Structural Elucidation of Silver(I) Amides and Their Application as Catalysts in the Hydrosilylation and Hydroboration of Carbonyls

Article abstract of DOI:10.1002/chem.202000169

This study details the isolation and characterisation of three novel silver(I) amides in solution and solid-state, [Ag(Cy₃P)(HMDS)] 2, [Ag(Cy₃P){N(TMS)(Dipp)}] 3 and [Ag(Cy₃P)₂(NPh₂)] 4. Their catalytic abilities have proved successful in hydroboration and hydrosilylation reactions with a full investigation performed with complex 2. Both protocols proceed under mild conditions, displaying exceptional functional-group tolerance and chemoselectivity, in excellent conversions at competitive reaction times. This work reveals the first catalytic hydroboration of aldehydes and ketones performed by a silver(I) catalyst.

Full text of DOI:10.1002/chem.202000169

A Journal of
Accepted Article
Title: Structural elucidation of silver(I) amides and their application as
catalysts in the hydrosilylation and hydroboration of carbonyls
Authors: Victoria Louise Blair, Samantha Alana Orr, John A Kelly, and
Aaron J Boutland
This manuscript has been accepted after peer review and appears as an
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the VoR from the journal website shown below when it is published
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content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.202000169
Link to VoR: http://dx.doi.org/10.1002/chem.202000169
Supported by

Chemistry - A European Journal
10.1002/chem.202000169
Structural elucidation of silver(I) amides and their application as
catalysts in the hydrosilylation and hydroboration of carbonyls
ꢀ
[
a]
Samantha A. Orr, John A. Kelly, Aaron J. Boutland and Victoria L. Blair*
ꢀ
[
13]
[14]
The groups of Rit and Bi simultaneously reported the use of
silver(I) salts AgSbF or AgOAc for the catalytic selective b-
Abstract: This study details the isolation and characterisation of
6
three novel silver(I) amides in solution and solid-state,
hydroboration of terminal alkynes and/or alkenes, respectively,
under base and ligand free conditions via a proposed radical
pathway.
[
[
Ag(Cy
Ag(Cy
3
P)(HMDS)] 2, [Ag(Cy
3
P){N(TMS)(Dipp)}]
3
and
3
P) (NPh )] 4. Their catalytic abilities have proved
2
2
successful in hydroboration and hydrosilylation reactions with a
full investigation performed with complex 2. Both protocols
proceed under mild conditions, displaying exceptional functional
group tolerance and chemoselectivity, in excellent conversions at
competitive reaction times. This work reveals the first catalytic
hydroboration of aldehydes and ketones performed by a silver(I)
catalyst.
Moving away from traditional salts, Kobayashi combined Lewis
acidic silver with the Brønsted amido base HMDS (HMDS =
hexamethyldisilazide) to give AgHMDS which was shown to
catalyse asymmetric [3+2] cycloaddition reactions of Schiff bases
[
15]
[16]
with a-aminophosphonates and/or olefins in high yields and
enantioselectivities in the presence of supporting chiral
a
[
17]
bisphosphine ligand (Figure 1). Interestingly, in the absence of
the chiral supporting ligand AgHMDS showed little to no catalytic
activity. To the best of our knowledge this represents the only
example of a silver(I) amide system used in catalysis
Among the Group 11 coinage metals, silver is often overlooked
or neglected in synthesis due to its relatively moderate Lewis
[
1]
acidity, ease of reduction and photosensitivity. Despite these
drawbacks, the reasonable cost of silver salts (relative to other
expensive transition metals) combined with the ability of silver to
Inspired by this study, we sought to design a silver(I) amide
pairing that would be successful as
a
catalyst in
[
2]
hydrofunctionalisation reactions. These typically involve M-H
intermediates, which are unstable and extremely rare in silver
chemistry with only two examples structurally characterised to
act as a s- and/or p-Lewis acid, have placed them as
indispensable reagents in various organic transformations
[
3]
including as additives in Pd-catalysed transformations, as
effective Lewis acid catalysts, as well as promoters in
[
18,19]
date.
Therefore, designing a pre-catalyst that allows in-situ
[
4]
[5,6]
access to a stable silver(I) hydride species would be of benefit in
such catalytic systems.
carboxylation,
enantioselective asymmetric reactions,
[
7]
heterocyclisations and cycloadditions.
Compelled by the general lack of knowledge on silver(I) amide
complexes, from both a structural and reactivity viewpoint, we
now describe the synthesis, solution and solid-state
characterisation of three monomeric silver(I) amide complexes
and their application in the catalytic hydrosilylation and
hydroboration of a range of aldehydes and ketones.
A key aspect of why silver is so suited to these catalytic
transformations is its tunable Lewis acidity. By careful choice of
counter-ion (e.g. halide, perchlorate, triflate) the Lewis acidity can
be modulated (weaker or stronger) and manipulated to achieve a
desired outcome in synthetic organic transformations. However,
in most cases these reactions can often require additional
additives, such as supporting ligands, base(s), and/or elevated
temperatures, with the actual composition of the active Ag(I)
species generally unknown. Some silver salts have emerged as
promising reagents in catalytic hydrosilylation and more recently
[
8,9]
[10]
hydroboration of unsaturated substrates.
Both AgOTf
[
11]
(
Figure 1) and AgPF
6
with addition of an appropriate phosphine
or NHC co-ligand respectively, have shown to be effective and
efficient in the hydrosilylation of aldehydes, albeit at elevated
temperatures (70-100°C), while ketones still remain a challenge.
Significantly these catalytic hydrosilylation reactions are proposed
[
9,10]
to involve ‘M-H’ intermediates
as the active catalytic species,
although characterisation has proved elusive. In marked contrast,
progress in Ag(I) catalysed hydroboration reactions are still in
[
12]
their infancy. Yoshida and co-workers, were the first to report
catalytic hydroboration of terminal alkynes using B Pin (pin =
pinacol) employing an Ag(I)-NHC complex and KOtBu.
Figure 1. Summary of silver mediated catalysis.
2
2
The target silver(I) amide complexes were synthesized using
salt metathesis. Addition of the appropriate lithium amide to a THF
suspension of AgCl and Cy
3
P
1
(Scheme 1) afforded
P){N(TMS)(Dipp)}] and
2
)] 4. Emphasising the importance of the soft
[
[
Ag(Cy
Ag(Cy
3
P)(HMDS)] 2, [Ag(Cy
P) (NPh
3
3
[a]
Dr S. A. Orr, Dr J. A. Kelly, A. J. Boutland, Dr V. L. Blair
School of Chemistry
3
2
phosphine donor, changing to an oxygen or nitrogen Lewis donor,
resulted in repeated decomposition and precipitation of Ag(0).
Complexes 2 - 4 are pale yellow to colourless solids, hydrocarbon
soluble, thermally robust, and stable for weeks at 25°C upon
Monash University
Wellington Road, Clayton, Melbourne VIC, Australia 3800
E-mail: Victoria.blair@monash.edu.au
Supporting information for this article is given via a link at the end of
the document.
3
exclusion of light. Interestingly, addition of an excess Cy P to
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Chemistry - A European Journal
10.1002/chem.202000169
1
09
1
107
31
1
109
31
complexes 2 and 3 did not result in any additional phosphine
Ag nuclei. This results in J( Ag- P) and J( Ag- P)
coupling constants of 480 Hz and 556 Hz respectively, which fall
coordination to silver.
[
25]
in the range of previously reported silver(I) complexes.
Whereas complex 4 shows a singlet at 28.8 ppm belonging to the
Cy P ligand, attributed to rapid exchange equilibria in solution.
3
The relative stability of complexes 2 - 4 prompted us to probe
their reactivity in catalytic systems. Although hydroboration and
hydrosilylation reactions have been studied extensively with
[
26–29]
various metal systems,
to the best of our knowledge, there
are no examples employing silver(I) amides.
Employing our benchmark reagent benzaldehyde, we
investigated the most effective candidate for catalyzing carbonyl
hydroboration, 2-4, probing the structure activity relationship if
any. The reaction was performed with pinacolborane (HBpin) and
ꢀ
5
mol% of each catalyst (Entries 1-3, Table 1) at room
Scheme 1. Synthesis of Ag(I) amide complexes 2 - 4.
temperature in an amber J. Young’s NMR tube and monitored by
1
ꢀ
H NMR spectroscopy. Catalysts 2 and 4 performed well reaching
Single crystals suitable for X-ray diffraction studies were
obtained for complexes 2 - 4. Due to the isostructural nature of 2
and 3 (see ESI) only 2 will be discussed in detail. All three
complexes 2 - 4 are monomeric in the solid state. The silver atom
in 2 adopts an almost perfect P-Ag-N linear angle of 177.02 (4)°
with a short Ag-N bond length of 2.0746 (17) Å (Figure 2). This is
similar to that of 2.079 (2) Å reported in the NHC silver(I) amide
quantitative conversion in less than 30 minutes (Entries 1 and 3,
Table 1), whereas catalyst 3 required extended reaction times not
[
23]
yielding a single product.
studies owing to its ease of synthesis using commercially
available starting reagents and a stoichiometric amount of Cy
Catalyst 2 was selected for further
3
P
ligand. Initial studies were performed in benzene, owing to the
hydrocarbon solubility of our catalysts. However, we explored a
[
20]
complex [Ag(SItBu)(HMDS)]
(SItBu
=
1,3-di-tert-butyl-
8
more polar solvent, D -THF, to contrast the reaction outcome
imidazolin-2-ylidene) while being significantly shorter than that
(Entry 4, Table 1). Comparatively, this inhibited the reaction
considerably, reaching only 18 % conversion after 0.5 hours.
Finally, to confirm the silver(I) amide is more catalytically active
than the silver(I) chloride, complex 1 was studied (Entry 5, Table
1) which showed less than 50% conversion after 3 days.
[
21]
found in tetrameric [{Ag(HMDS)}
In contrast, 4 adopts a distorted trigonal planar geometry due to
the large steric constraint of the two coordinated Cy P ligands.
4
]
(average Ag-N = 2.147 Å).
3
This steric constraint results in the lengthening of the Ag-N bond
to 2.258 (2) Å. To the best of our knowledge structural
characterisation of monomeric silver(I) amide complexes, in
[
a]
Table 1. Hydroboration of benzaldehyde optimization.
[
20]
ꢀ
which a Brønsted base is bound to the silver centre are scarce
O
OBpin
H
[
22–24]
Ag cat. (5 mol %)
HBpin (1.2 eq.)
though tetrameric and dimeric structures are more common.
H
H
solvent (0.5 mL)
rt
5
a
6a
Entry
Catalyst
Solvent
Yield [%]
99
Time [h]
1
2
3
4
5
2
3
4
2
1
C
C
C
6
6
6
D
D
D
6
6
6
0.5
7
[
b]
81
>99
18
0.3
0.5
72
8
D -THF
C
6
D
6
43
ꢀ
[a] Reaction conditions: substrate (1 mmol), HBpin (1.2 mmol), 5 mol%
catalyst and 10 mol% internal standard hexamethylcyclotrisiloxane in 0.5
mL of solvent at room temperature. [b] 97% conversion of aldehyde.
Figure 2. Molecular structure of [Ag(Cy
Ag(Cy P) (NPh
and hydrogen atoms are omitted for clarity. Selected bond lengths
Å] and angles [°] for 2: Ag(1)-N(1), 2.0746(17); Ag(1)-P(1),
.3404(10), N(1)-Ag(1)-P(1), 177.02(4); and 4: Ag(1)-N(1), 2.258
2); Ag(1)-P(1), 2.4680(6); Ag(1)-P(2), 2.4718(7); N(1)-Ag(1)-
P(1), 114.84(8); N(1)-Ag(1)-P(2), 114.94(8); P(1)-Ag(1)-P(2),
30.23(2).
3
P)(HMDS)] 2 and
[
3
2
2
)] 4 in the solid state. Ellipsoids are set at 50%
To study the scope of these Ag-mediated transformations, a
range of carbonyls were studied. Preparing one equivalent of
substrate in an amber J. Young’s NMR tube, along with 5 mol%
catalyst loading of 2, and 1.2 equivalents of HBpin, they were
[
2
(
1
11
monitored by H and B NMR spectroscopy. The successful
outcome is an atom economical method that proved efficient for
both aldehydes and ketones, resulting in excellent yields (88 – 99
1
1
13
31
6 6
Examination of the H, C and P NMR spectra in C D of
%
) of the desired valuable boronic acids 6a-n, Table 2.
complexes 2 - 4 reveal the solid-state structure is retained in
Exceptional tolerance of sensitive functional groups and
chemoselectivity was displayed by the catalyst, including electron
withdrawing groups (6a-d, Table 2), as well as electron donating,
coupled with steric hindrance 6e-f, Table 2. Hydroboration of
aliphatic substrate 6g was also achieved, reaching 94% in a
moderate two hours. Acetophenone derivatives (6h-6l, Table 2)
underwent hydroboration albeit reaction times were generally
solution with characteristic resonances of the amido and
3
phosphine (Cy P) ligands (see ESI). Most characteristic is their
3
1
differing P spectra due to deshielding of the phosphine ligand
upon complexation to silver. In complex 2 a broad doublet at 37.0
1
107/109
31
ppm with a J(
observed, whilst for 3 a set of doublets of doublets at 41.9 ppm
Ag- P) coupling constant of 503 Hz is
1
07
and 37.7 ppm are detected due to spin-spin coupling of Ag and
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Chemistry - A European Journal
10.1002/chem.202000169
o
[10]
longer than for aldehydes. Exceptions were electron deficient
substrates 5j and 5l, where greater than 95% conversion was
obtained in less than 15 minutes. Aliphatic and aromatic cyclic
systems also work well (6m and 6n, Table 2) in this catalytic
system. To the best of our knowledge this is the first report of a
silver catalyzed hydroboration of aldehydes and ketones.
70 C to reach 48 % of silyl ether product 7g. Moving to slightly
more challenging ketone substrates, the ‘pre-catalyst’ highlighted
its boundaries. Substrates, acetophenone and benzophenone,
1
displayed low conversions even after 24 hours monitoring by H
NMR spectroscopy (Table 2). This is unsurprising when
compared with
a
recently reported silver(I) system
Encouraged by our findings we extended our study to the
(AgPF :Ligand:Base) that observed negligible conversion after 24
6
o
[11]
hydrosilylation of carbonyls, employing Ph
2
SiH
2
due to optimum
hours at 100 C and a copper(I) catalyst requiring 44h to reach
[
23]
[30]
selectivity’s and conversion times noted (see ESI). The same
range of aromatic substituted benzaldehydes bearing various
functional groups were investigated (Table 2) which underwent
full conversion of benzophenone. Replacing the methyl with a
trifluoromethyl group, dramatically enhanced reactivity (7j) whilst,
2
introducing a p-NO group facilitated successful hydrosilylation
1
successful hydrosilylation. Monitoring by H NMR spectroscopy,
reactivity. Polycyclic aromatic hydrocarbon, 9-fluorenone, showed
quantitative formation of the corresponding silyl ether 7m.
However, conversion of an aliphatic cyclic species 7n was
negligible.
revealed more than one species was forming for products 7b, 7c,
7
d, 7j (Table 2), hence these were isolated (ESI) to determine the
yield of desired alcohol product.
In contrast to complex silver systems that require additional
ligands, metal(s) or base(s) to achieve catalytic activity, our
simple pre-catalyst is molecularly well defined. To gain
mechanistic insights and to understand the active catalytic
Table 2. Hydroboration and hydrosilylation of carbonyls using
[
a]
HBpin or Ph
2
2
SiH catalyzed by 2.
[
X]
O
Ph SiH
O
2
2
species, we performed a series of stoichiometric control
H
or
Cat. 2 (5 mol %)
, rt
R
[Si] = SiPh H
[B] = Bpin
H
+
2
H
[X] =
HBpin
experiments. Precedence in the literature suggests a metal
hydride pathway, however recent studies of silver catalyzed
R
(1.2 eq.)
C
6
D
6
hydroboration of olefins postulated
a
radical based
[
13,14]
[
X]
[X]
mechanism.
[
X]
O
O
O
H
H
H
H
To determine the first step in the cycle, generally accepted to
be the formation of the ‘active catalyst’, the stoichiometric reaction
H
H
Br
b [B] = 99%, 0.2h
b [Si] = 99% (84%)
NC
of [Ag(Cy
3
P)(HMDS)] (2) and HBpin in an equimolar ratio was
6
6c [B] = 99%, 0.2h
[b] [c]
7c [Si] = 99% (72%) ,
6
7
a [B] = 99%, 0.5h
a [Si] = 94%, 1h
[b]
[c]
1
11
7
,
performed at room temperature in C
6
D
6
. After 2 hours H and
B
0
.25h
0.25h
NMR spectra indicated the complete formation of HMDS-Bpin
with a singlet resonance corresponding to the newly formed B-N
[
X]
O
[X]
[
X]
11
H
H
O
H
H
O
bond in the B NMR at d 25.8 ppm. Interestingly, this resonance
H
H
can be observed in our catalytic measurements (Figure S55). This
outcome is in keeping with both metathesis and radical pathways,
CF3
6
d [B] = 97%, 4h
d [Si] = 96% (70%)
.25h
OMe
[
b]
[c]
7
,
6e [B] = 99%, 6h
7e [Si] = 79%, 3h
6f [B] = 97%, 8h
7f [Si] = 95%, 3h
arising from either the by-product of forming of a ‘AgH’ containing
0
.
species, (Scheme 2) or as a result of generating a Bpin radical
from homolytic cleavage of HBpin (see ESI). For clarity, a control
reaction was performed employing standard conditions in the
presence of a radical scavenger TEMPO. This did not influence
[
X]
[
X]
[X]
O
O
O
H
H
H
H
1
1
the outcome of the reaction, with B NMR showing full conversion
6
7
g [B] = 94%, 2h
g [Si] = 98%, 3h
6i [B] = 88%, 6h
7i [Si] = 20%, 24h
6
7
h [B] = 93%, 2h
h [Si] = 10%, 24h
1
to the desired product, along with an extremely broad H NMR
spectrum. This would support a dominant s-bond metathesis
pathway for hydroboration, albeit a secondary radical pathway
must not be overlooked.
[
X]
[X]
[
X]
O
O
H
O
H
H
CF3
O2N
I
6
j [B] = 99%, 0.25h
6l [B] = 96%, 0.2h
[c,d]
7l [Si] = 56% (65%)
[
b]
[c]
6k [B] = 90%, 7.5h
k [Si] = <5%, 24 h
[b]
7
j [Si] = 99% (77%)
.25h
,
,
7
0
24h
[
X]
[
X]
O
H
O
H
6
n [B] = 98%, 3h
6
m [B] = 93%, 2h
7
n [Si] = <5%, 24h
7
m [Si] = 97%, 2h
[
a] Reaction conditions: substrate (1 mmol), Ph
mmol), 5 mol% [Ag(Cy P)(HMDS)] (2) and 10 mol% internal standard
hexamethylcyclotrisiloxane in C at room temperature. [b] Conversion of
2 2
SiH or HBpin (1.2-1.5
3
6
D
6
substrate. [c] Yield of corresponding alcohol product. [d] Reaction
quenched after 30 h.
Benzaldehyde (7a) underwent hydrosilylation employing
[
30–32]
conditions comparable with typical coinage metal catalysts.
Noteworthy, is the efficient hydrosilylation of tert-butylaldehyde in
hours at room temperature, improving upon limitations of an
earlier reported protocol by Stradiotto which required 24 hours at
Scheme 2. Proposed catalytic mechanism for hydroboration of
carbonyls by silver(I) amides via a silver(I) hydride intermediate.
3
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Chemistry - A European Journal
10.1002/chem.202000169
We propose our molecular (Cy
3
P)-solvated silver(I) amide ‘pre-
2011, 50, 4893–4896.
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species formed upon reaction with HBpin (Scheme 2). The
carbonyl then inserts the silver(I) hydride yielding a silver alkoxide
intermediate that undergoes s-bond metathesis via a transition
state with HBpin to yield the desired alkoxyboronate ester product
and regenerate the catalyst.
[
[
[
17]
18]
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mechanism it was found that, the presence of the radical
scavenger TEMPO hinders reactivity, extending the reaction time.
This would suggest that both a hydride and radical pathway are
feasible, with reaction conditions determining the optimum route.
In conclusion, we have fully characterized three rare monomeric
silver(I) amides in the solid and solution state and explored their
preliminary catalytic abilities, taking the first steps in catching up
with other coinage metal based catalytic systems. This study
represents the first hydroboration of carbonyls, employing a
silver(I) amide pre-catalyst. The advantageous mild conditions
used for hydroboration and hydrosilylation are competitive in the
4
027.
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[
25]
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Moubaraki for his assistance with NMR spectroscopy. This
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Chemistry - A European Journal
10.1002/chem.202000169
EntryꢀforꢀtheꢀTableꢀofꢀContentsꢀ
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The Allure of Silver: Utilizing monomeric silver(I) amides as
molecular defined pre-catalysts, the first silver mediated
hydroboration of a range of aldehydes and ketones has been
achieved. Catalytic hydrosilylation of carbonyls has also shown
2 2
success employing Ph SiH . Both mechanisms are proposed to
proceed via a ‘AgH’ intermediate.
Institute and/or researcher Twitter usernames: @VickiBlairGroup
@
ChemistryMonash
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This article is protected by copyright. All rights reserved.