Catalytic N-Si coupling as a vehicle for silane dehydrocoupling: Via α-silylene elimination

Article abstract of DOI:10.1039/c7dt04507g

Exploration of (N₃N)ZrNMe₂ (1, N₃N = N(CH₂CH₂NSiMe₃)₃^3-) as a catalyst for the cross-dehydrocoupling or heterodehydrocoupling of silanes and amines suggested silylene reactivity. Further studies of the catalysis and stoichiometric modeling reactions hint at α-silylene elimination as the pivotal mechanistic step, which expands the 3p elements known to engage in this catalysis and provides a new strategy for the catalytic generation of low-valent fragments.

Full text of DOI:10.1039/c7dt04507g

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PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
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Catalytic N–Si Coupling as a Vehicle for Silane Dehydrocoupling
via α-Silylene Elimination†
Karla A. Erickson,a,b Michael P. Cibuzar,a Neil T. Mucha,a,c and Rory Waterman*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Exploration of (N3N)ZrNMe2 (1, N3N = N(CH2CH2NSiMe3)33–) as a evidence that zirconium amido derivatives can liberate silylene
catalyst for the cross-dehydrocoupling or heterodehydrocoupling fragments, an insight that may avail more facile routes to the
of silanes and amines suggested silylene reactivity. Further study catalytic generation of R2Si: fragments and related synthetic
of the catalysis and stoichiometric modeling reactions hint at an α- chemistry.
silylene elimination as the pivotal mechanistic step, which
Literature observations of Zr(NMe2)4 reactivity were readily
expands the 3p elements known to engage in this catalysis and replicated but no catalysis was identified.7 For example,
avails a new strategy for catalytic generation of low-valent treatment of phenylsilane with 10 mol % of Zr(NMe2)4 gave
fragments.
Ph(NMe2)SiH2, Ph(NMe2)2SiH, and a yellow precipitate
consistent with [(Me2N)3Zr(μ-H)(μ-NMe2)2]2Zr.7a It was
hypothesized that increased solubility of Zr(NMe2)4 may lead
to catalysis, but replication of the above reaction with one
equivalent of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene
(IMes) also gave stoichiometric N–Si products and a similar
precipitate. Given the success of triamidoamine-supported
zirconium in dehydrocoupling catalysis,6, 8 we next considered
this ligand to increase catalyst solubility.
An increased premium has been placed on Si–N
heterodehydrocoupling as a reaction that affords products of
high synthetic utility and interest.1 For example, silazanes have
been of use as silylating agents,2 bases,3 ligands for catalysts,
and as ceramic or polymer precursors.4 While excellent work
has been done in this area discovering and understanding
metal and non-metal catalysts,1 general catalysts for this
reaction that tolerate both sterically encumbered substrates or
that provide selectivity between a single or multiple Si–N bond
forming events on the same substrate (one or two reactions at
RNH2 or RR’SiH2, for example) remain challenges. Despite
advances in from each Hill and Sadow in development of group
Treatment of mixtures of silanes and amines with 10 mol %
of (N3N)Zr derivatives resulted in limited in catalytic activity.
For example, heating phenylsilane with excess dimethylamine
9
in the presence of 10 mol % of (N3N)ZrNMe2
(1
) to 80 °C in
benzene-d6 resulted in 60% formation of Ph(NMe2)SiH2 versus
phenylsilane over 24 hours (~90% conversion after 48 hours)
with apparent decomposition of (N3N)ZrNMe2 to a complex
mixture of unidentified products (eqn (1)). The limited efficacy
of (N3N)Zr derivatives for N–Si dehydrocoupling was not
immediately clear given their past success in P–Si and P–Ge
bond forming catalysis.8c The reaction of phenylsilane with
2 metal catalysts,1c, zirconium is an interesting potential
5
candidate being relatively abundant while readily engaging in
dehydrocoupling catalysis.6 Supporting that hypothesis are
reports of Zr(NMe2)4 reacting with silanes to give N–Si bonds,7
though that chemistry is limited to stoichiometric N–Si bond
formation and subsequent formation of a poorly soluble
polymetallic hydride product. We report herein our
exploration of catalytic N–Si bond formation by zirconium.
Despite meeting limited success in improving upon literature
catalysts, this work has led to suggestions of silylene reactivity
which is unique within this field. Further studies within provide
isopropylamine in the presence of 10 mol % of 1 at 80 °C in
benzene-d6 produced minimal Ph(NMe2)SiH2.§ However, some
diphenylsilane was also observed by 1H NMR spectroscopy and
1
confirmed in H-29Si HSQC experiments. Silane (SiH4) was not
identified in these reactions, and a similar phenyl migration
has been reported by Tilley to proceed via a cationic Hf–Ph
intermediate.10 The possibility of a rare early transition-metal
catalyzed redistribution was nevertheless intriguing because
critical metal-mediated silicon catalysis, including the Direct
Process and redistribution reactions,11 appear to involve
unsaturated silicon derivatives such as silylenes (R2Si:).
Aggressive study of such transition-metal silylene (LnM=SiR2)
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compounds has yielded substantial reactivity and new that were low and unreliable between experiments.
catalysts.12 Likewise, useful organosilane products can be Redistribution products were not observed.
prepared utilizing silylene fragments generated via photolysis
followed by trapping with organic reagents,13 but the direct reactivity. Reaction of
Silanes featuring π-basic substituents gave different
2
with Ph(X)SiH2 (X = NMe2 or Cl) yielded
; Cl)8d, 9 derivatives as the solely
generation of silylene fragments via metal catalysis, such as
elimination, remains an untapped area.
α
known (N3N)ZrX (X = NMe2 ,
1
identifiable metal-containing product by H NMR spectroscopy
1
(eqn (2)). Significant decomposition of
2 was also observed.
Phenylsilane was observed as a byproduct for both substrates.
(1)
Tilley identified that dehydropolymerization of stannanes
appear to occur via
-stannylene elimination.14 In group 15,
stibine and -arsinidene elimination reactions have also been
(2)
α
α-
Mass balance suggests that the byproduct from reactions
α
of
2 with Ph(X)SiH2 (X = NMe2 or Cl) is phenylsilylene (PhHSi).
reported, and form small rings or distibenes or disarsenes,
respectively.8b, 15 Layfield first realized catalytic trapping of a
phosphinidene fragments using bis(NHC) iron and cobalt
The observation of phenylsilane, even in deuterated solvents,
may be related to the low conversion and substantial
degradation of zirconium compounds in the reaction.
Nevertheless, such a transformation has precedent. Andersen
and coworkers have shown that cerocene hydrides react with
haloalkanes or ethers to give Ce–X (F, Cl, OR) bonds and the
corresponding alkane.20 These reactions appear to proceed via
catalysts,16 while we have expanded on
α-phopshinidene
elimination as a route to organophosphines via trapping.17
These observations and the value of organosilanes argue for
exploration of
α-silylene elimination and the possibility of
resultant organosilane synthesis.
a two-step process involving C
formation followed by methylidene elimination and trapping
by hydrogen—a stoichiometric -carbene elimination
–H bond activation and H2
The suggestion of silylene chemistry prompted
investigation of zirconium-silyl derivatives supported by the
[κ5-N,N,N,N,C-
) with one
α
triamidoamine
ligand.
Reaction
of
(
reaction.20 Based on the same arguments that Andersen has
made, it is presumed that the formation of the strong Zr–N
bond is a driving force for silylene elimination. Prior studies
suggest that Zr–N bonds are among the strongest for (N3N)ZrX
family of compounds based on structural evidence and
computational models.18
(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH2]Zr
2
equivalent of primary or secondary aryl or alkyl silane failed to
produce a silyl complex of the type (N3N)ZrSiRnH3–n (N3N =
N(CH2CH2NSiMe3)33–). Extended reactions resulted in the
apparent decomposition of
derivative may be unstable with respect to cyclometalation
and restoration of . It is already known that (N3N)ZrX
derivatives can rapidly exchange the pseudoaxial X ligand, and
that if X is of sufficient steric bulk,
is favored.8b, 18 To test this
hypothesis, was treated with one equivalent of phenylsilane-
d3, which rapidly afforded a mixture of PhSiHD2, PhSiH2D, and
2. It was suspected that any silyl
While the relative stability of a Zr–N bond might appear to
2
be detrimental to catalysis,
stoichiometric N–Si bond formation,8d which suggested that
catalytic -silylene elimination may be possible. A testable
hypothesis emerged: Does catalytic N–Si bond formation
enable -silylene elimination? Dehydrocoupling of silanes with
, a reaction that is unsuccessful with (vide supra), would
test this hypothesis.
Treatment of phenylsilane in benzene-d6 at 80 °C with as
little as 5 mol % of gave a mixture of silicon-containing
1 is already known to undergo
2
α
2
19
α
PhSiH3 as well as 2-dn, illustrating equilibrium formation of a
1
2
disfavored silyl derivative (Scheme 1).
1
products, including predominately 1,2-diphenyldisilane
(PhSiH2)2 (2%), Ph(NMe2)SiH2 (3%) and low molecular weight
1
linear and cyclic oligosilanes (5%) as characterized by H and
29Si NMR spectroscopy (eqn (3)).21 These reactions require
heating for several days at 80 °C to achieve limited conversion
of phenylsilane. With increased catalyst loading, typically to 20
Scheme 1. Pathway for the incorporation of deuterium on 2 from phenylsilane via a
presumed silyl intermediate, (N3N)ZrSiD2Ph.
mol %, Ph(NMe2)2SiH,
a non-productive byproduct, is
With evidence for a transient silyl compound, more
aggressive efforts to solicit reactivity were explored. Heating
generated. Diphenysilane was far less reactive towards the
catalysis. After five days of heating at 80 °C (20 mol % catalyst
loading), 10% conversion to Ph2(NMe2)SiH, was measured. No
reaction was observed between either PhMeSiH2 or Ph3SiH
and the catalyst over five days at 80 °C.
mixtures of
2
with excess (2
–
10 equiv.) phenylsilane resulted
with trace quantities of
in the ultimate decomposition of
2
hydrogen, 1,2-diphenyldisilane, and oligosilanes in conversions
2 | Dalton Trans., 2017, 00, 1-3
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2% (PhSiH2)2
1
5 mol%
PhSiH3
3% Ph(NMe2)SiH2
5% oligosilanes
benzene-d6,
80 C,
°
5 days, -H2
(3)
These observations and literature precedent lead to the
proposed catalytic cycle (Scheme 2). The first step in the
catalysis appears to be a Si–N heterodehydrocoupling reaction
between
transformation necessarily produces a zirconium hydride that
is known to rapidly dehydrogenate to the metallacycle 2 19
The
stoichiometric reactions then suggest that Ph(NMe2)SiH2 ring
opens , resulting in a silyl intermediate (N3N)ZrSiHPhNMe2
that is poised for -silylene elimination and restoration of
The phenylsilylene fragment could then insert into the Si
1 and phenylsilane resulting in Ph(NMe2)SiH2. This
.
2
α
1.
–
H
bond of another equivalent of phenylsilane to yield the
disilane product, which is consistent with literature
precedent.13, 14c, 22
Scheme 2. Proposed catalytic cycle for the dehydrocoupling of phenylsilane using
(N3N)ZrNMe2 (1).
In the catalysis, formation of Ph(NMe2)2SiH presumably
results from the reaction of
situ. This process would be catalyst deactivating, consuming
multiple equivalents of NMe2 and leaving , which is unstable
in the presence of excess phenylsilane (vide supra).
Decomposition of limits consumption of starting
phenylsilane. There is insufficient formation of Ph(NMe2)SiH2
to suggest that the decomposition occurs solely from , but
1 with Ph(NMe2)SiH2 generated in
H
H
1
10 mol %
+
PhSiH3 10Ph
Ph
benzene-d6,
Ph
Ph
2
°
80 C
(4)
1
The limitations of
and Corey’s report of phenylsilane dehydropolymerization
using Cp2Zr(NMe2)2 ( ) was intriguing given their observations
of high activity and formation of Ph(NMe2)SiH2 as
1 invited consideration of other catalysts,
2
3
the complex mixture of decomposition products are similar in
both the stoichiometric and catalytic reactions. The working
hypothesis is that competitive N–Si bond formation occurs
between phenylsilane and the amido arms of the
triamidoamine ligand to strip the ligand off zirconium. While
this is consistent with the formation of Si–NMe2 derivatives,
there is no direct evidence to support this pathway given the
complex mixtures of decomposition products. The competitive
degradation process and the apparent instability of (N3N)Zr–
silyl derivatives preclude a detailed mechanistic analysis of the
a
byproduct.25 Because this catalysis is established, only trapping
reactions were pursed. Reaction of phenylsilane with three
equivalents of the organic trapping reagents diphenylacetylene
or 2,3-dimethyl-1,3-butadiene in the presence of 10 mol % of
3
yielded no evidence of a silole and small quantities of PhH2Si-
SiH2Ph and PhH2SiNMe2. Competitive silane polymerization
was observed in the case of 2,3-dimethyl-1,3-butadiene,
whereas diphenylacetylene stunted catalysis entirely.
Replicating that reaction with diethyldisulfide as the trap
afforded Ph(EtS)2SiH26 in 21% conversion as identified by NMR
system key to prior instances of
α
–elimination.14b There is,
however, precedent for silylene elimination. Pannell and co-
workers have reported photo-driven iron-catalyzed silylene
elimination.23
(1H, H/29Si HSQC) spectroscopy and GC/MS (eqn (5)). Such a
1
trapping reaction represents the microscopic reverse of known
generation of silylene from dithiolsilanes.23a
Trapping was pursued as potential verification of silylene
formation. Phenylsilane was treated with 10 equivalents of a
SEt
3
10 mol %
+
PhSiH3 2 (EtS)2
Ph Si H
SEt
trap in the presence of 10 mol % of
1 at 80 °C in benzene-d6.
benzene-d6,
80 °C, 24 hours,
-H2
For traps such as 2-butyne, terminal alkynes, dienes and
disulfides, reactions failed to afford organosilanes products,
21%
(5)
and decomposition of
trapping to competitive reaction of
much of which has already been described.18 In the case of phenylsilane and phenylsilane-d3 under the same conditions
diphenylacetylene as a trap, some formation of cis-stilbene using . It was suspected that generation of PhHDSi–SiD2Ph or
(~24%) was observed (eqn (4)).‡ Control reactions of H2 and PhH2Si–SiHDPh must be the result of phenylsilylene or
diphenylacetylene in the presence of give much lower phenylsilylene-d1 insertion into Si–D or Si–H bond,
conversions to cis-stilbene than reactions with phenylsilane, respectively. In the 1H and 2H NMR spectra, respectively, broad
1
resulted. We attribute the lack of
2
with these reagents,
A competition experiment was performed between
1
1
a
which is unsurprising given that 1 and related derivatives are multiplets at the chemical shift of 1,2-diphenyldisilane were
poor hydrogenation catalysts with H2.8a The reduction of an identified, representing about 6% of the Si–H intensity by 1H
alkyne by a silane is an unusual transformation, but a report by NMR integration. Attempts to accurately assign products using
Marciniec indicates one potential route.24
simulated spectra was hampered by poor simulation quality. A
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highly complex resonance was observed in the 29Si NMR
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spectrum at approximately δ 61.2, indicative of multiple
Table
1.
Summary
of
observations
and
mechanistic
implications
#
Observation
PhSiH3 + Me2NH + 1(cat) → Ph(NMe2)SiH2
Implication(s)
1
Insufficient data for mechanistic suggestion, though prior work would suggest σ-bond
metathesis.
2
3
PhSiH3 + iPrNH2 + 1(cat) → Ph(NMe2)SiH2 + Ph2SiH2
2 + PhSiD3 → 2-d1
Absence of SiH4 is inconsistent with redistribution, and Ph transfer from a Zr–Ph intermediate
(a la Tilley) is possible.
Deuterium incorporation on the trimethylsilyl substituent must arise from Si–D activation at
2, which demonstrates that a Zr-silyl is unstable with respect to cyclometalation.
This system is not competent for silane dehydrocoupling, despite transient Zr-silyl (#3).
Reactivity consistent with Andersen’s methylidene elimination with cerocenes suggests a
silylene intermediate.
4
5
PhSiH3 + 2(cat) → decomposiꢀon
2 + Ph(NMe2)SiH2 → 1 + PhSiH3
2 + PhClSiH2 → (N3N)ZrCl + PhSiH3
PhSiH3 + 1(cat) → (PhSiH2)2
6
7
This catalysis may proceed via α-silylene elimination based on observation 5. An alternative is
the generation of a hydride that would rapidly form 2 and a σ-bond metathesis pathway, but
2 is not catalytically active (# 4).
PhSiH3 + R2S2 + 3(cat) → Ph(SR)2SiH
This reaction is consistent with silylene trapping by disulfide. An alternative may be disulfide
splitting with adventitious hydrogen followed by two sequential Si–S heterodehydrocoupling
events, but neither RSH nor Ph(RS)SiH2 was observed by NMR.
pentaphenylsilole.36 In a limited set of reactions of
products and non-first order spin systems, but again, accurate
simulations could not be made. While the observation of
apparent crossover products is encouraging, these products
may also arise from H/D exchange reactions, such as reaction
phenylsilane and diphenylacetylene with catalytic 1,
1,2,3,4,5-pentaphenylsilole was observed by 1H NMR
spectroscopy with confirmation by comparison to an
authentic sample.56 However, conditions that reliably favor
this product could not be identified.
of 1,2-diphenyldisilane and D2 catalyzed by 2. Therefore, this
experiment represents, at best, supporting evidence of this
reactivity rather than direct proof.
1(a) J. F. Dunne, S. R. Neal, J. Engelkemier, A. Ellern and A. D.
Sadow, J. Am. Chem. Soc., 2011, 133, 16782; (b)
Reichl and D. H. Berry, Adv. Organomet. Chem., 1999, 43
J. L.
In sum,
1 is a catalyst for the heterodehydrocoupling of
,
amines and silanes with limited efficacy. It is also a poorly
effective silane dehydrocoupling catalyst, but a series fo
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Ephritikhine and M. S. Eisen, J. Organomet. Chem., 2000,
,
observations from stoichiometric and trapping reactions of
and zirconocene (Table 1) support the idea that these
zirconium compounds engage in -silylene elimination. This
1
3
α
610, 49; (f)
W. Xie, H. Hu and C. Cui, Angew. Chem. Int.
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Conflicts of interest
Organometallics, 2016, 35, 1674; (m)
N. Li and B.-T. Guan,
There are no conflicts to declare.
Adv. Synth. Catal., 2017, 359, 3526; (n) A. Baishya, T.
Peddarao and S. Nembenna, Dalton Trans., 2017, 46, 5880;
(o) C. Bellini, T. Roisnel, J.-F. Carpentier, S. Tobisch and Y.
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,
This work was supported by the U.S. National Science
Foundation (CHE-1265608 and CHE-1565658). We are pleased
to contribute this in celebration of the 65th birthday of Phil
Power, a deeply creative chemists whose work never ceases to
inspire.
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Notes and references
§ Reaction of isolated (N3N)ZrNHiPr with PhSiH3 fails to give any
measurable N-Si products under similar conditions.
‡ It is known that photochemically generated phenylsilylene is
trapped with diphenylacetylene to give 1,2,3,4,5-
J. F. Dunne, S. R. Neal, J. Engelkemier, A. Ellern and A. D.
Sadow, J. Am. Chem. Soc., 2011, 133, 16782.
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4 | Dalton Trans., 2017, 00, 1-3
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DOI: 10.1039/C7DT04507G
Table of contents entry for
Catalytic N–Si Coupling as a Vehicle for Silane Dehydrocoupling via α-Silylene
Elimination
Karla A. Erickson, Michael P. Cibuzar, Neil T. Mucha, and Rory Waterman
Zirconium compounds appear to promote the liberation of silylene fragments via and N–Si
coupling event.