Mononuclear phenolate diamine zinc hydride complexes and their reactions with CO2

Article abstract of DOI:10.1021/om400679n

The synthesis, characterization, and zinc coordination chemistry of the three proligands 2-tert-butyl-4-[tert-butyl (1)/methoxy (2)/nitro (3)]-6-{[(2′-dimethylaminoethyl)methylamino]methyl}phenol are described. Each of the ligands was reacted with diethylzinc to yield zinc ethyl complexes 4-6; these complexes were subsequently reacted with phenylsilanol to yield zinc siloxide complexes 7-9. Finally, the zinc siloxide complexes were reacted with phenylsilane to produce the three new zinc hydride complexes 10-12. The new complexes 4-12 have been fully characterized by NMR spectroscopy, mass spectrometry, and elemental analyses. The structures of the zinc hydride complexes have been probed using VT-NMR spectroscopy and X-ray diffraction experiments. These data indicate that the complexes exhibit mononuclear structures at 298 K, both in the solid state and in solution (d ₈-toluene). At 203 K, the NMR signals broaden, consistent with an equilibrium between the mononuclear and dinuclear bis(μ-hydrido) complexes. All three zinc hydride complexes react rapidly and quantitatively with carbon dioxide, at 298 K and 1 bar of pressure over 20 min, to form the new zinc formate complexes 13-15. The zinc formate complexes have been analyzed by NMR spectroscopy and VT-NMR studies, which reveal a temperature-dependent monomer-dimer equilibrium that is dominated by the mononuclear species at 298 K.

Full text of DOI:10.1021/om400679n

Article
pubs.acs.org/Organometallics
Terms of Use CC-BY
Mononuclear Phenolate Diamine Zinc Hydride Complexes and Their
Reactions With CO2
Neil J. Brown,† Jonathon E. Harris,† Xinning Yin,† Ian Silverwood,‡ Andrew J. P. White,†
Sergei G. Kazarian,‡ Klaus Hellgardt,‡ Milo S. P. Shaffer,*,† and Charlotte K. Williams*,†
†Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ, U.K.
‡Department of Chemical Engineering, Imperial College London, South Kensington, London SW7 2AZ, U.K.
S
* Supporting Information
ABSTRACT: The synthesis, characterization, and zinc
coordination chemistry of the three proligands 2-tert-butyl-4-
[tert-butyl (1)/methoxy (2)/nitro (3)]-6-{[(2′-
dimethylaminoethyl)methylamino]methyl}phenol are de-
scribed. Each of the ligands was reacted with diethylzinc to
yield zinc ethyl complexes 4−6; these complexes were
subsequently reacted with phenylsilanol to yield zinc siloxide
complexes 7−9. Finally, the zinc siloxide complexes were
reacted with phenylsilane to produce the three new zinc hydride complexes 10−12. The new complexes 4−12 have been fully
characterized by NMR spectroscopy, mass spectrometry, and elemental analyses. The structures of the zinc hydride complexes
have been probed using VT-NMR spectroscopy and X-ray diffraction experiments. These data indicate that the complexes exhibit
mononuclear structures at 298 K, both in the solid state and in solution (d8-toluene). At 203 K, the NMR signals broaden,
consistent with an equilibrium between the mononuclear and dinuclear bis(μ-hydrido) complexes. All three zinc hydride
complexes react rapidly and quantitatively with carbon dioxide, at 298 K and 1 bar of pressure over 20 min, to form the new zinc
formate complexes 13−15. The zinc formate complexes have been analyzed by NMR spectroscopy and VT-NMR studies, which
reveal a temperature-dependent monomer−dimer equilibrium that is dominated by the mononuclear species at 298 K.
quantitatively with carbon dioxide, at 298 K and 0.5 bar of
pressure, to produce trinuclear zinc formate clusters. However,
some of the carbene ligands also react with carbon dioxide,
leading to partial adduct decomposition.
INTRODUCTION
■
Zinc hydride complexes and clusters have attracted attention as
efficient catalysts for the hydrosilylation of carbon dioxide, for
the methanolysis of silanes, and for the hydrozincation of
olefins.1 Furthermore, tris(pyrazolyl)hydroborate zinc hydride
complexes have been studied as potential models for the active
site of zinc-dependent metalloenzymes, such as liver alcohol
dehydrogenase or carbonic anhydrase.2 The insertion of carbon
dioxide into well-defined zinc hydride complexes is relevant for
an improved understanding of the key steps in the hydro-
silylation catalytic cycle and as a potential model for reactions
occurring on the surface of heterogeneous Cu/ZnO/Al2O3
catalysts for carbon dioxide hydrogenation.3 Nevertheless, the
range of well-defined zinc hydride complexes remains narrow
and studies of carbon dioxide insertion into zinc hydride bonds
are limited.
Zinc dihydride, ZnH2, is a thermally unstable material whose
precise structure remains unknown, although its properties
indicate that it is a polymer.4 It is a powerful reducing agent
for example, it reduces coordinated pyridine molecules5but it
is inert to reaction with carbon dioxide.6 Very recently, Okuda
has published the first examples of carbene zinc dihydride
adducts, which exhibit dimeric structures containing both
terminal and bridging hydride moieties.7 These dimeric
structures are maintained in the solid state (X-ray diffraction
experiments) and in solution (C6D6). The complexes are labile
in solution, undergoing ligand exchange reactions, and react
Various zinc hydride complexes, of the formulation LZnH,
have been reported where L, a monoanionic ancillary ligand, is
selected from amino/pyridyl amides,1c,8 tris(pyrazoyl)-
hydroborates,2,9 3,5-disubstituted pyrazoles,10 phosphorane
iminates,11 β-diketiminates,12 alkoxides,6,13 2,6-dialkylphenyls,14
pyridyl-substituted tris(trimethylsilyl)methanides,15 tris(4,4-
dimethyl-2-oxazolinyl)phenylborate,1b,16 acetimidinato,17 and
tris(2-pyridylthio)methyl.1a,18 These complexes exhibit a
range of structures, including clusters,15 cubanes,6,11,13
dimers,1c,12a,14,17,19 and mononuclear structures.2b,9b,12d,16,18
The carbon dioxide insertion chemistry of only a few of these
hydride complexes has been studied. The tetranuclear cubane
hydrido zinc alkoxide complexes insert carbon dioxide slowly,
but the reaction is accelerated by substituting one zinc vertex of
the cube with a lithium ion.6 However, the cubane decomposes
completely during carbon dioxide insertion, presumably due to
reactions with both the alkoxide and hydride ligands, to yield
hydrated zinc formate polymers.6 Harder and co-workers
reported 2,6-diisopropylphenyl-substituted β-diketiminate zinc
hydride complexes which are dimeric in the solid state but
Received: July 9, 2013
Published: February 24, 2014
© 2014 American Chemical Society
1112
dx.doi.org/10.1021/om400679n | Organometallics 2014, 33, 1112−1119

Organometallics
Article
Scheme 1. Syntheses of Zinc Hydride Complexes 10−12 and Zinc Formate Complexes 13−15, Coordinated by
a
Diaminophenolate Ancillary Ligands
a
General reagents and conditions: (i) 1 equiv of ZnEt2, 298 K, 16 h; (ii) 1 equiv of HOSiPh3, 298 K, 16 h; (iii) 1 equiv of PhSiH3, 298 K, 16 h; (iv) 1
atm of CO2, 298 K, 1 h.
mononuclear in solution (d8-THF, 298 K).12c These complexes
react with carbon dioxide, over 30 min at 298 K, to yield
dimeric diformato complexes, which are proposed to exhibit
mononuclear structures in solution (d6-benzene, 298 K).12e
Zinc hydride complexes stabilized by tris(pyrazolyl)-
hydroborate,9b,3a tris(pyridylthio)methane,17 and tris(4,4-di-
methyl-2-oxazolinyl)phenylborate20 are all reported to be
mononuclear zinc hydrides in both the solid state and solution.
They react cleanly with carbon dioxide to yield mononuclear
zinc formate complexes.9b,18
Here, zinc hydride complexes have been prepared using
phenolate diamine ligands (Scheme 1), selected because they
have excellent precedent for the efficient coordination of zinc.21
Furthermore, the use of a chelating phenolate ligand is
desirable, as it is expected to be significantly more resistant
to protonolysis side reactions than β-diketiminate or tris-
(pyrazolyl)hydroborate ligands. Finally, the ligand is not
expected to undergo any competitive carbon dioxide insertion
chemistry. This ligand class has proved effective for the
isolation of zinc, gallium, and indium alkoxide complexes, which
show high activities as catalysts for lactide polymerization.21,22
Herein, we report the synthesis of a series of phenol diamine
ligands, differing according to the p-phenolate substituent, and
their use as ancillary ligands to synthesize a series of new zinc
alkoxide and hydride complexes. The reaction of the zinc
hydride with CO2 affords new zinc formate complexes, and the
rate at which this takes place is also investigated. An improved
understanding of the reduction of carbon dioxide by these
complexes may be relevant to better understand the role of
various catalysts and enzymes.
refluxing N,N,N′-trimethylenediamine, paraformaldehyde, and
t
the relevant 4-subsitituted 2-tert-butylphenol (R = Bu (1),
OMe (2), NO2 (3)). The resulting products were isolated as
dark oils (1, 2) or as a yellow powder (3). Subsequent reaction
of these proligands with 1 equiv of ZnEt2, in pentane (or THF,
for R = NO2) enabled isolation of the ethylzinc complexes 4−6
(51−63%), where 4 and 5 are white powders and the nitro-
containing 6 is a yellow powder. Analysis of the complexes by
1H NMR spectroscopy revealed that the nature of the
substituent on the phenyl ring affected the resonances of the
zinc-bound ethyl group. Thus, the ethyl resonances are
observed at higher chemical shifts for 4 and 5, (5 (R =
t
OMe), δ 0.44, 1.62 ppm; 4 (R = Bu), δ 0.44, 1.63), in
comparison to complex 6 (6 (R = NO2), δ 0.37, 1.45 ppm).
Treatment of complexes 4−6 with 1 equiv of triphenylsilanol
enabled clean transformation to the zinc siloxide complexes 7−
9 (51−98%). For these complexes, the 1H NMR spectra
revealed that the nature of the substituents on the phenolate
ring resulted in negligible changes in the siloxide phenyl
t
multiplets (8 (R = OMe), δ 8.00, 7.31; 7 (R = Bu), δ 7.98,
7.26; 9 (R = NO2), δ 7.95, 7.28). Subsequent reaction of
complexes 7−9 with 1 equiv of phenylsilane each yielded the
corresponding air-sensitive zinc hydride complexes 10−12
(46−60%).
The infrared (IR) spectra for complexes 10−12 each showed
an intense zinc hydride stretch at approximately 1720 cm−1
(Nujol mull; Figure S4, Supporting Information). The single
intense IR resonance suggests that the complexes exist, at 298
K, as mononuclear zinc hydride species with a terminal zinc−
hydride bond. There are only a few other examples of such
terminal zinc hydrides, and these have all shown Zn−H
resonances in a similar region of the IR spectrum (tris(2-
pyridylthio)methane)zinc hydride,18 1729 cm−1; (tris(4,4-
dimethyl-2-oxazolinyl)phenylborate)zinc hydride,16 1770
cm−1). In contrast, di-/multinuclear zinc complexes12c with
RESULTS AND DISCUSSION
■
Zinc Complex Syntheses. The diamino phenol proligands
1−3 were selected as suitable coordinating groups for a series
of new zinc hydride complexes (Scheme 1); only 1 has been
reported previously.21 The proligands 1−3 were prepared by
1113
dx.doi.org/10.1021/om400679n | Organometallics 2014, 33, 1112−1119

Organometallics
Article
Figure 1. Region of the VT 1H NMR (d8-toluene) spectra where zinc hydride resonances are observed, for 10, collected at temperatures from 303 to
203 K (for the full spectra see Figure S1, Supporting Information).
bridging zinc hydride moieties show Zn−H resonances at
significantly lower frequencies, generally ∼1500 cm−1.
Scheme 2. Proposed Equilibrium between Monomeric and
Dimeric Structures for Complex 10
The zinc hydride complexes 10−12 were also characterized
using 1H NMR spectroscopy, where a sharp singlet at
approximately 4.10 ppm (d6-benzene) is observed for all
complexes, regardless of the nature of the ancillary ligand (4.10
(10), 4.09 (11), and 3.99 ppm (12)). The lack of significant
influence of the ancillary ligand on the Zn−H bond is in clear
contrast to trends observed for the zinc ethyl complexes.
Nevertheless, these phenolate-ligated mononuclear zinc hydride
complexes show resonances at chemical shifts somewhat lower
than those for the other three known mononuclear zinc hydride
complexes (ZnH (298 K, C6D6): (tris(2-pyridylthio)methane)
zinc hydride,17 δ 5.60 ppm; 2-[(2,6-diisopropylphenyl)amino]-
4-[(2,6-diisopropylphenyl)imino]pent-2-enyl}zinc hydride,12d
δ
5.02 ppm; (tris(4,4-dimethyl-2-oxazolinyl)phenylborate)zinc
hydride,15 δ 4.27 ppm).
the same ancillary ligand.21 The formation of dimeric
complexes via bridging of the phenolate oxygen atom is
unlikely, due to steric repulsions between the tert-butyl
substituents.
In order to study the solution structure of these complexes,
1
variable-temperature H NMR studies were undertaken using
complex 10 (d8-toluene, 303−203 K, Figure 1). These
experiments suggest that a temperature-dependent mono-
mer−dimer equilibrium exists, with the mononuclear hydride
species being present at 298 K and the equilibrium shifting
toward a dinuclear (dimeric) μ-hydride complex, at reduced
temperatures (Scheme 2). The equilibrium is expected to be
entropically driven. Thus, decreasing the temperature from 303
to 203 K leads to a gradual increase in the hydride chemical
shift, with concomitant broadening, from a sharp signal at 3.91
ppm (303 K) to a broadened signal at 4.12 ppm (203 K). Even
at 203 K, coalescence was not achieved. At 203 K, the
methylene resonances due to the ancillary ligand also broaden,
indicative of changes in the coordination geometry of the ligand
at reduced temperatures. The dimer is proposed to form via
hydride bridging ligands, supported by the significant changes
in spectroscopic features of the hydride ligands (chemical shift)
on reduction of the temperature and also by analogy to
previously prepared dimeric zinc alkoxide complexes featuring
At 298 K, changes in the solution concentration from 0.1 to
0.01 M did not result in any change to the chemical shifts or
peak line widths in the observed spectrum, thus ruling out
concentration-dependent equilibria. The addition of 1 equiv of
a strong donor molecule (pyridine) also did not result in any
changes to the spectra, providing further evidence for the
mononuclear zinc hydride structure at room temperature. It is
relevant that related β-diiminate zinc hydride complexes, which
were proposed to be mononuclear in solution (d8-toluene or d8-
THF), at 298 K were also shown to undergo an entropically
driven equilibrium which lies toward the dimeric species at
lower temperatures.12d
Solution DOSY NMR experiments were used to compare the
hydrodynamic radius of 10, in d8-toluene, with that estimated
from the X-ray crystal structure (see the Supporting
Information for details and spectra). The solution hydro-
dynamic radius was determined as 4.75 Å (toluene, 298 K), and
1114
dx.doi.org/10.1021/om400679n | Organometallics 2014, 33, 1112−1119

Organometallics
Article
the radius determined from the crystal structure is 5.11 Å; these
results are in reasonable agreement and indicate the presence of
a monomer at 298 K. When the solution was cooled to 233 K,
the solution hydrodynamic radius increased to 12.09 Å, in line
with the proposed temperature-dependent monomer−dimer
equilibrium (see the Supporting Information for full details and
spectra). DFT calculations (computed at B3LYP, 3-21g*; see
the Supporting Information for further details) of the optimized
geometry, for complex 10 as a dimer, showed a radius of 9.68 Å.
For these lower temperature DOSY experiments, there is a
greater disparity between the experimental and calculated
values, although there are also more limitations to using DFT
data vs. that obtained by X-ray diffraction experiments to
predict the radius. Thus, the evidence currently supports the
formation of a dimer at lower temperature; a higher nuclearity
cluster (such as a trimer) cannot be ruled out, but we do note
that this ancillary ligand exerts significant steric hindrance,
which might disfavor the formation of such species.
pent-2-enyl}zinc hydride,12d 1.46(2) Å; 2-[(2,4,6-
trimethylphenyl)amino]-4-[(2,6-diisopropylphenyl)imino]-
pent-2-enyl}(4-(dimethylamino)pyridyl)zinc hydride12f,21
,
1.49(2) Å. The distance of 1.75(3) Å seen in 10 is significantly
longer than all of these.22
However, all of these structures were derived from single-
crystal X-ray diffraction studies, a technique which has a
fundamental problem with locating hydrogen atoms. The
structure of the simple dizinc complex bis(μ2-(2-dimethylami-
no-N-methylethylamido)-N′,μ-N)bis(hydridozinc)8b,c had the
positions of the two terminal hydride atoms determined using
neutron diffraction, showing the Zn−H distance to be 1.62(6)
Å (the complex has crystallographic Ci symmetry), which is not
significantly different from that seen in 10. Still, it is not clear
whether the apparently long nature of the Zn−H bond in 10 in
comparison to those in other X-ray crystal structures represents
a real chemical difference or is just an artifact of the inherent
problems X-ray crystallography has with hydrogen atoms.
Reactivity of 10−12 with CO2. The reactions between
zinc hydride complexes 10−12 (d8-toluene) and CO2 (1 bar)
proceeded smoothly, at 298 K over 20 min, and resulted in
quantitative (by 1H NMR spectroscopy) formation of the
corresponding zinc formate complexes 13−15. Although NMR
and IR spectroscopic data were consistent with the clean
formation of the formate complexes, and in the case of 14 an
analytically pure material was prepared, the elemental analyses
for 13 and 15 were not in agreement with the expected values,
nor were they consistent, despite being prepared multiple
times. It is proposed that residual water/protic impurities, most
likely in the carbon dioxide, led to partial decomposition of the
hydride precursors, thereby interfering with the elemental
X-ray Crystal Structure of 10. The molecular structure of
10 (Figure 2) was also resolved by a single-crystal X-ray
1
analyses. The H NMR spectra show the complete disappear-
ance of the signals at ∼4 ppm, assigned to the Zn−H groups,
and the appearance of signals at ∼8.50 ppm, assigned to zinc
formate resonances. The 13C{1H} NMR spectra also show the
appearance of a resonance at ∼170 ppm, assigned to the
carbonyl carbon of the formate. In common with complexes
10−12, changing the electronic nature of the phenolate ligand
does not significantly influence the chemical shift of the formate
group in complexes 13−15 (ZnO2CH: 13, δ (d8-toluene) 8.51;
14, δ (C6D6), 8.64 ppm). Again, these new phenolate-
coordinated zinc formate complexes show chemical shifts
lower than that for a previously reported zinc formate complex
(LZnO2CH (where L = tris(2-pyridylthio)methane):17 δ 9.53
ppm). The formate moiety is likely bound in a κ2 fashion to a
single zinc center (in the solid state at 298 K), as evidenced by
infrared spectroscopy, where the difference between the
symmetric and asymmetric formate stretches (Δν) was ≤31
cm−1 (Δν: 13, 21 cm−1; 14, 26 cm−1; 15, 31 cm−1).23 However,
Figure 2. Crystal structure of 10 (50% probability ellipsoids except for
H(1), which has been drawn as an arbitrarily sized sphere). Selected
bond lengths (Å) and angles (deg); Zn−H(1) 1.75(3), Zn−O(1)
1.9462(12), Zn−N(8) 2.1272(15), Zn−N(11) 2.1447(14); O(1)−
Zn−N(8) 93.88(5), O(1)−Zn−N(11) 99.78(5), N(8)−Zn−N(11)
86.15(6).
1
solution VT H NMR spectra of 13 also indicate that there is
likely to be an entropically driven monomer−dimer equilibrium
(Figure S2, Supporting Information), with the formate
resonance shifting from 8.48 ppm (298 K) to 8.93 ppm (203
K). By analogy to the previous investigation of the zinc hydride
complex 10, it is proposed that these formate complexes exist
as monomers at 298 K, with the formate group chelating to a
single zinc center. At reduced temperatures, it is likely that a
dimeric complex forms with bridging formate ligands.
In order to establish that the formate was formed from the
carbon dioxide insertion into the zinc−hydride bond, isotopi-
cally labeled 13CO2 was used to synthesize 13C-13. This
complex showed a single signal due to the 13C of the formate at
170 ppm. The VT-13C{1H} NMR spectra (Figure 3) of 13C-13
diffraction study, which shows a mononuclear structure with a
single terminal hydride bound to a zinc center with a distorted-
tetrahedral geometry. Only a few crystal structures of similar
monozinc hydride complexes have previously been reported.
The Zn−H distances are as follows: (tris(2-pyridylthio)-
methane)zinc hydride, 1.51(3) Å;17 (tris(4,4-dimethyl-2-
oxazolinyl)phenylborate)zinc hydride,15 1.525(16) Å; 2-[(2,6-
diisopropylphenyl)amino]-4-[(2,6-diisopropylphenyl)imino]-
1115
dx.doi.org/10.1021/om400679n | Organometallics 2014, 33, 1112−1119

Organometallics
Article
Figure 3. VT 13C NMR spectra of 13c−13, in d8-THF. Spectra were collected at the temperatures 313 K (top), 273 K (middle), and 203 K
(bottom). For the full spectra, see Figure S3 (Supporting Information).
also supported the proposed temperature-dependent mono-
mer−dimer equilibrium. A single signal was observed in the
carbonyl region at 313 K, assigned to the mononuclear species
(170 ppm); when the temperature was lowered to 273 K, two
signals were observed that were assigned to the mononuclear
(170 ppm) and dinuclear (173.5 ppm) complexes. Further
cooling to 203 K led to a single signal being observed (173.5
ppm) due to the dinuclear complex.
The reactions of 10−13 with CO2 were examined, using a
Specac Reaction Cell Golden Gate ATR (see the Supporting
Information), so as to quantify the rates of CO2 insertion
(Figure 4 illustrates the IR spectra resulting from the reaction
of 11 and CO2 (in toluene), at 2 bar of pressure and 298 K).
The reaction proceeded cleanly over 30 min, with the ZnH
stretch (1740 cm−1) disappearing at the same rate as new zinc
formate resonances evolved, in the region of 1600 cm−1. These
new resonances are assigned to the symmetric and asymmetric
vibrational modes of the zinc formate moiety. From the IR
spectra, the changes in concentration of zinc hydride and zinc
formate against time were determined (Figure S6, Supporting
Information). Using an initial rates method (5−15% con-
version), the rate of formation of zinc formate (or consumption
of zinc hydride) was determined: kobs = 0.033 M min−1 (Figure
S7, Supporting Information). However, a control experiment to
determine the rate of dissolution of carbon dioxide, in toluene
under identical conditions, revealed that the initial rate (5−
15%) was almost identical, kobs = 0.034 M min−1 (Figure S9,
Supporting Information). Thus, the rate of carbon dioxide
insertion into these zinc hydride complexes is limited by the
solubility of carbon dioxide in toluene. Thus far, it has not
proved feasible to modify the experimental procedure so as to
overcome this limitation. The use of a solvent with significantly
higher CO2 transport rates, through increased CO2 solubility or
diffusion, is limited by the high reactivity of the zinc hydride
group; for example, the hydrides are incompatible with
functional groups including carbonates, carboxylates, amides,
etc.
Figure 4. Stack plot of the ATR-IR spectra showing CO2 insertion
into 11 to form 14, where negative peaks show loses and positive
peaks show gains. All spectra are referenced to the original spectrum of
11, when t = 0 min. Reaction conditions: [11] = 0.1 M, toluene, 298
K, 2 bar of CO2.
CONCLUSIONS
■
A new series of mononuclear zinc hydride complexes, ligated by
phenolate diamine ancillary ligands, has been prepared. The
complexes are mononuclear in both the solid and liquid (d8-
toluene) states at 298 K, but they demonstrate an entropically
driven equilibrium between mono- and dinuclear species at
lower temperatures. This work adds to the few other examples
1116
dx.doi.org/10.1021/om400679n | Organometallics 2014, 33, 1112−1119

Organometallics
Article
CDCl3): δ (ppm) 6.79 (d, 1H, ArH), 6.41 (d, 1H, ArH), 3.74 (s, 3H,
OCH3), 3.64 (s, 2H, CH2), 2.54 (m, 2H, NCH2CH2N), 2.48 (m, 2H,
NCH2CH2N), 2.31 (s, 6H, N(CH3)2), 2.21 (s, 3H, NCH3), 1.40 (s,
9H, C(CH3)3). 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 151.7,
150.8, 137.9, 122.8, 112.7, 111.3 (s, Ar), 62.1 (s, CH2), 57.2 (s,
C(CH3)3), 55.8 (s, OCH3), 54.4 (s, NCH3), 45.8 (s, NCH2CH2N),
41.9 (s, NCH3), 35.0 (s, NCH3), 29.5 (s, C(CH3)3). MS (ESI+): m/z
295 [M+]. Anal. Found (calcd) for C17H30N2O2: C, 69.27 (69.35); H,
10.18 (10.27); N, 9.45 (9.51).
of mononuclear zinc hydrides, and the complexes are useful
precursors for further reactions with CO2, and other insertion
reactions, relevant to catalysis. The kinetic measurements show
that CO2 insertion (298 K, 2 bar) is fast (<30 min, kobs ≥ 0.033
M min−1) but is limited by gas transport under these
conditions. Future work is warranted using compatible solvents
with a higher CO2 solubility and further improvements to the
experimental design. Nevertheless, the current kinetic findings
are significant for others studying CO2 insertion, under related
conditions, and provide further insight into the high reactivity
of zinc hydride in various catalytic cycles.
2-tert-Butyl-4-nitro-6-{[(2′-dimethylaminoethyl)-
methylamino]methyl}phenol (3). A solution of N,N,N′-trimethy-
lethylenediamine (0.87 g, 8.55 mmol), paraformaldehyde (0.33 g, 11.1
mmol), and 2-tert-butyl-4-nitrophenol (1.51 g, 7.69 mmol) in ethanol
(50 mL) was heated, under reflux and nitrogen, for 14 h. The solution
was cooled, HBr (1.6 mL, 29.4 mmol) was added, and the solution was
neutralized with NaHCO3 and extracted with CHCl3 (3 × 50 mL).
The organic layer was dried, and the solvent was removed to give a
brown oil. The crude product was purified by column chromatography
(silica gel, 3/7 CH2Cl2/Et2O) to afford a yellow solid (0.82 g, 2.91
EXPERIMENTAL SECTION
■
Materials. 4-Nitro-2-tert-butylphenol,24 compound 1,21 and 421
were synthesized according to literature procedures. All other reagents
were purchased directly from Sigma-Aldrich. Unless otherwise stated,
all reactions were conducted under a nitrogen atmosphere, either using
standard Schlenk techniques or in a nitrogen-filled glovebox. All
solvents were dried by distillation from sodium and were degassed
prior to use by performing three freeze−pump−thaw cycles.
Deuterated solvents were dried over calcium hydride, followed by
three freeze−thaw cycles before use.
1
mmol, 34%). H NMR (400 MHz, CDCl3): δ (ppm) 8.12 (d, 1H,
ArH), 7.82 (d, 1H, ArH), 3.70 (s, 2H, CH2), 2.62 (m, 2H,
NCH2CH2N), 2.53 (m, 2H, NCH2CH2N,), 2.33 (s, 3H, NCH3),
2.25 (s, 6H, N(CH3)2), 1.42 (s, 9H, C(CH3)3). 13C{1H} NMR (100
MHz, CDCl3): δ (ppm) 164.4, 139.1, 137.7, 123.3, 122.8, 122.6 (s,
Ar), 59.9 (s, CH2), 56.4 (s, C(CH3)3), 53.8 (s, NCH3), 45.4 (s,
NCH2CH2N), 41.9 (s, NCH3), 35.2 (s, NCH3), 29.2 (s, C(CH3)3).
MS (ESI+): m/z 309 [M+]. Anal. Found (calcd) for C16H27N3O3: C,
61.78 (62.11); H, 8.74 (8.80); N, 13.35 (13.58).
Spectroscopic Methods. In general, NMR spectra were collected
1
on a Bruker AV-400 instrument. H DOSY experiments were kindly
conducted by Mr. Peter Haycock at Imperial College London and
were measured on a Bruker Av500 spectrometer running TopSpin3
and equipped with a z-gradient bbo/5 mm tunable probe and a BSMS
GAB 10 A gradient amplifier providing a maximum gradient output of
5.35 G/cmA. The spectra were collected at a frequency of 500.13 MHz
with a spectral width of 5500 Hz (centered on 4.5 ppm) and 32768
data points. A relaxation delay of 12 s was employed along with a
diffusion time (large delta) of 50 ms and a longitudinal eddy current
delay (LED) of 5 ms. Bipolar gradient pulses (little delta) of 4 ms and
homospoil gradient pulses of 1.1 ms were used. The gradient strengths
of the two homospoil pulses were −17.13% and −13.17%. Sixteen
experiments were collected with the bipolar gradient strength, initially
at 2% (first experiment) and linearly increased to 95% (16th
experiment). All gradient pulses were smoothed-square shaped
(SMSQ10.100), and after each application a recovery delay of 200
us was used. The data were processed using an exponential function
with a line broadening of 1 Hz. Further processing was achieved with
dosym (NMRtec) software using the gifa-maxent processing method
and the parameter preset 5. Transmission infrared (IR) spectroscopy
was measured on a PerkinElmer Spectrum 100 FTIR spectrometer,
using Nujol (dried over sodium) as a mull and NaBr plates. ATR-IR
spectra were recorded using a “Reaction Cell Golden Gate ATR”
accessory supplied by Specac and attached to a custom-made gas
handling manifold. The accessory uses a diamond reflection element
with single-bounce geometry built into the base of a reactor that allows
heating and pressurization. Measurements were carried out a Bruker
Tensor 27 FTIR spectrometer using a liquid nitrogen cooled MCT
detector. CO2 was industrial grade from BOC and was used without
further purification. Elemental analyses were carried out using a Carlo
Erba CE1108 elemental analyzer, and samples were manipulated under
an inert atmosphere (helium glovebag), by Mr. S. Boyer at London
Metropolitan University, North Campus, Holloway Road, London N7,
U.K.
[
OMeLZnEt] (5). To a solution of 2 (1.13 g, 3.84 mmol) in pentane
(10 mL) was slowly added ZnEt2 (0.52 g, 4.22 mmol), and the mixture
was stirred at 298 K for 16 h. The white precipitate was filtered and
1
dried under vacuum (0.75 g, 1.96 mmol, 51%). H NMR (400 MHz,
C6D6): δ (ppm) 7.27 (d, 1H, ArH), 6.55 (d, 1H, ArH), 3.64 (s, 3H,
OCH3), 3.29 (d, 1H, CH2), 3.04 (d, 1H, CH2), 2.11 (m, 1H,
NCH2CH2N), 1.89 (s, 3H, NCH3), 1.80 (s, 9H, C(CH3)3), 1.77 (m,
1H, NCH2CH2N), 1.73 (s, 6H, N(CH3)2), 1.62 (t, 3H, CH3), 1.55 (m,
2H, NCH2CH2N), 0.44 (q, 2H, CH2). 13C{1H} NMR (100 MHz,
C6D6): δ (ppm) 161.9, 148.6, 139.6, 122.5, 114.7, 114.6 (s, Ar), 62.0
(s, CH2), 57.1 (s, C(CH3)3), 55.9 (s, OCH3), 52.3 (s, NCH3), 46.6,
45.6 (s, NCH2CH2N), 44.9 (s, NCH3), 35.9 (s, NCH3), 30.1 (s,
C(CH3)3), 14.0 (s, CH3), −3.9 (s, CH2). Anal. Found (calcd) for
C19H34N2O2Zn: C, 58.92 (58.84); H, 8.91 (8.84); N, 7.17 (7.22).
[
NO2LZnEt] (6). To a solution of 3 (300 mg, 0.97 mmol) in toluene
(10 mL) was slowly added ZnEt2 (119 mg, 0.97 mmol), and the
mixture was stirred at 298 K for 16 h. The yellow precipitate was
filtered and dried under vacuum (214 mg, 0.56 mmol, 57%). 1H NMR
(400 MHz, C6D6): δ (ppm) 8.62 (d, 1H, ArH), 7.99 (d, 1H, ArH),
2.98 (d, 1H, CH2), 2.69 (d, 1H, CH2), 1.83 (m, 2H, NCH2CH2N),
1.70 (s, 3H, NCH3), 1.60 (s, 3H, NCH3), 1.58 (s, 9H, C(CH3)3), 1.56
(s, 3H, NCH3), 1.54 (t, 3H, CH3), 1.45 (m, 1H, NCH2CH2N), 1.33
(m, 1H, NCH2CH2N), 0.37 (q, 2H, CH2). 13C NMR (100 MHz,
C6D6): δ (ppm) 175.3, 139.7, 135.4, 126.9, 124.8, 122.7 (s, Ar), 61.0
(s, CH2), 56.9 (s, C(CH3)3), 52.1 (s, NCH3), 47.0, 45.6 (s,
NCH2CH2N), 45.0 (s, NCH3), 35.8 (s, NCH3), 29.8 (s, C(CH3)3),
13.9 (s, CH3), −3.9 (s, CH2). Anal. Found (calcd) for C18H31N3O3Zn:
C, 53.48 (53.67); H, 7.67 (7.76); N, 10.36 (10.43).
[
tBuLZnSiOPh3] (7). A solution of 4 (1.00 g, 2.43 mmol) and
HOSiPh3 (0.67 g, 2.43 mmol), dissolved in toluene (20 mL), was
stirred at 298 K for 16 h. The solvent was removed, and the white
precipitate was washed with pentane (20 mL) and filtered to yield the
2-tert-Butyl-4-methoxy-6-{[(2′-dimethylaminoethyl)-
methylamino]methyl}phenol (2). A solution of N,N,N′-trimethy-
lethylenediamine (2.00 g, 19.6 mmol), paraformaldehyde (0.76 g, 25.5
mmol), and 3-tert-butyl-4-hydroxyanisole (3.53 g, 19.6 mmol) in
ethanol (100 mL) was heated at reflux under nitrogen for 14 h. The
solution was cooled and the volume reduced by 50 mL. HBr (1.6 mL,
29.4 mmol) was added, and the solution was neutralized (NaHCO3).
The solution was washed with CHCl3 (3 × 70 mL) and dried with
MgSO4, the solvent was removed under vacuum, and the resulting
material was washed with pentane (25 mL) to yield the product as a
white powder (3.56 g, 12.7 mmol, 65%). 1H NMR (400 MHz,
1
product as a white powder (1.57 g, 2.38 mmol, 98%). H NMR (400
MHz, C6D6): δ (ppm) 7.98 (m, 5H, SiPh3), 7.60 (d, 1H, ArH), 7.26
(m, 10H, SiPh3), 6.80 (d, 1H, ArH), 3.55 (d, 1H, CH2), 2.82 (d, 1H,
CH2), 2.24 (m, 1H, NCH2CH2N), 1.81 (s, 3H, NCH3), 1.78 (s, 4H,
NCH3), 1.77 (s, 9H, C(CH3)3), 1.71 (m, 1H, NCH2CH2N), 1.49 (s,
3H, NCH3), 1.46 (s, 9H, C(CH3)3), 1.33 (m, 1H, NCH2CH2N).
13C{1H} NMR (100 MHz, C6D6): δ (ppm) 164.9, 141.3, 138.7 (s, Ar),
135.9, 135.7 (s, SiPh3), 129.0, 127.8 (s, SiPh3), 126.2, 124.7, 121.5 (s,
Ar), 63.2 (s, CH2), 57.1 (s, C(CH3)3), 51.0 (s, NCH3), 47.6, 45.1 (s,
NCH2CH2N), 44.2 (s. NCH3), 35.9 (s, NCH3), 34.2 (s, C(CH3)3),
1117
dx.doi.org/10.1021/om400679n | Organometallics 2014, 33, 1112−1119

Organometallics
Article
32.3, 30.2 (s, C(CH3)3). Anal. Found (calcd) for C38H50N2O2SiZn: C,
added (10 mL), and the yellow precipitate was then isolated by
centrifugation (3900 rpm, 20 min) and dried under vacuum (87 mg,
0.23 mmol, 58%). 1H NMR (400 MHz, C6D6): δ (ppm) 8.61 (d, 1H,
ArH), 7.97 (s, 1H, ArH), 3.99 (s, 1H, ZnH), 3.03 (d, 1H, CH2), 2.71
(d, 1H, CH2), 1.90 (m, 1H, NCH2CH2N), 1.78 (s, 3H, NCH3), 1.69
(s, 3H, NCH3), 1.59 (m, 12H, NCH3 and C(CNCH2CH2N). 13C{1H}
NMR (100 MHz, C6D6): δ (ppm) 139.4, 135.5, 135.1, 126.3, 124.2,
121.1 (s, Ar), 60.2 (s, CH2), 56.3 (s, C(CH3)3), 51.5 (s, NCH3), 44.7
(m, NCH2CH2N), 44.6 (s, NCH3), 35.1 (s, NCH3), 29.2 (s,
C(CH3)3). IR (Nujol): ν (cm−1) 1755 (ZnH). Anal. Found (calcd)
for C16H27N3O3Zn: C, 51.15 (51.28); H, 7.16 (7.26); N, 11.02
(11.21).
68.97 (69.12); H, 7.64 (7.63); N, 4.15 (4.24).
[
OMeLZnSiOPh3] (8). To a solution of 5 (358 mg, 1.29 mmol) in
benzene (10 mL) was added HOSiPh3 (500 mg, 1.29 mmol), and the
mixture was stirred at 298 K for 16 h. The solvent was removed to
yield the product as a white crystalline powder which required no
1
further purification (410 mg, 0.65 mmol, 51%). H NMR (400 MHz,
C6D6): δ (ppm) 8.01 (d, 5H, SiPh3), 8.00 (d, 1H, ArH), 7.31 (m, 10H,
SiPh3), 6.41 (d, 1H, ArH), 3.60 (s, 3H, OCH3), 3.53 (d, 1H, CH2),
2.75 (d, 1H, CH2), 2.17 (m, 1H, NCH2CH2N), 1.80 (s, 6H,
N(CH3)2), 1.72 (s, 9H, C(CH3)3), 1.56 (m, 1H, NCH2CH2N), 1.49
(s, 3H, NCH3), 1.34 (m, 2H, NCH2CH2N). 13C{1H} NMR (100
MHz, C6D6): δ (ppm) 161.7, 149.5 142.3 (s, Ar), 140.4, 136.0 (s,
SiPh3), 129.2, 128.8 (s, SiPh3), 122.1, 115.2, 115.0 (s, Ar), 63.0 (s,
CH3), 57.5 (s, C(CH3)3), 56.1 (s, OCH3), 51.2 (s, NCH3), 47.8, 45.3
(s, NCH2CH2N), 44.5 (s, NCH3), 36.1 (s, NCH3), 30.3 (s, C(CH3)3).
Anal. Found (calcd) for C35H44N2O3SiZn: C, 66.15 (66.28); H, 7.07
(6.99); N, 4.37 (4.42).
[
tBuLZnCO2H] (13). In an evacuated Young’s tap NMR tube
containing a frozen solution of 10 (30 mg, 0.08 mmol), in d8-toluene
(0.6 mL), CO2 (1 atm) was introduced to 1 bar of pressure and the
solution was warmed to 298 K. After 30 min at 298 K, without any
stirring or shaking, the reaction was complete and the product was
1
identified by NMR and IR spectroscopy. H NMR (400 MHz, d8-
[
NO2LZnSiOPh3] (9). To a solution of 6 (174 mg, 0.45 mmol) in
toluene): δ (ppm) 8.51 (s, 1H, O2CH), 7.52 (d, 1H, ArH), 6.81 (d,
1H, ArH), 3.43 (d, 1H, CH2), 3.07 (d, 1H, CH2),, 2.12 (s, 3H, NCH3),
2.08 (m, 1H, NCH2CH2N), 1.87 (s, 6H, N(CH3)2), 1.74 (s, 9H,
C(CH3)3), 1.61 (m, 2H, NCH2CH2N), 1.40 (s, 9H, C(CH3)3), 1.24
(m, 1H, NCH2CH2N). 13C{1H} NMR (100 MHz, d8-THF): δ (ppm)
170.0 (s, O2CH), 156.7, 136.3, 135.8, 126.5, 124.6, 122.6 (s, Ar), 63.1
(s, CH2), 57.2 (s, C(CH3)3), 52.2 (s, NCH3), 46.6, 45.0 (m,
NCH2CH2N), 36.2 (s, NCH3), 34.5 (s, NCH3), 32.5 (s, C(CH3)3),
30.5 (s, C(CH3)3). IR (ATR): ν (cm−1) 1608, 1587 (ZnO2CH).
Satisfactory elemental analyses could not be obtained for this
compound.
benzene (10 mL) was added HOSiPh3 (142 mg, 0.45 mmol), and the
mixture was stirred at 298 K for 16 h. The solvent was then removed
to yield the product as a yellow crystalline powder which required no
1
further purification (174 mg, 0.27 mmol, 60%). H NMR (400 MHz,
C6D6): δ (ppm) 8.57 (d, 1H, ArH), 7.95 (m, 5H, SiPh3), 7.85 (d, 1H,
ArH), 7.28 (m, 10H, SiPh3), 3.16 (d, 1H, CH2), 2.46 (d, 1H, CH2),
1.89 (m, 1H, NCH2CH2N), 1.71 (s, 3H, NCH3), 1.66 (s, 3H, NCH3),
1.59 (m, 1H, NCH2CH2N), 1.51 (s, 9H, C(CH3)3), 1.33 (s, 3H,
NCH3), 1.22 (m, 1H, NCH2CH2N), 1.16 (m, 1H, NCH2CH2N).
13C{1H} NMR (100 MHz, C6D6): δ (ppm) 174.5, 141.5, 140.1 (s, Ar),
136.0, 135.6 (s, SiPh3), 129.2, 127.9 (s, SiPh3), 126.9, 124.5, 121.7 (s,
Ar), 61.6 (s, CH2), 56.8 (s, C(CH3)3), 50.7 (s, NCH3), 47.6, 44.8 (s,
NCH2CH2N), 44.1 (s, NCH3), 35.6 (s, NCH3), 29.4 (s, C(CH3)3).
Anal. Found (calcd) for C34H41N3O4SiZn: C, 62.79 (62.91); H, 6.32
(6.37); N, 6.38 (6.47).
[
OMeLZnCO2H] (14). In an evacuated NMR tube containing a
frozen solution of 11 (30 mg, 0.083 mmol) in d8-toluene (0.6 mL),
CO2 (1 atm) was introduced and the solution was warmed to 298 K.
After 30 min at 298 K, with no stirring or shaking, the reaction was
complete. 1H NMR (400 MHz, C6D6): δ (ppm) 8.64 (s, 1H, O2CH),
7.27 (d, 1H, ArH), 6.51 (d, 1H, ArH), 3.62 (s, 3H, OCH3), 3.34 (d,
1H, CH2), 3.05 (d, 1H, CH2), 2.09 (s, 3H, NCH3), 1.83−1.62 (m,
10H, N(CH3)2 and NCH2CH2N), 1.78, (s, 9H, C(CH3)3), 1.62 (m,
4H, NCH2CH2N). 13C{1H} NMR (100 MHz, C6D6): δ (ppm) 170.0
(s, O2CH), 161.2, 149.2, 140.3, 136.0, 122.1, 114.8 (s, Ar), 62.4 (s,
CH2), 56.7 (s, C(CH3)3), 55.9 (s, OCH3), 51.7 (s, NCH3), 46.1
(NCH2CH2N), 44.7 (NCH3), 35.8 (NCH3), 30.2 (C(CH3)3). IR
(ATR): ν (cm−1) 1612, 1586 (ZnO2CH). Anal. Found (calcd) for
C18H30N2O4Zn: C, 53.41 (53.54); H, 7.56 (7.49); N, 6.85 (6.94).
[
tBuLZnH] (10). To a solution of 7 (300 mg, 0.46 mmol) in toluene
(10 mL) was added phenylsilane (49 mg, 0.46 mmol). The solution
was stirred at 298 K for 16 h. The solvent was removed and pentane
added (10 mL). The white precipitate was isolated by centrifugation
(3900 rpm, 20 min) and dried under vacuum (68 mg, 0.27 mmol,
1
60%). H NMR (400 MHz, C6D6): δ (ppm) 7.64 (d, 1H, ArH), 6.89
(d, 1H, ArH), 4.10 (s, 1H, ZnH), 3.47 (d, 1H, CH2), 3.01 (d, 1H,
CH2), 2.32 (m, 1H, NCH2CH2N), 1.94 (s, 3H, NCH3), 1.87 (s, 9H,
C(CH3)3), 1.72 (s, 6H, NCH3), 1.62 (m, 2H, NCH2CH2N), 1.48 (s,
9H, C(CH3)3), 1.25 (m, 1H, NCH2CH2N). 13C{1H} NMR (100
MHz, C6D6): δ (ppm) 164.8, 138.3, 134.8, 128.2, 124.4, 121.9 (s, Ar),
62.3 (s, CH2), 56.8 (s, C(CH3)3), 51.9 (s, NCH3) 47.2, 45.1 (s,
NCH2CH2N), 35.8 (s, NCH3), 34.1 (s, NCH3), 32.3 (s, C(CH3)3),
30.3 (s, C(CH3)3). IR (Nujol) ν (cm−1) 1723 (ZnH). Anal. Found
(calcd) for C20H30N2OZn: C, 62.14 (62.25); H, 9.32 (9.40); N, 7.14
(7.26).
[
NO2LZnCO2H] (15). In an evacuated NMR tube containing a
frozen solution of 12 (30 mg, 0.080 mmol) in d2-tetrachloroethane
(0.6 mL), CO2 (1 atm) was introduced and the solution was warmed
to 298 K. After 30 min at 298 K, with no stirring or shaking, the
reaction was complete and the product identified by NMR and IR
1
spectroscopy. H NMR (400 MHz, d2-TCE): δ (ppm) 8.31 (s, 1H,
[
OMeLZnH] (11). To a solution of 8 (300 mg, 0.48 mmol) in
O2CH), 8.14 (d, 1H, ArH), 7.88 (d, 1H, ArH), 3.79 (d, 1H, CH2),
3.70 (d, 1H, CH2), 2.83 (m, 2H, NCH2CH2N), 2.70 (m, 2H,
NCH2CH2N), 2.61 (s, 3H, NCH3), 2.52 (s, 3H, NCH3), 2.35 (s, 3H,
NCH3), 1.41 (s, 9H, C(CH3)3). 13C{1H} NMR (100 MHz, d2-TCE):
δ (ppm) 174.2 (s, Ar), 170.7 (s, O2CH), 140.2, 134.9, 126.4, 124.2,
121.7 (s, Ar), 61.1 (s, CH2), 56.8 (s, C(CH3)3), 52.2 (s, NCH3), 46.8,
46.2 (s, NCH2CH2N), 45.0 (NCH3), 35.1 (NCH3), 29.1 (C(CH3)3).
IR (ATR): ν (cm−1) 1614, 1583 (ZnO2CH). Satisfactory elemental
analyses could not be obtained for this compound.
toluene (10 mL) was added PhSiH3 (51 mg, 0.48 mmol), and the
solution was stirred at 298 K for 16 h. The solvent was removed and
pentane added (10 mL). The solution was stirred for 30 min, followed
by centrifugation (3900 rpm, 20 min) to separate the fine precipitate,
1
which was then dried under vacuum (76 mg, 0.22 mmol, 46%). H
NMR (400 MHz, C6D6): δ (ppm) 7.29 (d, 1H, ArH), 6.54 (d, 1H,
ArH), 4.09 (s, 1H, ZnH), 3.64 (s, 3H, OCH3), 3.34 (d, 1H, CH2), 2.98
(d, 1H, CH2), 2.13 (m, 1H, NCH2CH2N), 1.91 (s, 3H, NCH3), 1.82
(s, 9H, C(CH3)3), 1.77 (s, 3H, NCH3), 1.72 (s, 3H, NCH3), 1.63 (m,
2H, NCH2CH2N), 1.48 (m, 1H, NCH2CH2N). 13C{1H} NMR (100
MHz, C6D6): δ (ppm) 161.2, 148.7, 139.7, 122.3, 114.5, 110.0 (s, Ar),
61.6 (s, CH2), 56.7 (s, C(CH3)3), 55.7 (s, OCH3), 51.9 (s, NCH3),
47.1, 47.0 (s, NCH2CH2N), 45.0 (s, NCH3) 35.6 (s, NCH3), 29.9 (s,
C(CH3)3). IR (Nujol): ν (cm−1) 1749, 1732 (ZnH). Anal. Found
(calcd) for C17H30N2O3Zn: C, 56.70 (56.75); H, 8.29 (8.40); N, 7.66
(7.79).
ASSOCIATED CONTENT
■
S
* Supporting Information
Figures, text, tables, and a CIF file giving crystallographic data
for structure 10, VT NMR (1H and 13C) and DOSY spectra,
details of the DFT models generated, and full details of the
ATR-IR experiments conducted. This material is available free
of charge via the Internet at http://pubs.acs.org.
[
NO2LZnH] (12). To a solution of 9 (260 mg, 0.40 mmol) in toluene
(10 mL) was added phenylsilane (47 mg, 0.44 mmol), and the mixture
was stirred at 298 K for 16 h. The solvent was removed, pentane was
1118
dx.doi.org/10.1021/om400679n | Organometallics 2014, 33, 1112−1119

Organometallics
Article
Harder, S. Chem. Commun. 2009, 3455. (e) Schulz, S.; Eisenmann, T.;
Schmidt, S.; Blaser, D.; Westphal, U.; Boese, R. Chem. Commun. 2010,
46, 7226. (f) Bendt, G.; Schulz, S.; Spielmann, J.; Schmidt, S.; Blaser,
D.; Wolper, C. Eur. J. Inorg. Chem. 2012, 3725.
AUTHOR INFORMATION
Corresponding Author
*E-mail for C.K.W.: c.k.williams@imperial.ac.uk.
■
(13) Marciniak, W.; Merz, K.; Moreno, M.; Driess, M. Organo-
metallics 2006, 25, 4931.
(14) Zhu, Z. L.; Fettinger, J. C.; Olmstead, M. M.; Power, P. P.
Organometallics 2009, 28, 2091.
(15) Coles, M. P.; El-Hamruni, S. M.; Smith, J. D.; Hitchcock, P. B.
Angew. Chem., Int. Ed. 2008, 47, 10147.
(16) Mukherjee, D.; Ellern, A.; Sadow, A. D. J. Am. Chem. Soc. 2010,
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The EPSRC (EP/H046380, EP/K035274/1, and DTG award
to J.E.H.) is acknowledged for funding this research.
132, 7582.
(17) Kahnes, M.; Gorls, H.; Westerhausen, M. J. Organomet. Chem.
2011, 696, 1618.
(18) Sattler, W.; Parkin, G. J. Am. Chem. Soc. 2011, 133, 9708.
(19) Fedushkin, I. L.; Eremenko, O. V.; Skatova, A. A.; Piskunov, A.
V.; Fukin, G. K.; Ketkov, S. Y.; Irran, E.; Schumann, H. Organometallics
2009, 28, 3863.
(20) Mukherjee, D.; Lampland, N. L.; Yan, K.; Dunne, J. F.; Ellern,
A.; Sadow, A. D. Chem. Commun. 2013, 49, 4334.
(21) Williams, C. K.; Breyfogle, L. E.; Choi, S. K.; Nam, W.; Young,
V. G., J.; Hillmyer, M. A.; Tolman, W. B. J. Am. Chem. Soc. 2003, 125,
11350.
(22) (a) Hild, F.; Heehaul, N.; Bier, F.; Wirsum, M.; Gourlaouen, C.;
Dagorne, S. Organometallics 2013, 32, 587. (b) Douglas, A. F.; Patrick,
B. O.; Mehrkhodavandi, P. Angew. Chem., Int. Ed. 2009, 47, 2290.
(23) Nakamoto, K., Infrared and Raman Spectroscopy of Inorganic and
Coordination Compounds Part B: Applications on Coordination,
Organometallic, and Bioinorganic Chemistry; Wiley: New York, 1997;
p 5960.
REFERENCES
■
(1) (a) Sattler, W.; Parkin, G. J. Am. Chem. Soc. 2012, 134, 17462.
(b) Mukherjee, D.; Thompson, R. R.; Ellern, A.; Sadow, A. D. ACS
Catal. 2011, 1, 698. (c) Kahnes, M.; Gorls, H.; Gonzalez, L.;
Westerhausen, M. Organometallics 2011, 29, 3098. (d) Enthaler, S.
ACS Catal. 2013, 3, 150. (e) Gao, Y.; Urabe, H.; Sato, F. J. Org. Chem.
1994, 59, 5521. (f) Gao, Y.; Harada, K.; Hata, T.; Urabe, H.; Sato, F. J.
Org. Chem. 1995, 60, 290. (g) Bette, V.; Mortreux, A.; Savoia, D.;
Carpentier, J. F. Adv. Synth. Catal. 2005, 347, 289. (h) Aldridge, S.;
Downs, A. J. Chem. Rev. 2001, 101, 3305.
(2) (a) Bergquist, C.; Koutcher, L.; Vaught, A. L.; Parkin, G. Inorg.
Chem. 2002, 41, 625. (b) Looney, A.; Han, R.; Gorrell, I. B.;
Cornebise, M.; Yoon, K.; Parkin, G.; Rheingold, A. L. Organometallics
1995, 14, 274.
(3) (a) Rombach, M.; Brombacher, H.; Vahrenkamp, H. Eur. J. Inorg.
Chem. 2002, 153. (b) Liao, F. L.; Zeng, Z. Y.; Eley, C.; Lu, Q.; Hong,
X. L.; Tsang, S. C. E. Angew. Chem., Int. Ed. 2012, 51, 5832. (c) Liao,
F. L.; Huang, Y. Q.; Ge, J. W.; Zheng, W. R.; Tedsree, K.; Collier, P.;
Hong, X. L.; Tsang, S. C. Angew. Chem., Int. Ed. 2011, 50, 2162.
(d) Behrens, M.; Studt, F.; Kasatkin, I.; Kuhl, S.; Havecker, M.; Abild-
Pedersen, F.; Zander, S.; Girgsdies, F.; Kurr, P.; Kniep, B. L.; Tovar,
M.; Fischer, R. W.; Norskov, J. K.; Schlogl, R. Science 2012, 336, 893.
(e) Sliem, M. A.; Turner, S.; Heeskens, D.; Kalidindi, S. B.; Van
Tendeloo, G.; Muhler, M.; Fischer, R. A. Phys. Chem. Chem. Phys.
2012, 14, 8170. (f) Schimpf, S.; Rittermeier, A.; Zhang, X.; Li, Z.-A.;
Spasova, M.; van den Berg, M. W. E.; Farle, M.; Wang, Y.; Fischer, R.
A.; Muhler, M. ChemCatChem 2010, 2, 214. (g) Chinchen, G. C.;
Denny, P. J.; Jennings, J. R.; Spencer, M. S.; Waugh, K. C. Appl. Catal.
1988, 36, 1.
(24) Charpentier, B.; Bernardon, J. M.; Eustache, J.; Millois, C.;
Martin, B.; Michel, S.; Shroot, B. J. Med. Chem. 1995, 38, 4993.
(4) Ashby, E. C.; Watkins, J. J.; Greig, D.; Shriver, D. F. Inorg. Synth.
1977, 17, 6.
(5) Koning, A. J. D.; Boersma, J.; Vanderkerk, G. J. M. Tetrahedron
Lett. 1977, 2547.
(6) Merz, K.; Moreno, M.; Loffler, E.; Khodeir, L.; Rittermeier, A.;
Fink, K.; Kotsis, K.; Muhler, M.; Driess, M. Chem. Commun. 2008, 73.
(7) Rit, A.; Spaniol, T. P.; Maron, L.; Okuda, J. Angew. Chem., Int. Ed.
2013, 52, 4664.
(8) (a) Bell, N. A.; Kassyk, A. L. J. Organomet. Chem. 1988, 345, 245.
(b) Bell, N. A.; Moseley, P. T.; Shearer, H. M. M.; Spencer, C. B. J.
Chem. Soc., Chem. Commun. 1980, 359. (c) Bell, N. A.; Kassyk, A. L.
Inorg. Chim. Acta 1996, 250, 345. (d) Gutschank, B.; Schulz, S.; Blaser,
D.; Boese, R.; Wolper, C. Organometallics 2012, 29, 6133.
(9) (a) Brombacher, H.; Vahrenkamp, H. Inorg. Chem. 2004, 43,
6042. (b) Han, R.; Gorrell, I. B.; Looney, A. G.; Parkin, G. J. Chem.
Soc., Chem. Commun. 1991, 717. (c) Klaui, W.; Schilde, U.; Schmidt,
M. Inorg. Chem. 1997, 36, 1598.
(10) Snyder, C. J.; Heeg, M. J.; Winter, C. H. Inorg. Chem. 2011, 50,
9210.
(11) Krieger, M.; Neumuller, B.; Dehnicke, K. Z. Anorg. Allg. Chem.
1998, 624, 1563.
(12) (a) Hao, H. J.; Cui, C. M.; Roesky, H. W.; Bai, G. C.; Schmidt,
H. G.; Noltemeyer, M. Chem. Commun. 2001, 1118. (b) Prust, J.;
Hohmeister, H.; Stasch, A.; Roesky, H. W.; Magull, J.; Alexopoulos, E.;
Uson, I.; Schmidt, H. G.; Noltemeyer, M. Eur. J. Inorg. Chem. 2002,
2156. (c) Schulz, S.; Eisenmann, T.; Schuchmann, D.; Bolte, M.;
Kirchner, M.; Boese, R.; Spielmann, J.; Harder, S. Z. Naturforsch., B
2009, 64, 1397. (d) Spielmann, J.; Piesik, D.; Wittkamp, B.; Jansen, G.;
1119
dx.doi.org/10.1021/om400679n | Organometallics 2014, 33, 1112−1119