complex: Key Steps
for the Catalytic Hydrogenolysis of Disilanes
[a]
[a]
[a]
[a]
Sabrina I. Kalläne, Reik Laubenstein, Thomas Braun,* and Maren Dietrich
Abstract: Treatment of the platinum(0) complex [Pt(dppf)- of H SiPh at 1, resulted in the regeneration of 2 as well as in
2
2
(
nbe)] [1; dppf = 1,1′-bis(diphenylphosphanyl)ferrocene, nbe = the release of H SiPh . Treatment of HR SiSiR H with H (1.7 bar)
2 2 2 2 2
norbornene] with the 1,2-dihydrodisilanes HPh SiSiPh H or in the presence of 2 or 4 under moderate conditions led to the
2
2
HMe SiSiMe H gave [Pt(SiR H) (dppf)] (2, R = Ph; 4, R = Me) by catalytic formation of H SiR with TONs up to 25. The catalytic
2
2
2
2
2
2
oxidative addition of the Si–Si bond. The bis-silyl complexes 2 conversions are distinguished by a high selectivity for the hy-
and 4 react with H to give [Pt(H)(SiR H)(dppf)] (3, R = Ph; 5, drogenolysis of the 1,2-dihydrodisilanes, and no significant
2
2
R = Me) and H SiR . Adding HPh SiSiPh H to the hydrido silyl tendency for redistribution reactions at Si was observed.
2
2
2
2
complex 3, which can also be prepared through Si–H activation
Introduction
silane by Si–Si bond cleavage to regenerate cis-[Pt(SiMe Cl) -
2 2
[
9]
(
PEt ) ]. It was also demonstrated that [Pt(PEt ) ] is capable
3 2 3 3
The activation of Si–H and Si–Si bonds at transition-metal com-
of activating (EtO) SiSi(OEt) , Me SiSiMe , and HPh SiSiPh H by
3
3
3
3
2
2
[
1]
plexes can be considered as one of the key steps in transition-
oxidative addition to form bis-silyl complexes. The reaction of
EtO) SiSi(OEt) with [Pt(PEt ) ] in the presence of H gave one
[
2]
metal-catalyzed reactions such as hydrosilylations, disilyl-
(
3
3
3 3
2
[
3]
[4]
ations,
or dehydrogenative couplings of hydrosilanes.
equivalent of HSi(OEt) and the hydrido silyl complexes cis- and
3
Whereas the latter reaction has been investigated in detail, the
catalytic process involved in the reverse reaction pathway, the
cleavage of silicon–silicon bonds with H , still represents a chal-
lenge. The few examples for the hydrogenolysis of disilanes,
most of which are covered by patents, usually require harsh
[
10]
trans-[Pt(H){Si(OMe) }(PEt ) ]. However, with HPh SiSiPh H or
Me SiSiMe , catalytic hydrogenolysis reactions were realized.
3
3 2
2
2
[
11]
3
3
2
H SiPh can be synthesized by treatment of HPh SiSiPh H with
2
2
2
2
H2 (6 bar) at room temperature in the presence of a mixture
[
5]
of cis- and trans-[Pt(SiPh H) (PEt ) ] (TON = 18). Stoichiometric
2
2
3 2
[
6]
reaction conditions, and they are often accompanied by low
selectivity. Nevertheless, the catalytic conversion of HPh Si-
reactions reveal an equilibrium between the bis-silyl complexes
2
II
and H2 to give H SiPh and the hydrido silyl Pt complexes
2
2
SiPh H and dihydrogen to generate H SiPh at room tempera-
2
2
2
2
cis-/trans-[Pt(H)(SiPh H)(PEt ) ] and [(Et P) (H)Pt(μ-SiPh )(μ-η -
2
3 2
3
2
2
ture in the presence of [Rh(Cl)(PPh ) ] as catalyst was described
by Rosenberg. In the absence of H , however, the dehydrogena-
tive coupling of H SiPh is preferred. Radius et al. presented
the capability of [Ni (iPr Im) (cod)] (iPr Im = 1,3-diisopropyl-im-
idazolin-2-ylidene, cod = 1,5-cyclooctadiene) to catalyze the
hydrogenolysis of Ph MeSiSiMePh and PhMe SiSiMe Ph with
hydrogen (1.8 bar) at room temperature (TON = 20 and 15),
3
3
HSiPh )Pt(PEt )]. The latter hydrido complexes react with
2
3
2
HPh SiSiPh H generating cis- and trans-[Pt(SiPh H) (PEt ) ] and
2
2
2
2
3 2
[
7a]
2
2
[12]
H SiPh .
HSiMe3 was formed catalytically by treatment of
2
2
2
2
4
2
Me SiSiMe with H (1.7 bar) at 393 K using [Pt(PEt ) ] as cata-
3
3
2
3 3
lyst (TON = 18). In contrast to the hydrogenolysis of HPh Si-
2
2
2
2
2
SiPh H, we suggest for the catalytic process with Me SiSiMe
2
3
3
the intermediary regeneration of [Pt(PEt ) ], because cis-
3
3
[
7b]
whereas no reaction was found with Me SiSiMe .
We re-
3
3
[
Pt(H)(SiMe )(PEt ) ] shows no reactivity towards H or Me Si-
3 3 2 2 3
ported on a reaction cascade at platinum for the conversion
of ClMe SiSiMe Cl with dihydrogen to yield two equivalents of
[
12]
SiMe3.
2
2
Complexes containing 1,1′-bis(diphenylphosphanyl)ferro-
[
8–11]
HSiMe Cl.
The Si–Si activation product cis-[Pt(SiMe Cl) -
2
2 2
cene (dppf) and related derivatives as ligands are of particular
(
PEt ) ] gave, with H , the silane HSiMe Cl and trans-
3 2 2 2
[13]
[14]
interest for instance as catalysts.
A bite angle
change at
[
Pt(H) (PEt ) ], but the latter does not react with ClMe Si-
2
3 2
2
these complexes, which can be important for a catalytic proc-
SiMe Cl, which hampered the development of a catalytic proc-
2
ess, can occur through a low-energy pathway because of the
ess. However, adding PEt to trans-[Pt(H) (PEt ) ] furnished H
3
2
3 2
2
[15]
high flexibility of the iron-cyclopentadienyl unit.
Further-
and [Pt(PEt ) ] and the platinum complex reacted with the di-
3
3
more, the proximity of two metal centers might be another
factor that leads to some of the unique reactivities observed
for complexes containing dppf. It has been speculated that the
two metal centers may act in a cooperative fashion to activate
[
a] Department of Chemistry, Humboldt-Universität zu Berlin,
Brook-Taylor-Straße 2, 12489 Berlin, Germany
E-mail: thomas.braun@chemie.hu-berlin.de
[
16]
https://www2.hu-berlin.de/chemie/braun/
organic substrates.
In addition, dppf containing compounds
Eur. J. Inorg. Chem. 2016, 530–537
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can be of interest because of their electrochemical behav- tetraene), and [Pt(dppf)(trans-stilbene)].[18] For the hydrogen at-
[
17]
ior.
oms of the platinum bonded CH=CH moiety, a resonance with
1
95
Herein, we report on Si–Si and Si–H activation reactions of
Pt satellites (JPt,H = 65 Hz) is detected at δ = 2.87 ppm in
1
HR SiSiR H (R = Ph, Me) and H SiPh at the platinum(0) dppf the H NMR spectrum, which is consistent with the data for
2
2
2
2
[
19]
complex [Pt(dppf)(nbe)] (1, nbe = norbornene) to yield bis-silyl [Pt(nbe) ]. Suitable crystals of 1 were obtained from a benz-
3
and hydrido silyl complexes. Based on stoichiometric activation ene solution at room temperature. The molecular structure of
reactions, a catalytic hydrogenolysis of silicon–silicon bonds 1 in the solid state is illustrated in Figure 1 and selected bond
was developed that proceeds selectively under moderate con- lengths and angles are summarized in Table 1. The platinum
ditions.
atom is disordered, and a distorted tetrahedral coordination
sphere is revealed at the platinum centers. The bite angle at
the platinum atom of the dppf ligand [104.322(16)°] is slightly
Results and Discussion
II
[15a]
larger than in {Pt (dppf)} species,
angle in [Pt(dppf)(trans-stilbene)].
but in accordance to the
As expected, the coordi-
[
18b]
The complex [Pt(dppf)(nbe)] (1) was synthesized from a 1:1 mix-
ture of [Pt(nbe) ] and dppf (Scheme 1). The reaction proceeded
at room temperature and gave 1 in very high yield. Compound
nation of norbornene at Pt effects an elongation of the C35–
3
C36 double bond to 1.454(3) Å [for comparison: [Pt(nbe) ]:
3
[
19a]
1
.38(5)–1.41(2) Å].
The complex [Pt(dppf)(nbe)] (1) is a useful starting material
displays a singlet with 1 Pt satellites at δ = 29.6 ppm. The for the oxidative addition of the Si–Si bond in HR
SiSiR H (R =
platinum–phosphorus coupling constant (JPt,P = 3520 Hz) is in Ph, Me). Reactions at room temperature led to the formation
good agreement with those found for the platinum(0) com- of [Pt(SiPh H) (dppf)] (2) or [Pt(SiMe H) (dppf)] (4) within 1 h
plexes [Pt(dppf)(C H )], [Pt(dppf)(cot)] (cot
cycloocta- (Scheme 1). Note that a few other examples for the Si–Si bond
1
was characterized by NMR spectroscopic analysis, elemental
31
1
analysis and X-ray crystallography. The P{ H} NMR spectrum
95
2
2
2
2
2
2
=
2
4
Scheme 1. Synthesis of the bis-silyl and hydrido silyl complexes 2–5.
Eur. J. Inorg. Chem. 2016, 530–537 www.eurjic.org
531
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1
736 Hz) for 2 and at δ = 30.2 ppm (JPt,P = 1616 Hz) for 4.
Both coupling constants are in the typical range for platinum
[
8i,8j,8n,9–11]
phosphine cis-bis-silyl complexes,
might be attributed to the higher trans-influence
SiMe H moiety compared with the SiPh H ligand. The H NMR
and their difference
[
20]
of the
1
2
2
1
95
spectra reveal multiplet resonances with
.76 ppm for 2 and at δ = 4.50 ppm for 4 [virtual triplet for 2,
JPt,H = 75 Hz, JP,H(apparent) = 19 Hz; virtual triplet of septet for 4
JPt,H = 67 Hz, JP,H(apparent) = 20 Hz], which can be assigned to
the silicon-bonded hydrogen atoms. The signal of 2 simplifies
Pt satellites at δ =
5
[
21]
1
95
29
to a singlet with
Pt and Si satellites (JSi,H = 172 Hz) in a
3
1
195
P decoupling experiment. For complex 4, a septet with Pt
1
31
satellites was detected in the H{ P} NMR spectrum. The pres-
ence of the silyl ligands in 2 is also revealed by a doublet (J
=
P,Si
1
95
1
29 Hz) with Pt satellites (JPt,Si = 1140 Hz) at δ = –10.4 ppm
2
9
1
1
29
in the Si{ H} NMR spectrum. The H, Si HMBC NMR spectrum
of 4 displays a signal for a correlation of the silicon atoms with
the methyl hydrogen atoms, which appears as a doublet with
1
95
29
Pt satellites in the Si domain (JP,Si = 93 Hz, JPt,Si = 1080 Hz).
The identity of 2 was further confirmed by X-ray diffraction
analysis. An ORTEP diagram of the molecular structure is de-
picted in Figure 2; selected bond lengths and angles are re-
ported in Table 1. The structure shows an approximately square
planar arrangement of the chelating phosphine ligand and the
two silyl ligands at the platinum center. The silicon-bound
hydrogen atoms were found in the difference Fourier map and
refined isotropically. The Pt–Si bond lengths of 2.3569(6) and
Figure 1. ORTEP diagram of 1. The ellipsoids are drawn at the 50 % probability
level. The asymmetric unit cell contains a mixture of two isomers, which differ
in the position of the platinum atom (occupancy of 86.5 % for Pt01); only the
structure of the major conformer is shown. The hydrogen atoms are omitted
for clarity.
2
.3955(6) Å are consistent with those of other bis-silyl plati-
[
8d,8i,8m,8r,8t,8u,22]
num(II) complexes.
The bulky silyl groups result
in a Si1–Pt1–Si2 angle of 79.97(2)° {for comparison: 79.91(9)°
Table 1. Selected distances [Å] and angles [°] for 1, 2, and 3 with estimated
standard deviations in parentheses (X = C35, Y = C36 for 1; X = Si1, Y = Si2
for 2; X = H1, Y = Si1 for 3) (Cp = cyclopentadienyl).
[8d,8u]
in cis-[Pt(SiPh H) (PEt ) ]; 87.36(2)° in [Pt(SiPh H) (dppe)]}.
2
2
3 2
2
2
[
20]
Their strong trans influence led to an elongation of the Pt–P
bonds [2.3584(5) and 2.3479(5) Å] when compared with those
in 1. The metal–phosphorus distances are also slightly longer
Distance
1
2
3
P1–Pt1
P2–Pt1
Pt1–X
Pt1–Y
X–Y
2.2549(4)
2.2735(5)
2.143(2)
2.109(2)
1.454(3)
2.2549(4)
2.3584(5)
2.3479(5)
2.3569(6)
2.3955(6)
2.3192(4)
2.2830(4)
1.454
II
[15a]
than those in other Pt (dppf) species.
2.3366(4)
P1–Pt1
2.3584(5)
2.3192(4)
Angle
1
2
3
P1–Pt1–P2
X–Pt1–Y
104.322(16)
39.99(8)
98.612(19)
79.97(2)
103.400(14)
76.0
P1–Pt1–X
P1–Pt1–Y
P2–Pt1–X
P2–Pt1–Y
Cp1–Fe1–Cp2
145.17(6)
105.56(6)
109.98(6)
149.97(6)
176.84
94.67(2)
88.0
163.981(14)
168.4
92.585(14)
177.10
172.552(17)
165.788(18)
87.226(19)
178.55
[
a]
[
a] Angle between the ring centroid of the Cp ligands and the iron atom.
activation of 1,2-dihydrodisilanes at platinum complexes yield-
[
8k,8n,8r,8u,11]
ing bissilyl complexes have been reported.
We ob-
served no reactivity of 1 towards (MeO) SiSi(OMe) , Ph SiSiPh ,
3
3
3
3
or Me SiSiMe , even at 323 K. It has been shown that Si–Si
3
3
Figure 2. ORTEP diagram of 2. The ellipsoids are drawn at the 50 % probability
level. The C–H hydrogen atoms are omitted for clarity. The silicon-bonded
hydrogen atoms were found in the difference Fourier map.
activation reactions can proceed through an initial Si–H activa-
[
8n,8r,8u]
tion step.
Complexes 2 and 4 were identified by NMR spectroscopy
3
1
1
and elemental analysis. The P{ H} NMR spectra show, in each
The bis-silyl complexes 2 and 4 react with dihydrogen at
room temperature to form the hydrido silyl complexes
case, a singlet with 1 Pt satellites at δ = 29.7 ppm (JPt,P
95
=
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532
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[
Pt(H)(SiPh H)(dppf)] (3) or [Pt(H)(SiMe H)(dppf)] (5) and H1 and the silicon atom Si1. As expected, the Pt1–P2 bond of
2
2
H SiPh or H SiMe , respectively (Scheme 1). The complexes as 2.2830(4) Å is shorter than the Pt1–P1 bond of 2.3192(4) Å be-
2
2
2
2
well as the silanes were identified by NMR spectroscopy. Com- cause of the different ligands in the trans positions to the phos-
pound 3 was also synthesized independently by treatment of phorus atoms. Compared with 2, the platinum–phosphorus as
[
Pt(dppf)(nbe)] (1) with H SiPh . The Si–H cleavage reaction oc- well as platinum–silicon bond length are slightly shortened, and
2 2
curs immediately at room temperature.
the bite angle of the dppf ligand is widened. However, the Pt1–
3
1
1
The P{ H} NMR spectra of 3 and 5 each exhibit two dou- Si1 distance of 2.3366(4) Å in 3 is comparable to the corre-
1
95
[8g,8r]
blets with
atoms of the bidentate ligand. All resonances reveal a phos- platinum–phosphorus distances are similar to the Pt–P bonds
Pt satellites for the two inequivalent phosphorus sponding bond separation in [Pt(H)(SiPh
H)(PR ) ]
2 3 2
and the
[
23]
phorus–phosphorus coupling of JP, P = 18 Hz. The signals with in [Pt(H)(SiPh )(PR (CH ) PR )] (R = Cy, Ph).
3 2 2 4 2
the smaller platinum–phosphorus coupling constant [δ =
The complexes 2 and 3, bearing SiPh H ligands, are stable in
2
3.7 ppm (JPt,P = 1707 Hz) for 3 and δ = 34.2 ppm (JPt,P
3 =
solution, but reactivity studies at 4 and 5 revealed a different
behavior. Thus, a solution of 4 in benzene is not stable, and 4
converted completely into a product mixture containing,
1569 Hz) for 5] can be assigned to the phosphorus atom in the
trans position to the SiR H moiety due to the larger trans influ-
2
ence of the silyl ligand, whereas the signals at δ = 30.4 ppm
among other unidentified compounds, complex
5 and
(
5
JPt,P = 2052 Hz) for 3 and at δ = 30.0 ppm (JPt,P = 2146 Hz) for
are caused by the phosphorus atoms in the trans position to
the hydrido ligand. The hydrido ligands of 3 and 5 give rise to
[Pt(dppf) ] (6) after 9 d at room temperature. Furthermore, after
2
removal of the volatiles in vacuo from a reaction solution con-
taining 5, which was prepared from 4 and H , the bis-silyl com-
2
1
95
Pt satellites in the 1H NMR spectra at δ =
signals with
0.64 ppm for both complexes. For the silicon-bonded hydro-
gen atom, resonances at δ = 4.99 ppm (3) and at δ = 4.56 ppm
5) were detected. The signal for 3 appears as a doublet of
plex 4 was regenerated to some degree (ca. 20 %). However,
–
after treatment of 4 with H , small amounts of 6 were also
2
detected. An increase of the reaction time after exposure of 4
with dihydrogen led to a further conversion and to precipitation
of 6, which could then be isolated. For the equivalent phos-
(
29
195
doublet of doublets with Si and Pt satellites (JSi,H = 171 Hz,
JPt,H = 13 Hz) caused by a coupling to the phosphorus atoms
in the trans and cis position and the metal-bonded hydrogen
31
1
phorus atoms in 6 the P{ H} NMR spectrum reveals a singlet
resonance at δ = 6.9 ppm, which is shifted significantly to
higher field when compared to the signals of 1–5. The plati-
1
29
atom. The H, Si HMBC NMR spectrum of 3 shows a resonance
at δ = 8.3 ppm in the 29Si domain (JP,Si = 170 Hz, JPt,Si
040 Hz), which correlates with resonances for the SiPh H
=
num–phosphorus coupling constant of J = 3939 Hz indicates
Pt,P
1
0
2
the oxidation state of Pt and is in good agreement with the
couplings in [Pt{PPh (CH ) PPh } ] (n = 2,3).
1
group and the hydrido ligand in the H domain. For 5 a signal
at δ = –15.3 ppm (J = 135 Hz, J = 1030 Hz) was found in
[24]
2
2 n
2 2
P,Si
Pt,Si
To develop a catalytic process for the conversion of HPh Si-
2
2
9
1
29
the Si domain of the H, Si HMBC NMR spectrum. The molec-
ular structure in the solid state of 3 (Figure 3) was determined
by X-ray diffraction analysis. Selected bond lengths and angles
are summarized in Table 1. The platinum atom is coordinated
with an approximately square-planar geometry by the phos-
phorus atoms P1 and P2 of the dppf ligand, the hydrogen atom
SiPh H into the secondary silane, [Pt(H)(SiPh H)(dppf)] (3) was
2
2
treated with one equivalent of HPh SiSiPh H. The reaction af-
2
2
fords bis-silyl complex 2 with concomitant formation of H SiPh2
2
(
Scheme 1). Within one day at room temperature, 2 was quanti-
tatively regenerated from 3. This conversion, together with the
reaction of 3 with hydrogen to yield 2 and H SiPh , completes
2
2
a cyclic process. Note that 3 does not react with H SiPh at
2
2
room temperature, which suggests that hydrogen generation
through the reverse reaction steps is not favored. Accordingly,
investigations for a catalytic dehydrogenative coupling of
H SiPh using 2,2-dimethylbutene as hydrogen trapping agent
2
2
in the presence of 2 led only to the generation of trace amounts
of HPh SiSiPh H, even at higher temperature.
2
2
The reactivity of 2 as catalyst in the hydrogenolysis of
HPh SiSiPh H was then studied (Table 2). On treatment of
2
2
HPh SiSiPh H with hydrogen in the presence of 10 mol-% 2,
2
2
H SiPh was formed in substantial amounts (according to the
2
2
NMR spectroscopic analysis) after 20 h at room temperature.
On using 3 mol-% 2 as catalyst, an increase of the reaction
temperature was required. After 20 h at 313 K, H SiPh2 was
2
obtained in 24 % yield, whereas better yields were achieved at
3
33 K. After 2 d at 333 K, a TON of 25 was accomplished accord-
1
ing to H NMR spectroscopic analysis. We did not observe any
products of redistribution of the phenyl groups at Si in appreci-
able amounts, although such reactions were found to be medi-
Figure 3. An ORTEP diagram of 3. The ellipsoids are drawn at the 50 % proba-
bility level. The C–H hydrogen atoms are omitted for clarity. The silicon- and
platinum-bonded hydrogen atoms were found in the difference Fourier map.
[
4a,7,25]
ated frequently at transition-metal centers.
Finally, de-
spite the instability of 4 and 5 in solution, we were delighted
Eur. J. Inorg. Chem. 2016, 530–537
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533
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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to find that HMe SiSiMe H is also a viable substrate for catalytic lett–Packard) and an Agilent 5973 Network mass-selective detector
2
2
at 70 eV. Infrared spectra were recorded with a Bruker Vertex 70
spectrometer that was equipped with an ATR unit (diamond). The
microanalyses were obtained with a Euro EA HEKAtech elemental
analyzer.
hydrogenolysis under mild conditions (1.7 bar, room tempera-
ture) in the presence of 10 mol-% 4 (Table 2).
Table 2. Catalytic hydrogenolysis of disilanes using 2 or 4 as catalyst.
[
Pt(dppf)(nbe)] (1): A suspension of [Pt(nbe) ] (0.760 g, 1.59 mmol)
3
and dppf (0.880 g, 1.59 mmol) in benzene (6 mL) was stirred for 1 h
at room temperature. The volatiles were removed under vacuum.
The remaining yellow solid was washed with toluene (2 × 0.5 mL)
Conversion
into silane (%)
Disilane
Cat. (mol-%)
Temp.
Time
and dried in vacuo, yield 1.325 g (99 %). C41
H38FeP Pt·toluene
2
1
(
935.76): calcd. C 61.61, H 4.95; found C 61.60, H 4.99. H NMR
1
31
HPh
2
2
SiSiPh
2
2
H
H
2 (10)
2 (3)
r.t.
20 h
20 h
93
(300.1 MHz, C D ): δ = 7.94 (m, tm in the H{ P} NMR spectrum,
6 6
JH,H = 8 Hz, 8 H, CHPh), 7.14–7.00 (m, 12 H, CHPh), 4.28 (m, 4 H,
CHCp), 3.89 (m, 4 H, CHCp), 3.03 (m, 2 H, CH), 2.87 (br. s + Pt satellites,
JPt,H = 65 Hz, 2 H, CH), 1.80 (m, 2 H, CH ), 1.63 (dm, J = 7 Hz, 1
HPh
SiSiPh
333 K
60
74
2
d
2
H,H
HPh
2
SiSiPh
2
H
2 (3)
313 K
r.t.
20 h
2
3
24
44
52
H, CH ), 1.49 (m, 2 H, CH ), 0.64 (d, J
= 8 Hz, 1 H, CH ) ppm.
2
2
H,H
2
d
d
31
1
P{ H} NMR (121.5 MHz, C D ): δ = 29.6 (s + Pt satellites, J =
6
6
Pt,P
3520 Hz) ppm.
≥ 47 (76)[
≥ 65 (94)[
a]
HMe
2
SiSMe
2
H
4 (10)
20 h
2
a]
d
[Pt(SiPh H) (dppf)] (2): [Pt(dppf)(nbe)] (1) (79.0 mg, 94 μmol) and
2
2
HPh SiSiPh H (34.3 mg, 94 μmol) were dissolved in benzene
[
a] The amount of the gaseous product H
H NMR spectroscopic analysis; consumption of HMe
2
SiMe
2
dissolved in C
6
D
6
based on
2
2
1
(1.5 mL) and the reaction mixture was stirred for 2 h at room tem-
perature. The volatiles were removed under vacuum. The remaining
yellow solid was washed with n-hexane (3 × 1 mL) and dried in
vacuo, yield 93.0 mg (89 %). C H FeP PtSi ·benzene (1194.18):
2
SiSMe H (determined
2
by using an external standard) in parentheses.
5
8
50
2
2
1
calcd. C 64.37, H 4.73; found C 64.44, H 4.88. H NMR (300.1 MHz,
Conclusions
C D ): δ = 7.72 (m, 8 H, CHPh), 7.64 (m, 8 H, CHPh), 7.07 (m, 12 H,
6
6
CHPh), 6.89 (m, 12 H, CHPh), 5.76 (vt + Si and Pt satellites, s + Si and
Catalytic processes for the hydrogenolysis of HPh SiSiPh H and
1
31
2
2
Pt satellites in the H{ P} NMR spectrum, apparent J = 19 Hz,
P, H
HMe SiSiMe H to access H SiPh or H SiMe were developed.
2
2
2
2
2
2
JSi,H = 172 Hz, J
4
= 75 Hz, 2 H, SiH), 4.10 (m, 4 H, CHCp), 3.82 (m,
Pt,H
The development of such reaction routes are expected to be of
general interest because they generate hydrosilanes for further δ = 7.6/–10.5, 5.8/–10.5 (s + Si satellites in the H domain, J
H, CHCp) ppm. 1H, Si HMBC NMR (300.1 MHz/59.6 MHz, C D ):
29
6
6
1
=
Si,H
[
26]
29
1
syntheses.
Note that chlorinated disilanes are byproducts of 180 Hz). Si{ H} NMR (59.6 MHz, C D ): δ = –10.4 (d + Pt satellites,
6 6
3
1
1
the Müller–Rochow process and are consequently obtained in
large amounts in industry.
J
P,Si = 129 Hz, JPt,Si = 1140 Hz) ppm. P{ H} NMR (121.5 MHz, C
D ):
6 6
[
27]
δ = 29.7 (s + Pt satellites, JPt,P = 1736 Hz) ppm.
The presented catalytic processes are distinguished by a high
selectivity for the hydrogenolysis of 1,2-dihydrodisilanes and do
[
2
Pt(H)(SiPh H)(dppf)] (3): A solution of [Pt(dppf)(nbe)] (1) (245 mg,
2
90 μmol) in benzene (4.5 mL) was treated with H SiPh (54 μL,
2 2
not lead to the redistribution of substituents at silicon. Dihydro- 290 μmol) and the reaction mixture was stirred for 45 min at room
gen functions as hydrogen source and a {Pt(dppf)} species temperature. The volatiles were removed under vacuum. The re-
serve as catalyst. Putative reaction steps of the catalytic process maining yellow solid was washed with n-hexane (2 × 1 mL) and
dried in vacuo, yield 255 mg (94 %). Analytical C H FeP PtSi·ben-
were identified by stoichiometric reactions. The conversions in-
clude the Si–Si activation of a disilane at a platinum(0) precur-
sor to generate a bis-silyl complex as well as the reaction of the
bis-silyl complex with dihydrogen to yield one equivalent of the
secondary silane and a hydrido silyl complex. Finally, transfor-
mation of the latter with disilane into a second equivalent of
silane along with the regeneration of bis-silyl complexes was
realized.
46 40
2
zene (1011.88): calcd. C 61.72, H 4.58; found C 61.72, H 4.61. IR (ATR,
–
1 1
diamond): ν˜ = 2031 (PtH) cm . H NMR (300.1 MHz, C D ): δ = 8.06
6
6
1
31
(
(
(
dm, m in the H{ P} NMR spectrum, J = 7 Hz, 4 H, CH ), 8.00
P, H Ph
dm, m in the H{ P} NMR spectrum, J = 7 Hz, 4 H, CHPh), 7.87
m, 4 H, CHPh), 7.23–6.97 (m, 18 H, CHPh), 4.99 (ddd + Si and Pt
1
31
P, H
satellites, JP, H = 20 Hz, JP, H = 5 Hz, JH,H = 3 Hz, JSi,H = 171 Hz, JPt,H
3 Hz, 1 H, SiH), 4.18 (m, 2 H, CHCp), 4.05 (m, 2 H, CHCp), 3.78 (m, 2
H, CHCp), 3.72 (m, 2 H, CHCp), –0.64 (ddd + Pt satellites, J = 160 Hz,
=
1
P, H
29
1
JP, H = 20 Hz, JH,H = 3 Hz, JPt,H = 1020 Hz, PtH) ppm. H, Si HMBC
NMR (300.1 MHz/59.6 MHz, C D ): δ = 8.1/8.3 (d + Pt satellites in
6
6
the 29Si domain, JP,Si = 170 Hz, JPt,Si = 1040 Hz), 4.7/8.3, –0.7/8.3 (d
Experimental Section
1
29
in the H domain, J = 160 Hz, d in the Si domain, JP,Si = 170 Hz).
Si,H
General: The synthetic work was carried out either with a Schlenk
line or in a glove box in an atmosphere of argon. All solvents were
purified and dried by conventional methods and distilled in an at-
mosphere of argon before use. NMR spectra were recorded at 300 K
31
1
P{ H} NMR (121.5 MHz, C D ): δ = 33.7 (d + Pt satellites, J
8 Hz, JPt,P = 1707 Hz, 1 P, Ptrans to Si), 30.4 (d + Pt satellites, JP, P
8 Hz, JPt,P = 2502 Hz, 1 P, Ptrans to H) ppm.
=
=
6
6
P, P
1
1
with a Bruker DPX 300 or a Bruker Avance III 300 NMR spectrometer. Treatment of [Pt(SiPh H) (dppf)] (2) with H : A solution of
2
2
2
1
H NMR chemical shifts were referenced to residual C D H at δ =
[Pt(SiPh H) (dppf)] (2) (21.2 mg, 19 μmol) in C D (0.3 mL) in a
6
5
2 2 6 6
.16 ppm. 31P{ H} NMR spectra were referenced to external H PO
1
Young NMR tube was cooled to 77 K, degassed and pressurized
with H to 1 bar. After 3 d at room temperature, the NMR spectro-
7
3
4
2
9
at δ = 0.0 ppm, and the Si NMR spectra were referenced to exter-
2
nal SiMe at δ = 0.0 ppm. GC–MS spectra were measured with an scopic data of the reaction solution revealed a quantitative conver-
4
Agilent 6890N gas-phase chromatograph (Agilent 19091S-433 Hew- sion and the formation of [Pt(H)(SiPh H)(dppf)] (3) and H SiPh .
2
2
2
Eur. J. Inorg. Chem. 2016, 530–537
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534
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
Treatment of [Pt(H)(SiPh H)(dppf)] (3) with HPh SiSiPh H: A so-
JPt,H = 38 Hz, 6 H, SiCH ), –0.64 (dd + Pt satellites, s + Pt satellites
2
2
2
3
1
31
lution of [Pt(H)(SiPh H)(dppf)] (3) (9.6 mg, 10 μmol) in C D (0.3 mL) in the H{ P} NMR spectrum, J = 164 Hz, JP, H = 21 Hz, JPt,H = 1092 Hz,
2
6
6
P, H
1
29
was treated with HPh SiSiPh H (7.6 mg, 20 μmol). After 1 d at room
1 H, PtH) ppm. H, Si HMBC NMR (300.1 MHz/59.6 MHz, C D ): δ =
0.8/–15.3 (d + Pt satellites in the Si domain, JP,Si = 135 Hz, JPt,Si =
2
2
6 6
29
temperature, the NMR spectroscopic data of the reaction solution
quantitative conversion and the formation of 1030 Hz). 31P{ H} NMR (121.5 MHz, C D ): δ = 34.2 (d + Pt satellites,
1
revealed
a
6
6
[
Pt(SiPh H) (dppf)] (2) and H SiPh .
JP, P = 18 Hz, JPt,P = 1569 Hz, 1 P, Ptrans to Si), 30.0 (d + Pt satellites,
JP, P = 18 Hz, JPt,P = 2416 Hz, 1 P, Ptrans to H) ppm.
2
2
2
2
[
2
(
Pt(SiMe H) (dppf)] (4): A solution of [Pt(dppf)(nbe)] (1) (197 mg,
2 2
34 μmol) in benzene (4 mL) was treated with HMe SiSiMe H
40 μL, 234 μmol) and the reaction mixture was stirred for 1 h at
Isolation of [Pt(dppf)
(127 mg, 147 μmol) in benzene (2 mL) was cooled to 77 K, degassed
and pressurized with H to 1 bar. After stirring for 2 d at room
2 2 2
] (6): A solution of [Pt(SiMe H) (dppf)] (4)
2
2
room temperature. The volatiles were removed under vacuum. The
remaining yellow solid was washed with n-hexane (2 × 0.4 mL) and
dried in vacuo, yield 201 mg (99 %). C H FeP PtSi ·toluene
(
(
2
temperature, a yellow solid precipitated. The solution was filtered
off, the residue was washed with n-hexane (0.3 mL) and dried in
4
5
50
2
2
1
959.23): calcd. C 56.30, H 5.25; found C 56.41, H 5.24. H NMR
vacuo, yield 6 mg (10 %). C68
H
56Fe
2
P
4
Pt (1303.84): calcd. C 62.64, H
4.33; found C 61.99, H 4.52. H NMR (300.1 MHz, C ): δ = 7.85 (m,
dd in the 1H{ P} NMR spectrum, JH,H = 7 Hz, JH,H = 2 Hz, 16 H,
1
300.1 MHz, C D ): δ = 7.94 (m, 8 H, CH ), 7.08 (m, 12 H, CHPh),
D
6 6
6
6
Ph
1
31
31
4
.50 (vt sept + Pt satellites, sept + Pt satellites in the H{ P} NMR
spectrum, apparent JP, H = 20 Hz, JH,H = 3 Hz, JPt,H = 67 Hz, 2 H, SiH),
4
+
3
CHPh), 6.94–6.81 (m, 24 H, CHPh), 4.32 (m, 8 H, CHCp), 4.32 (t, JH,H =
2 Hz, 8 H, CHCp) ppm. 31P{ H} NMR (121.5 MHz, C
1
D ): δ = 6.9 (s +
6 6
.06 (m, 4 H, CHCp), 3.78 (m, 4 H, CHCp), 0.58 (dm + Pt satellites, d
1
31
Pt satellites in the H{ P} NMR spectrum, J
= 4 Hz, JPt,H
=
Pt satellites, JPt,P = 3939 Hz) ppm.
H,H
1
29
0 Hz, 12 H, CH ) ppm. H, Si HMBC NMR (300.1 MHz/59.6 MHz,
3
Catalytic Formation of H SiPh by Reaction of HPh SiSiPh H
2 2 2 2
2
9
C D ): δ = 0.6/–9.7 (d + Pt satellites in the Si domain, JP,Si = 93 Hz,
6
6
with H in the Presence of [Pt(SiPh H) (dppf)] (2): (a) A mixture
2 2 2
JPt,Si = 1080 Hz). 31P{ H} NMR (121.5 MHz, C D ): δ = 30.2 (s + Pt
1
6
6
of [Pt(SiPh H) (dppf)] (2) (5.4 mg, 5 μmol) and HPh SiSiPh H
2 2 2 2
satellites, JPt,P = 1616 Hz) ppm.
(17.6 mg, 48 μmol) in C D (0.5 mL) in a NMR pressure tube was
6
6
cooled to 77 K, degassed and pressurized with H to 1.7 bar. After
[
Pt(H)(SiMe H)(dppf)] (5): A solution of [Pt(SiMe H) (dppf)] (4)
2
2
2
2
1
13
20 h, the solution was analyzed by H and C NMR spectroscopy
(8.7 mg, 10 μmol) in benzene (0.3 mL) was cooled to 77 K, degassed
as well as by GC–MS. The data revealed the conversion of HPh Si-
and pressurized with H to 1 bar. After 1 d at room temperature,
the NMR spectroscopic data revealed the conversion of 4 and the
2
2
1
SiPh H into H SiPh was 93 % (according to the H NMR spectro-
2
2
2
scopic analysis). In addition, an unidentified compound was formed
in small amounts (3 %).
formation of [Pt(H)(SiMe H)(dppf)] (5) (90 % according to the
2
3
1
1
P{ H} NMR spectrum) and minor amounts of [Pt(dppf) ] (6) (10 %)
2
1
1
as well as of H SiMe (according to the H NMR spectrum). H NMR
(b) A mixture of [Pt(SiPh H) (dppf)] (2) (2.2 mg, 2 μmol) and HPh Si-
2
2
2
2
2
1
31
(300.1 MHz, C D ): δ = 8.00 (m, dm in the H{ P} NMR spectrum,
SiPh H (24.1 mg, 66 μmol) in C D (0.5 mL) in a NMR pressure tube
6
6
2 6 6
JH,H = 8 Hz, 4 H, CHPh), 7.96 (m, 4 H, CHPh), 7.84 (m, 1 H, CHPh), 7.72
was cooled to 77 K, degassed, and pressurized with H to 1.7 bar.
2
The solution was heated to 333 K and analyzed by H and C NMR
1
13
(m, 1 H, CHPh), 7.13–6.95 (m, 10 H, CHPh), 4.56 (m, 1 H, SiH), 4.24
(
m, 2 H, CHCp), 4.11 (m, 2 H, CHCp), 3.83 (m, 2 H, CHCp), 3.77 (m, 2 spectroscopy. The data revealed the conversion of HPh SiSiPh H
2
2
H, CH ), 0.80 (dd + Si and Pt satellites, d + Si and Pt satellites in
into H SiPh was 60 % after 20 h and 74 % after 2 d (according
2 2
to the H NMR spectroscopic analysis). In addition, an unidentified
Cp
31
1
1
the H{ P} NMR spectrum, J = 4 Hz, JP, H = 3 Hz, JSi,H = 118 Hz,
H,H
Table 3. Crystallographic data.
1
2
3
Empirical formula
Formula weight
Crystal size [mm ]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
C
41
H
38FeP
2
Pt·C
6
D
6
C
58
H
50FeP
2
PtSi
2
·C
6
D
6
C
46 2 6 6
H40FeP PtSi·2 C D
927.74
0.59 × 0.39 × 0.31
triclinic
P1¯
1200.18
0.67 × 0.35 × 0.17
triclinic
P1¯
1102.04
0.30 × 0.22 × 0.11
monoclinic
3
1
P2 /c
10.7186(9)
13.2016(12)
14.3597(13)
82.559(3)
81.225(3)
72.352(3)
1906.2(3)
2
1.616
4.163
2.188–29.196
100657
10.8926(18)
12.367(2)
20.192(3)
83.458(5)
78.038(5)
84.310(5)
2635.6(7)
2
1.279
3.073
2.353–28.768
120129
11.1536(4)
21.4275(8)
20.1661(8)
ꢀ
[°]
92.6450(10)
γ [°]
3
V [Å ]
4814.4(3)
4
1.520
3.333
2.153–29.658
161481
Z
3
Calcd. density [Mg/m ]
μ(Mo-K
) [mm–1
θ range [°]
α
]
Reflections collected
Independent reflections
10306
13677
13576
R
int
0.0503
1.038
0.0964
1.042
0.0403
1.045
Goodness-of-fit on F2
Completeness to max. θ
99.7 %
99.7 %
99.8 %
R
R
1
, ωR
, ωR
2
on all data
[I > 2σ(I )]
o
> 2σ(I )]
0.0200, 0.0497
0.0193, 0.0493
10069
0.0237, 0.0600
0.0233, 0.0596
13446
0.0230, 0.0430
0.0185, 0.0413
12345
1
2
o
o
Reflect. with [I
o
Largest diff. peak, hole [e A–3]
1.543/–0.792
1.886/–1.990
1.316/–0.597
Eur. J. Inorg. Chem. 2016, 530–537
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535
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
compound was formed in small amounts (3 and 6 %, respective-
ly).
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(
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2
2
2
1
02007055732A1, 2008.
SiPh H (26.3 mg, 72 μmol) in C D (0.5 mL) in a NMR pressure tube
2
6 6
[
[
6] R. Calas, G. Deleris, J. Dunogues, M. Lefort, C. Simmonet, J. Organomet.
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was cooled to 77 K, degassed, and pressurized with H to 1.7 bar.
2
1
13
The solution was heated to 313 K and analyzed by H and C NMR
spectroscopy. The data revealed the conversion of HPh SiSiPh H
2
2
into H SiPh was 24 % after 20 h, 44 % after 2 d, and 52 % after 3 d
2
2
1
(
according to the H NMR spectroscopic analysis). In addition, an
unidentified compound was formed in small amounts (1, 3, and
%, respectively).
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2
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2
2
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2 2 2 2
5
8 μmol) in C D6 [0.5 mL; containing toluene (5 μL) as external
6
standard] in a NMR pressure tube was cooled to 77 K, degassed,
1
13
and pressurized with H to 1.7 bar. The H and C NMR spectro-
2
scopic data revealed the consumption of HMe SiSiMe H was 76 %
2
2
2
3, 5744–5756; h) J. Braddock-Wilking, J. Y. Corey, K. A. Trankler, H. Xu,
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2
2
(
according to the 1H NMR spectroscopic analysis). In addition, an
unidentified compound was formed in small amounts (2 % after
d).
2
Structure Determination of the Complexes 1, 2, and 3: Crystals
of 1–3 precipitated from reaction solutions in C D at room temp.
6
6
7
5
1
957; o) Y. Tanaka, H. Yamashita, M. Tanaka, Organometallics 1995, 14,
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Crystallographic data are depicted in Table 3. Data collections were
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28]
[29]
2
square procedures based on F with all measured reflections
(
SHELXL-2013) with anisotropic temperature factors for all non-
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All non-metal-bonded hydrogen atoms were
[
[
[
[
added geometrically and refined by using a riding model.
CCDC 1419468 (for 1), 1419469 (for 2), and 1419470 (for 3) contain
the supplementary crystallographic data for this paper. These data
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Acknowledgments
The authors acknowledge the financial support by the Deut-
sche Forschungsgemeinschaft (DFG).
[
Keywords: Platinum · Silicon · Si–Si activation · Si–H
activation · Hydrogenolysis
[
3
98, 46–53.
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Received: October 21, 2015
Published Online: January 12, 2016
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