Catalytic insertion of E-H bonds (E = C, N, P, S) into heterocumulenes by amido-actinide complexes

Article abstract of DOI:10.1039/c5sc02746b

We report herein the actinide-mediated insertion of E-H bonds (E = C, N, P, S) into various heterocumulenes including carbodiimides, isocyanates, and isothiocyanates. The precatalysts are prepared by a simple, one-pot procedure using readily available sta

Full text of DOI:10.1039/c5sc02746b

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EDGE ARTICLE
Catalytic insertion of E-H bonds (E=C, N, P, S) into
heterocumulenes by amido-actinide complexes†
Received 00th January 20xx,
Accepted 00th January 20xx
Rami J. Batrice and Moris S. Eisen*
DOI: 10.1039/x0xx00000x
www.rsc.org/
We report herein the actinide-mediated insertion of E-H bonds (E=C, N, P, low-yielding multi-step ligand synthesis provides a further
S) into various heterocumulenes including carbodiimides, isocyanates, and challenge accompanying the production and application of this
isothiocyanates. The precatalysts are prepared by
procedure using readily available starting materials, and challenging amido-actinide complexes of the formula U[N(SiMe3)2]3 (
insertions are achieved with excellent selectivity in short reaction times. [(Me3Si)2N]2An[κ2-(N,C)-CH2Si(CH3)2N(SiMe3)] (An=U (
), Th (
a
simple, one-pot complex. Recently, we have shown that a series of simple
) and
))
1
2
3
Spectroscopic data are utilised to propose the active catalytic mechanism (Fig. 1) are capable of effecting the efficient oligomerisation or
and derive thermodynamic activation parameters, which are described in cyclotrimerisation of terminal alkynes,53 the sole example of a
this study. The only example of an actinide-mediated C-H bond insertion catalytic transformation employing this class of complexes
into a carbon-heteroatom bond is presented within this study.
prior to the work described in this study. These complexes are
generated in a one-pot process using readily available starting
materials and have already shown impressive stoichiometric
55
making them exceptionally attractive in their
reactivity,54,
Introduction
use as catalysts. In our attempt to uncover new reactivity with
this class of complexes, we have applied them toward the
catalytic insertion of E-H bonds into heterocumulenes (Y=C=X),
wherein E= C, N, P, or S, and Y=RN, and X=RN, O, or S. Most
interestingly was the catalytic insertion of C-H bonds into
carbodiimides, the only example of actinide-mediated C-H
insertion into a C-X unsaturated bond to date.
The structural and catalytic behaviour of the actinides has
attracted considerable attention in recent years owing to their
unique coordination geometries,1-10 as well as their impressive
reactivity profiles in numerous stoichiometric and catalytic
processes.
hydrosilylations,20-22
Hydroaminations,11-18
hydroalkoxylations,19
alkyne
polymerisations,23-29
oligomerisations,30-32 and numerous small molecule
activations28, 33-40 represent a few of the advancements made
in this field. However, the insertion of heterocumulenes into
E-H bonds (E=N, P, S) has only recently appeared in the scope
of accessible reactions in f-block chemistry.41-47 The guanidine,
phosphaguanidine, and thiourea products obtained have
found considerable utility as ligands in coordination
compounds,48 medicinal applications,49 and synthons for
challenging organic transformations.50
Previously, the effects of opening the coordination sphere
of an actinide catalyst was achieved in cyclopentadienyl-
actinide systems by the use of an ansa-bridged
tetramethylcyclopentadienyl ligand, resulting in markedly
increased activity and selectivity.56 In the catalytic study of the
amido-actinide complexes (1-3), the coordinative unsaturation
is considerably increased as compared to the analogous
actinide(imidazolin-2-iminato) complex, similarly providing
superior reactivity over the previously reported system. These
findings open the scope of possible catalytic transformations
toward new, challenging reactions.
Carbodiimides in particular have been shown to insert
stoichiometrically into the actinide-carbon bond of Cp*2AnMe2
(An=U,
Th),
giving
rise
to
the
corresponding
pentamethylcyclopentadienyl-amidinate complexes of the
early actinides,51 however only in this year was the process
made catalytic, mediated by a mono(imidazolin-2-iminato)
thorium(IV) complex and often accompanied by extended
reaction times and moderate conversions.52 Moreover, the
Fig. 1 Precatalysts employed for the catalytic insertion of E-H bonds into
heterocumulenes.
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R
R
Results and Discussion
N
N
ER1R2
[An]
[An]
ER1R2
H-ER1R2
R
N
C
N
R
The catalytic reactions of N,N’-diisopropylcarbodiimide (DIC),
di-p-tolylcarbodiimide (DTC), phenylisocyanate, and
R
R
N
N
H
4
[An] ER1R2
(a)
phenylisothiocyanate with a series REH moieties are presented
below. To establish the potential reactivity of these complexes,
the insertion of aniline into diisopropylcarbodiimide was
monitored using 1H NMR spectroscopy (Fig. 2), showing the
reaction progress as a function of DIC consumption and
guanidine formation, (Fig. 2, (a) and (b), respectively). Further
investigation of the mode of activation of the actinide centre
was performed by independent addition of aniline and DIC. In
each of the uranium and thorium complexes, it is seen that
complete displacement of the hexamethyldisilazane occurs
after the addition of anline, and that conservation of the
precatalyst oxidation state is maintained throughout the
reaction. Conversely, the reaction with DIC necessitated
elevated temperatures to activate the metal centre. These
findings inform us that activation of the precatalyst is achieved
by the amine moiety to generate the catalytically active
species. Attempts to isolate the intermediates generated and
characterisation by crystallisation were unsuccessful, however
previous studies have shown that activation of the thorium
X
X
N
Ph
N
C
X
H-ER1R2
ER1R2
Ph
N
H
ER1R2
7
Ph
R
N
N
ER3
[An]
ER3
H-ER3
R
N
C
N
R
R
R
N
N
H
R
6
[An] ER3
(b)
(c)
X
X
N
Ph
N
C
X
H-ER3
ER3
Ph
[An]
N
ER3
H
8
Ph
ER1R2
ER1
1,3 H shift
R
for R2=H
R
R
R
N
N
H
N
N
H
H
4
5
R = iPr (a), -tolyl (b)
p
X = O (c), S (d)
H-ER1R2 = PhNH2 (e), oMeO-PhNH2 (f),
oMe-PhNH2 (g), pCl-PhNH2 (g),
iPrNH2 (i), Et2NH (j), Ph2PH (k)
H-ER3 = PhCH2SH (l), (H3C)3SiCCH (m),
PhCCH (n)
complex
3 with terminal alkyne similarly results in complete
displacement of the amido moieties.53 It is worth note that the
order of addition of the reagents to the precatalyst solution
did not markedly affect the reaction rate or product
distribution. The nature of the REH substrate additionally
affects the outcome of the insertion product (Fig. 3); where E
Fig. 3 Catalytic insertion of E-H into heterocumulenes mediated by precatalysts 1-3.
performed in the presence of 100 equivalents of
is a monoprotic nucleophile, product
insertion product. However, when E is a diprotic nucleophile
(such as a primary amine), isomerisation of compound is
possible, yielding product as the major product. The
4 is obtained as the sole
heterocumulene and REH moiety. It is seen that complexes 1-3
efficiently mediate the insertion of various anilines, effecting
the transformation to the desired guanidines in excellent yield
within 4-12 hours (Table 1, entries 1-12). Each of the products
4
5
isomerisation with diprotic nucleophiles is dependent on the
resulting guanidine generated, wherein the formation of the
C=N bond is directed toward the more electron withdrawing
arm of the structure. The insertion of a series of REH moieties
into diisopropylcarbodiimide, mediated by the three actinide
was detected as the analogous product
5 by tautomerisation
forming the ipso-C=E bond (Fig. 3 (c)). When aliphatic amines
were employed, the conversion is markedly decreased,
yielding at best 31% of 1,1-diethyl-2,3-diisopropylguanidine
(Table 1, entry 16), indicating that the formation of the
actinide-aliphatic amine bond is more energetically stable and
less susceptible to insertion by the carbodiimide. Using
complexes presented (1-3), was investigated and the results
summarised in Table 1. All experiments presented herein were
diphenylphosphine as the REH species showed moderate
conversions to the phosphaguanidine using catalysts
1 and 2
(Table 1, entries 17 and 18). Particularly impressive, however,
was the quantitative conversion of phosphine to the desired
product in 2 hours by the thorium metallacycle
entry 19). The substantially higher activity of the thorium
precatalyst ( ) is an outcome of the electron deficiency of the
3 (Table 1,
3
metal centre. As the electrophilicity of the metal centre
increases, the protonolysis by the nucleophilic phosphine is
accelerated. The 5f electrons of the uranium catalysts
decreases electrophilicity at the metal, but additionally
participate in π-back-bonding interactions to phosphine,
inhibiting the catalytic turnover,
Fig. 2 Reaction progress of aniline insertion into DIC by complex 1 at 50 °C; DIC
consumption (a) and guanidine formation (b).
2 | J. Name., 2015, 00, 1-3
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Table 1 Catalytic reactions of diisopropylcarbodiimide with E-H species mediated by
complexes 1-3a
(Table 1, entry 20). It is interesting to note the lower activity of
the thorium complex
complexes employed in the reaction with ortho-anisidine
(Table 1, entries 4- ). It is proposed that the highly
(3) as compared to the uranium
6
electrophilic thorium catalyst forms a dative coordination to
the o-methoxy functionality of the aniline, thus inhibiting the
catalytic turnover.
Encouraged by the diversity of E-H moieties demonstrating
favourable reactivity in the actinide-mediated insertion,
attention was turned to the possibility of insertion of a C-H
bond, a process hitherto unseen in actinide chemistry for
heteroatom-containing multiple bonds. Performing this
reaction with trimethylsilyl- or phenyl-acetylene generated the
desired insertion product with all complexes in excellent yield
and short reaction times (Table 1, entries 23-28), providing the
substituted amidine. The insertion of 3,3-dimethylbutyne was
observed in 51 and 81% conversion after 24 hours after
R=
Reaction
Time (h)
Entry
Precatalyst
Convb (%)
Product
(R2EH/REH)
1
1
2
3
1
2
3
1
2
3
1
2
3
1
3
1
3
1
2
3
3
1
2
1
2
3
1
2
3
6
9
>99
>99
94
2
PhNH2
5ae
3
4
4
3
>99
93
5
oMeO-PhNH2
oMe-PhNH2
pCl-PhNH2
12
24
6
5af
5ag
5ah
6
96
heating in the presence of complexes
(Table 1, entries 21 and 22), generating N,N’-diisopropyl-4,4-
dimethylpent-2-ynimidamide. The analogous reaction
performed with complex produced alkyne dimerization
1 and 2, respectively
7
>99
93
8
12
6
3
9
95
product, however no detectable insertion into the
carbodiimide was observed. This finding illustrates the
competitive process between the alkyne oligomerisation and
insertion into the heterocumulene, revealing a lower barrier
energy for insertion into the C≡C bond, favouring the former
process (Fig. 4). These reactions were additionally attempted
using 1-hexyne, however oligomerisation forming organic
enynes was dominant, generating a mixture of products from
competitive insertions.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
9
>99
>99
>99
5
12
4
24
24
24
24
24
24
2
iPrNH2
Et2NH
4ai
4aj
15
23
31
Similar
reactions
were
performed
using
58
di-p-tolylcarbodiimide (DTC) as the heterocumulene source,
Ph2PH
53
4ak and the results are presented in Table 2. Initial analysis of the
reactions performed with DTC revealed superb substrate
>99
>99
51
conversions in moderate reaction times. The reaction of
BnSH
2
6al
aromatic amines with DTC generated the corresponding
24
24
9
guanidines in excellent yield after heating at 75 °C (Table 2,
tBuCCH
6am
entries 1-12). The most apparent trend of these reactions is
81
the shorter reaction times when utilising the thorium
96
metallacycle (3), and the observed acceleration of the reaction
Me3SiCCH
PhCCH
24
12
9
96
6an
6ao
rate as a more electron deficient aniline is used (Table 2,
entries 3, 6, 9, and 12). This trend in reactivity is an expected
corollary of the decreased electron donation from the aniline
derivatives to the metal centre, resulting in a weaker, more
labile bond, and allowing for a more rapid insertion of the
carbodiimide into the Th-N bond. Similar short reaction times
are observed for the insertion of Ph2PH using the thorium
>99
97
24
18
97
>99
aReaction conditions: ~3.5 μmol precatalyst (1 mol%), 600 μL C6D6, 75 °C.
bDetermined by 1H NMR of the crude reaction mixture.
whereas the thorium complex (3) (lacking 5f electrons) is
unable to perform this stabilising interaction and allows for
rapid protonolysis and insertion. The insertion of benzylthiol
was attempted with each of the uranium precatalysts,
however upon addition of the thiol, immediate formation of a
green precipitate was observed, which reacted no further after
Fig. 4 Competitive alkyne and carbodiimide insertion into actinide-acetylide bond.
heating. The thorium complex 3, conversely, reacted within
two hours to near-quantitative conversion toward product 6al
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Table 2 Catalytic reactions of di-p-tolylcarbodiimide with E-H species mediated by
complexes 1-3a
alkynes was studied, and the results presented in Table 3. It is
most notable that the catalytic insertion into these substrates
was only achieved using the uranium complexes; this
observation is justified by the greater bond-disruption
enthalpy of the Th-O and Th-S bond as compared to the
uranium analogues (Th-O = 208.0, U-O = 181.0, Th-S = 145.2,
and U-S = 121.9 kcal mol-1).58 These bonding energies indicate
a higher barrier of insertion into the Th-S or Th-O species,
which is not exceeded under the given reaction conditions,
additionally supporting the observed reactivity of the thorium
Reaction
complex
with
ortho-anisidine.
The
insertion
of
Entry Precatalyst R= (R2EH/REH)
Convb (%)
Product
Time (h)
diphenylphosphine gives only moderate conversions using
either uranium complex with both heterocumulenes (Table 3,
entries 1, 2, 5, and 6), and a similar trend is observed using
benzylthiol, however the reaction of this E-H moiety with
1
2
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
3
24
24
6
89
93
PhNH2
5be
3
>99
91
phenylisocyanate mediated by the uranium(III) complex (
shows an enhanced reactivity as compared to the uranium(IV)
complex ( ), providing a 99% conversion to product 8cl after
1)
4
24
24
24
24
24
9
2
5
oMeO-PhNH2
oMe-PhNH2
pCl-PhNH2
>99
90
4bf
4bg
5bh
24 hours at 75 °C (Table 3, entry 3).
6
Analysis of the rate order reveals first order kinetics in
precatalyst, heterocumulene, and REH, giving rise to the rate
equation 1:
7
96
8
>99
>99
98
ꢀꢁ ꢃ ꢄꢅꢆꢇ ∙ ꢈꢉꢊꢋꢊꢌꢍꢎꢋꢏꢐ ∙ ꢈꢑꢒꢓꢏꢐ ∙ ꢈꢊꢔꢕꢌꢕꢔꢖꢏꢐ
9
(1);
ꢀꢂ
10
11
12
13
14
15
16
17
24
24
6
(a more thorough presentation of the kinetic rate law is
presented within the Supporting Information). The mechanism
of activation was studied using DIC and aniline. The first step is
a rapid protolytic cleavage by the aniline which displaces all
hexamethyldisilazide moieties at room temperature (Fig. 5,
step (a)), followed by rapid reversible migratory insertion of
94
>99
98
12
24
24
6
Ph2PH
BnSH
85
4bk
6bl
83
Table 3 Catalytic reactions of phenylisocyanate or phenylisothiocyanate with E-H
species mediated by complexes 1 and 2a
>99
>99
3
R1
R2
aReaction conditions: ~3.5 μmol precatalyst (1 mol%), 600 μL C6D6, 75 °C.
bDetermined by 1H NMR of the crude reaction mixture.
E
cat.
C6D6, 75 °C
N
C
X + H-ER1R2
N
H
X
7
precatalyst (
and ) (Table 2, entries 13-15).
Performing these reactions with benzylthiol resulted in
rapid insertion into DTC for complexes and (Table 2, entries
16 and 17), however the reaction with precatalyst again
3) as compared to the uranium precatalysts (1
R3
2
E
cat.
C6D6, 75 °C
N
C
X + H-ER3
1
3
N
X
H
2
8
resulted in the formation of an intractable green precipitate,
which formed immediately upon addition of the thiol. This is
most likely due to the formation of insoluble U(IV) dimers
bridged by the thiol moiety, which has been previously shown
to occur, especially for U(IV) metallocene systems.57 Similar
reactions were performed with aliphatic amines and terminal
alkynes, however no catalytic turnover was observed in any of
these reactions, showing that the insertion of the electron
deficient carbodiimide is unable to surpass the bonding energy
of the actinide-nitrogen and actinide-carbon bonds described.
The scope of these reactions illustrating the robust nature
of these complexes was expanded further yet in the insertion
into isocyanates and isothiocyanates. Using phenylisocyanate
and phenylisothiocyanate as the heterocumulene source, the
insertion of diphenylphosphine, benzylthiol, and terminal
Entry Precatalyst Ph-N=C=X R= (R2EH/REH) Convb (%) Product
1
2
3
4
5
6
7
8
1
2
1
2
1
2
1
2
52
64
99
68
49
55
47
52
Ph2PH
BnSH
Ph2PH
BnSH
7ck
8cl
O
7ck
8dk
S
aReaction conditions: ~3.5 μmol precatalyst (1 mol%), 600 μL C6D6, 75 °C, 24 h.
bDetermined by 1H NMR of the crude reaction mixture.
4 | J. Name., 2015, 00, 1-3
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Deuterium-labelling studies in the reaction of PhND2 with
DIC revealed a KIE of 1.22, indicating protolytic cleavage of the
guanidinate to be the rate-determining step of the catalytic
cycle. Preliminary studies in our group show the possibility of
using group 4 metal complexes to effect similar chemical
transformations. The investigation of further catalytic
transformation using these actinide precatalysts is currently
underway.
U[N(SiMe3)2]3
3 REH
3 HN(SiMe3)2
[U] ER
R1
N
ER
R1
R1
N
N
C
N
R1
H
turnover
limiting
Notes and references
REH
1.
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H. S. La Pierre, A. Scheurer, F. W. Heinemann, W.
Hieringer and K. Meyer, Angew Chem Int Ed Engl, 2014,
53, 7158-7162.
R1
N
[U]
N
R1
2.
ER
3.
P. L. Arnold, C. J. Stevens, J. H. Farnaby, M. G. Gardiner, G.
S. Nichol and J. B. Love, J. Am. Chem. Soc., 2014, 136,
10218-10221.
Fig. 5 Plausible mechanism of the actinide-mediated catalytic insertion of E-H bond into
carbodiimide.
4.
5.
P. L. Diaconescu and C. C. Cummins, Inorg. Chem., 2012,
51, 2902-2916.
DIC into the An-N bond (step (b)). A slow protolytic cleavage by
an additional equivalent of amine (step (c)) is operative
(turnover limiting step) to complete the catalytic cycle with
concomitant liberation of the organic product and
regeneration of the active catalyst. Deuterium labelling studies
were performed in this reaction using aniline-N,N-d2, revealing
B. Vidjayacoumar, S. Ilango, M. J. Ray, T. Chu, K. B. Kolpin,
N. R. Andreychuk, C. A. Cruz, D. J. H. Emslie, H. A. Jenkins
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R. E. Jilek, L. P. Spencer, D. L. Kuiper, B. L. Scott, U. J.
Williams, J. M. Kikkawa, E. J. Schelter and J. M. Boncella,
Inorg. Chem., 2011, 50, 4235-4237.
6.
a
primary kinetic isotope effect (kH/kD = 1.22), further
7.
8.
M. J. Monreal, S. I. Khan, J. L. Kiplinger and P. L.
Diaconescu, Chem. Commun., 2011, 47, 9119-9121.
O. J. Cooper, D. P. Mills, J. McMaster, F. Tuna, E. J. L.
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D. Patel, F. Tuna, E. J. L. McInnes, J. McMaster, W. Lewis,
A. J. Blake and S. T. Liddle, Dalton Trans., 2013, 42, 5224-
5227.
supporting the protonolysis of the guanidinate is the turnover
limiting step of the catalytic cycle (Figure 5, step (c)).
Thermodynamic
parameters
were
experimentally
calculated from 1H NMR data of aniline insertion into DIC using
Eyring plots (see Supporting Information), and the enthalpy of
9.
activation (ΔH‡) for complexes
1-3 were found to be 9.9(1),
10.5(1), and 9.7(1) kcal mol-1, respectively,showing a low
energetic barrier to the actinide-mediated insertion. The
10.
11.
12.
13.
14.
15.
16.
17.
W. J. Evans, N. A. Siladke and J. W. Ziller, Chem. Eur. J.,
2010, 16, 796-800.
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proposed
σ-bond metathesis by aniline via a four-centred
transition state is additionally supported by the remarkably
low entropies of activation (ΔS‡) of -49.5(3), -48.0(4), and -
52.8(3) e.u., respectively, for complexes 1-3. Calculating the
Gibbs energy of activation (ΔG‡) for these reactions at 75 °C
showed extremely similar values for each of the precatalysts
employed (27.1(1), 27.2(1), and 28.1(1) kcal mol-1 for
1-3,
respectively).
Conclusions
This work presents a series of simple coordinative unsaturated
amido-actinide complexes capable of performing the catalytic
insertion of E-H bonds into heterocumulenes, where E=C, N, P,
or S. The insertion into carbodiimides showed excellent
reaction rates and functional group tolerances. The insertion
18.
19.
20.
21.
of terminal alkynes represents
actinide-mediated catalysis. The
a
new facet of
insertion into
phenylisocyanate and phenylisothiocyanate showed a more
limited reactivity, however the reaction performed with
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the
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phosphanecarboxamide and carbamothioate.
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