POP-rhodium-promoted C-H and B-H bond activation and C-B bond formation

Article abstract of DOI:10.1021/acs.organomet.5b00176

The square-planar monohydride complex RhH{xant(PⁱPr₂)₂} (1; xant(PⁱPr₂)₂ = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) activates C-H bonds of arenes. Heating of benzene solutions of 1 at 80 °C affords RhPh{xant(PⁱPr₂)₂} (2). Under the same conditions, toluene gives Rh(m-tolyl){xant(PⁱPr₂)₂} (3a) and Rh(p-tolyl){xant(PⁱPr₂)₂} (3b) in a 78:22 molar ratio, whereas m-xylene leads to Rh(C₆H₃-3,5-Me₂){xant(PⁱPr₂)₂} (4). At room temperature, fluorobenzene and 1,3-difluorobenzene generate Rh(C₆H₄-2-F){xant(PⁱPr₂)₂} (5) and Rh(C₆H₃-2,6-F₂){xant(PⁱPr₂)₂} (6), respectively. Complex 1 also promotes the B-H bond activation of pinacolborane (HBpin) and catecholborane (HBcat). The reactions initially give the trans-dihydride derivatives RhH₂(BR₂){xant(PⁱPr₂)₂} (BR₂ = Bpin (7), Bcat (8)), which lose H₂ to afford the square-planar Rh(BR₂){xant(PⁱPr₂)₂} (BR₂ = Bpin (9), Bcat (10)). Complex 2 reacts with HBpin to regenerate 1 and to give Ph-Bpin. Similarly, complex 9 regenerates 1 and gives Ph-Bpin by reaction with benzene. In agreement with these transformations, complex 1 catalyzes the direct C-H borylation of arenes. The selectivity of the process appears to be governed by the kinetic of the C-H bond activations of the arenes. Benzylic borylation is not observed for methylbenzenes. The first X-ray structure of a square-planar rhodium-boryl complex is also reported.

Full text of DOI:10.1021/acs.organomet.5b00176

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Article
pubs.acs.org/Organometallics
POP−Rhodium-Promoted C−H and B−H Bond Activation and C−B
Bond Formation
Miguel A. Esteruelas,* Montserrat Olivan, and Andrea Velez
́
́
́ ́ ́ ́
Departamento de Química Inorganica, Instituto de Síntesis Química y Catalisis Homogenea (ISQCH), Centro de Innovacion en
Química Avanzada (ORFEO−CINQA), Universidad de Zaragoza - CSIC, 50009 Zaragoza, Spain
S
* Supporting Information
ABSTRACT: The square-planar monohydride complex RhH-
{xant(PiPr2)2} (1; xant(PiPr2)2 = 9,9-dimethyl-4,5-bis-
(diisopropylphosphino)xanthene) activates C−H bonds of
arenes. Heating of benzene solutions of 1 at 80 °C affords
RhPh{xant(PiPr2)2} (2). Under the same conditions, toluene
gives Rh(m-tolyl){xant(PiPr2)2} (3a) and Rh(p-tolyl){xant-
(PiPr2)2} (3b) in a 78:22 molar ratio, whereas m-xylene leads
to Rh(C6H3-3,5-Me2){xant(PiPr2)2} (4). At room temperature,
fluorobenzene and 1,3-difluorobenzene generate Rh(C6H4-2-
F){xant(PiPr2)2} (5) and Rh(C6H3-2,6-F2){xant(PiPr2)2} (6),
respectively. Complex 1 also promotes the B−H bond
activation of pinacolborane (HBpin) and catecholborane
(HBcat). The reactions initially give the trans-dihydride derivatives RhH2(BR2){xant(PiPr2)2} (BR2 = Bpin (7), Bcat (8)),
which lose H2 to afford the square-planar Rh(BR2){xant(PiPr2)2} (BR2 = Bpin (9), Bcat (10)). Complex 2 reacts with HBpin to
regenerate 1 and to give Ph-Bpin. Similarly, complex 9 regenerates 1 and gives Ph-Bpin by reaction with benzene. In agreement
with these transformations, complex 1 catalyzes the direct C−H borylation of arenes. The selectivity of the process appears to be
governed by the kinetic of the C−H bond activations of the arenes. Benzylic borylation is not observed for methylbenzenes. The
first X-ray structure of a square-planar rhodium−boryl complex is also reported.
facilitates transformations, which are disfavored with the
classical more rigid PNP and PCP systems. With this in
mind, we have recently initiated a research program on POP
complexes of groups 8 and 9 metals, in the search for new
transition metal catalysts.13 Thus, following the procedure used
by Werner to generate [RhCl(PiPr3)2]2,14 we prepared the
INTRODUCTION
■
C−H bond functionalization reduces the production of toxic
byproducts thereby contributing to the growing field of
reactions with decreased environmental impact.1 One of the
most efficient reactions is the direct borylation of hydrocarbons,
which represents a powerful tool for the functionalization of
feedstocks,2 in combination with cross-coupling methodologies
or specific transformations developed for organoboranes.3
The borylation of arenes without the need for directing
groups is a challenge in the field of C−H bond functionaliza-
tion because it provides products with complementary
regioselectivity, which appears to be determined by steric
factors.4 In this context, significant progress is being made by
using iron,5 cobalt,6 rhodium,7 and iridium8 catalysts with bis-
pinacolborane (B2pin2) and pinacolborane (HBpin). The
processes take place via stoichiometric reactions involving the
sequential cleavage of both C−H9 and B−H10 bonds and the
formation of B−C and H−H bonds on the metal center of a
transition metal complex. Accordingly, the study of these
elemental steps is of great interest.
square-planar derivative RhCl{xant(PiPr2)2} (xant(PiPr2)2
=
9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene).13e In
agreement with the impact generated by the pincer ligands in
homogeneous catalysis,15 rhodium complexes containing POP
ligands had previously shown to be catalysts of interesting
organic reactions including the hydroacylation of alkenes and
alkynes,16 the hydroformylation of olefins,17 the methanol
carbonylation,18 the intramolecular hydroamination of un-
protected primary aminoalkenes,19 or the carbothiolation of
alkynes.20 In parallel with our work, Goldman has observed that
the cationic dihydride [RhH2{xant(PiPr2)2}]+ functions as a
modestly active alkane dehydrogenation catalyst,21 and
recently, Manners and Weller have shown that [Rh-
(xantphos)]+ promotes dehydrocoupling and dehydropolyme-
rization of amine-boranes22 and the hydroboration of alkenes
with amine-boranes.23
Complexes containing diphosphine pincer ligands show
marked abilities to stabilize uncommon species as a
consequence of the disposition of their donor ligands.11
Among the ligands of this type, those based on POP skeletons
have a particular interest due to the hemilabile properties of the
central oxygen atom. Their reversible κ3-κ2 conversion12
Received: March 3, 2015
© XXXX American Chemical Society
A
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Scheme 1
Complex RhCl{xant(PiPr2)2} is transformed into the square-
planar monohydride RhH{xant(PiPr2)2} by reaction with
KOiPr in 2-propanol (Scheme 1).13e This compound, which
is a notable example of four-coordinate group 8 metal hydride
derivative,24 has been also prepared by Goldman’s group21 by
means of a two-step procedure involving the initial oxidative
addition of H2 to the starting chloro-derivative and the
subsequent reaction of the resulting rhodium(III)-dihydride
with KOtBu in benzene. The π-basicity of the chloride ligand
enhances the nucleophilicity of MX{xant(PiPr2)2} (M = Rh, Ir;
X = Cl, H) fragments with regard to the hydride.13e,f As a result,
there is a marked difference in stability between the
rhodium(III) species resulting from the oxidative addition
processes to the corresponding square-planar complexes. Thus,
while the Si−H bond activation of silanes promoted by the
chloro complex leads to stable rhodium(III) derivatives, the
oxidative addition of the Si−H bond to the monohydride
generates dihydride-silyl species, which are unstable and lose H2
to afford square-planar rhodium(I)-silyl compounds (Scheme
1); that is, the hydride ligand decreases the nucleophilicity of
the RhX{xant(PiPr2)2} fragment enhancing the lability of the
saturated rhodium(III) species. The chloride by hydride
replacement should therefore increase the catalytic potentiality
of the system. This reason prompted us to select to the
monohydride complex RhH{xant(PiPr2)2} to investigate the
elemental steps involved in the direct C−H borylation of
arenes. This paper reports the C−H bond activation of arenes,
the B−H bond activation of boranes, and the stoichiometric
and catalytic formation of aryl boronate esters promoted by the
square-planar rhodium monohydride.
Scheme 2
RESULTS AND DISCUSSION
■
1. C−H Bond Activation Reactions. The square-planar
monohydride complex RhH{xant(PiPr2)2} (1) activates
aromatic C−H bonds of benzene, toluene, and m-xylene. The
reactions lead to aryl−rhodium(I) complexes and release
molecular hydrogen. The selectivity of the processes involving
the substituted benzenes depends upon the position of the
substituents (Scheme 2).
Figure 1. ORTEP diagram of complex 2 (50% probability ellipsoids).
Hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and
angles (deg): Rh(1)−P(1) = 2.2460(12), 2.2530(12), Rh(1)−P(2) =
2.2293(12), 2.2333(12); Rh(1)−O(1) = 2.214(3), 2.216(3), Rh(1)−
C(1) = 1.977(4), 1.979(5); P(1)−Rh(1)−P(2) = 164.28(5),
163.00(4), P(1)−Rh(1)−O(1) = 82.15(8), 82.35(8), P(2)−Rh(1)−
O(1) = 83.38(8), 82.62(8), O(1)−Rh(1)−C(1) = 179.14(14),
177.45(14).
Heating of benzene solutions of 1 at 80 °C for 48 h affords
the phenyl derivative RhPh{xant(PiPr2)2} (2) in a quantitative
manner, although it was isolated as a red solid in 33% yield due
to its high solubility in the usual organic solvents. Complex 2
was characterized by X-ray diffraction analysis. The structure
has two chemically equivalent but crystallographically inde-
pendent molecules in the asymmetric unit. Figure 1 shows a
drawing of one of them. As expected, the Rh{xant(PiPr2)2}
skeleton is T-shaped, with the metal situated in the common
vertex and P(1)−Rh(1)−O(1), P(2)−Rh(1)−O(1), and
P(1)−Rh(1)−P(2) angles of 82.15(8)° and 82.35(8)°,
83.38(8)° and 82.62(8)°, and 164.28(5)° and 163.00(4)°,
respectively. Thus, the geometry around the rhodium atom is
almost square-planar, with the phenyl group trans disposed to
the oxygen atom (O(1)−Rh(1)−C(1) = 179.14(14)° and
177.45(14)°). The greatest deviation from the best plane
through Rh(1), C(1), P(1), O(1), and P(2) atoms is 0.0716 Å
in a molecule and 0.0874 Å in the other one and involves to
P(2). The metalated aromatic ring lies almost perpendicular to
the coordination plane with dihedral angles of 85.93° and
79.45°. The Rh(1)−C(1) bond lengths of 1.977(4) and
1.979(5) Å compare well with those found in the scarcely
reported square-planar aryl-rhodium(I) complexes (1.84−2.10
Å).25 The 13C{1H} and 31P{1H} NMR spectra of 2, in benzene-
d6, at room temperature are consistent with the structure given
in Figure 1. In the 13C{1H} NMR spectrum, the most
noticeable resonance is that corresponding to the phenyl
metalated carbon atom, which appears at 162.0 ppm as a
double triplet with C−Rh and C−P coupling constants of 41.2
and 12.2 Hz, respectively. In agreement with equivalent PiPr2
B
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groups, the 31P{1H} NMR spectrum shows at 36.4 ppm a
doublet with a typical P−Rh(I) coupling constant of 177.1 Hz.
Stirring of toluene solutions of 1 at 80 °C for 24 h produces
the quantitative transformation of the starting monohydride
into the tolyl derivatives Rh(m-tolyl){xant(PiPr2)2} (3a) and
Rh(p-tolyl){xant(PiPr2)2} (3b), which are formed in approx-
imately 78:22 molar ratio. Benzylic bond activation is not
observed, despite the fact that products of this type have been
observed previously in related reactions using methyl-
substituted benzenes.26 The cleavage of the meta- and para-
CH bonds is preferred with regard to the ortho-CH bond
rupture from both thermodynamic and kinetic points of view,
whereas the meta−C-H bond cleavage is the statistically
preferred and has been the observed one for the majority of
transition metal precursors.27 Only a few half-sandwich systems
favor the formation of the para products over the meta
isomers.28 The mixture of isomers was isolated as red crystals in
22% yield. The X-ray structure of one of them reveals the
cocrystallyzation of 3a and 3b in a 71:29 molar ratio (see
Supporting Information). Although accurate structural param-
eters could not be obtained, the data prove the C−H bond
activation of both positions of the substrate. The 13C{1H}
NMR spectrum of the meta isomer 3a, in benzene-d6, at room
temperature is consistent with the low symmetry of the tolyl
ligand. Thus, it shows five tolyl-resonances, at 140.6, 136.9,
126.0, 125.2, and 119.5 ppm, along with the signal due to the
metalated carbon atom, which is observed at 161.6 ppm as a
double triplet with C−Rh and C−P coupling constants of 40.5
and 12.6 Hz, respectively. In the 31P{1H} NMR spectrum, the
diphosphine displays a doublet, with a P−Rh coupling constant
of 177.8 Hz, at 35.9 ppm. In agreement with its higher
symmetry, the para isomer 3b gives rise to three tolyl
resonances at 139.5, 126.8, and 125.6 ppm, in the 13C{1H}
NMR spectrum, along with the signal corresponding to the
metalated carbon atom which overlaps with that of 3a. A
doublet with a P−Rh coupling constant of 178.2 Hz, at 35.6
ppm, in the 31P{1H} NMR spectrum is also a characteristic
feature of this isomer.
Thermolysis of 1 in m-xylene, at 80 °C, for 24 h gives rise to
the quantitative formation of the xylenyl derivative Rh(C6H3-
3,5-Me2){xant(PiPr2)2} (4), as a result of the cleavage of the
aromatic C−H bond of the substrate equidistant to the methyl
substituents. The exclusive formation of 4 agrees well with that
observed by Brookhart and Templeton27a and Puddephatt29
about the C−H bond activation of m-xylene on platinum(IV)
and platinum(II) precursors. Complex 4 was isolated as red
crystals in 42% yield. As expected for the positions of the aryl
substituents, the 13C{1H} NMR spectrum of 4, in benzene-d6,
at room temperature shows three xylenyl resonances, at 138.6,
126.2, and 120.8 ppm, along with a double triplet (JC−Rh = 40.2
Hz, JC−P = 12.4 Hz) at 161.1 ppm assigned to the metalated
carbon atom. In accordance with 2 and 3, the 31P{1H} NMR
spectrum of 4 contains at 35.6 ppm a doublet with a P−Rh
coupling constant of 178.3 Hz.
Scheme 3
in ortho position with regard to the substituent, whereas
complex 1 rapidly evolves into Rh(C6H3-2,6-F2){xant(PiPr2)2}
(6) in 1,3-difluorobenzene, as a consequence of the cleavage of
the C−H bond of the arene situated between the fluorine
atoms (i.e., ortho to both substituents). The reason for the
observed selectivity appears to be thermodynamic in origin. In
this context, it should be noted that the M-C bond energy
increases with the ortho-fluorine substitution, becoming
between 2 and 3 times higher than the C−H bond energy
depending upon the metal fragment.31 The ortho-fluorine effect
has been explained in terms of an increase of the ionic
component of the M−C bond through inductive effect of the
ortho-fluorine atom.9d The reactivity of 1 toward fluorobenzene
and 1,3-difluorobenzene agrees well with that recently reported
by Braun for RhH(PEt3)3,32 containing monodentated
phosphines instead of a POP pincer. However, it is in contrast
with the behavior observed for the saturated compounds
33
OsTp{κ1-C[NC5H3Me]}(η2-CH2CH2)2
and [OsTp-
34
(CH2CH2PiPr3)(η2-CH2CH2)2]BF4 (Tp = hydridotris-
(pyrazolyl)borate), which activate fluorobenzene, 1,3-difluor-
obenzene, and substituted 1,3-chlorobenzenes, via σ-bond
metathesis, to afford products resulting from the cleavage of
the C−H bond more distant from the substituents.
Complexes 5 and 6 were isolated as orange solids in 91% and
73% yield, respectively, and characterized by X-ray diffraction
analysis. The structures prove the ortho-activation of the
substrates. Figure 2 shows a drawing of 5. Like for 2, the
coordination geometry around the rhodium atom is almost
square-planar with the diphosphine coordinated in a mer-
fashion (P(1)−Rh(1)−O(1) = P(1A)-Rh(1)−O(1) =
82.73(2), P(1)−Rh(1)−P(1A) = 161.13(4)°) and the aryl
group trans disposed to the oxygen atom (C(1)−Rh(1)−O =
179.90(14)°). The Rh(1)−C(1) bond length of 1.994(4) Å is
statistically identical with those of 2. The 13C{1H} and 31P{1H}
NMR spectra of this compound, in benzene-d6, at room
temperature are consistent with the structure shown in Figure
2. Thus, as expected, the 13C{1H} NMR spectrum shows six
resonances between 168 and 111 ppm for the inequivalent
carbon atoms of the metalated ring, whereas the 31P{1H} NMR
spectrum contains at 40.0 ppm a double doublet (JP−Rh = 167.6
Hz, JP−F = 4.2 Hz) for the equivalent PiPr2 groups of the
diphosphine. The structure of 6 (Figure 3) resembles those of 2
and 5 with P(1)−Rh(1)−O = P(1A)-Rh(1)-O, P(1)−Rh-
P(1A) and C(1)−Rh(1)−O angles of 82.782(10)°,
161.611(18)° and 179.45(6)°, respectively. The Rh(1)−C(1)
distance of 1.9898(19) Å is statistically identical with those of
both 2 and 5. Although the resonance corresponding to the
The square-planar monohydride complex 1 also activates a
C−H bond of fluorobenzene and 1,3-difluorobenzene30 at
room temperature. The reactions are even faster that those with
toluene and m-xylene. There are further marked differences in
selectivity. In contrast with the methyl counterparts, the
activations take place close to the fluorine substituents (Scheme
3). Stirring of 1 in fluorobenzene for 3 h gives rise to the
quantitative formation of Rh(C6H4-2-F){xant(PiPr2)2} (5), as a
result of the cleavage of the C−H bond of the solvent disposed
C
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2. B−H Bond Activation Reactions. In agreement with
the marked diagonal relationship between boron and silicon,
which is also evident in the chemistry of the platinum group
metals,35 complex 1 reacts with pinacolborane (HBpin) and
catecholborane (HBcat) to afford boryl derivatives (Scheme 4),
which are diagonal counterparts of the silyl complexes shown in
Scheme 1.
The addition of 1.0 equiv of the boron hydrides, at −15 °C,
to toluene solutions of 1 gives rise to the immediate and
quantitative formation of the trans-dihydride-rhodium(III)
compounds RhH2(BR2){xant(PiPr2)2} (BR2 = Bpin (7), Bcat
(8)), in a diastereoselective process with specific B−H
orientation.36 The oxidative addition takes place along the
O−Rh−H axis with the boron atom directed toward the
hydride ligand. The mutually trans disposition of the hydride
Figure 2. ORTEP diagram of complex 5 (50% probability ellipsoids).
Hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and
angles (deg): Rh(1)−P(1) = 2.2520(8), Rh(1)−O(1) = 2.193(3),
Rh(1)−C(1) = 1.994(4); P(1)−Rh(1)−P(1A) = 161.13(4), P(1)−
Rh(1)−O(1) = 82.73(2), P(1A)−Rh(1)−O(1) = 82.73(2), O(1)−
Rh(1)−C(1) = 179.90(14).
1
ligands is strongly supported by the H NMR spectra of these
complexes, which show only one high field resonance. It
appears at about −6.0 ppm as a double triplet with H−Rh ad
H−P coupling constants of about 23 Hz and between 16 and
13 Hz, respectively. In accordance with the single character of
the Rh−B bonds, the 11B{1H} NMR spectra contain a broad
resonance at 33.3 ppm for 7 and at 34.7 ppm for 8. The
equivalent PiPr2 groups display, at 68.3 ppm for 7 and 63.8 ppm
for 8, a doublet with a P−Rh coupling constant of about 130
Hz in the 31P{1H} NMR spectra.
The high trans influence of the hydride ligand37 makes
unstable the trans-dihydride complexes 7 and 8. Thus, At room
temperature, in solution, they lose molecular hydrogen to
afford the boryl derivatives Rh(BR2){xant(PiPr2)2} (BR2 = Bpin
(9), Bcat (10)), which were isolated as red solids in 93% (9)
and 70% (10) yield. The trans disposition of the hydride
ligands prevents the three-centered transition state for the
hydrogen reductive elimination. However, the previously
mentioned hemilability of the phosphine oxygen atom makes
feasible the trans−cis-isomerization, which allows the formation
of a transitory dihydrogen intermediate as a previous step to the
hydrogen release.
Figure 3. ORTEP diagram of complex 6 (50% probability ellipsoids).
Hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and
angles (deg): Rh(1)−P(1) = 2.2521(3), Rh(1)−O = 2.1850(13),
Rh(1)−C(1) = 1.9898(19); P(1)−Rh(1)−P(1A) = 161.611(18),
Complex 9, plus HBpin, is also formed in a quantitative
manner by reaction of compound 1 with one equivalent of
B2pin2.
P(1)−Rh(1)−O(1) = 82.782(10), P(1A)−Rh(1)−O(1)
82.781(10), O(1)−Rh(1)−C(1) = 179.45(6).
=
Complex 9 has been characterized by X-ray diffraction
analysis. In this context, it should be noted that boryl
complexes of rhodium(I) are very rare,38 in particular four-
coordinate species. As far as we know only the compounds
Rh(BR2)(PEt3)3 (BR2 = Bpin, Bcat, BO2C5H10)24f,39 and
Rh(BR2)(PPh3)3 have been previously characterized, but
not by X-ray diffraction analysis. Figure 4 shows a drawing of
the molecule. The coordination geometry around the rhodium
metalated aryl carbon atom is missing in the 13C{1H} NMR
spectrum, it reflects the symmetry of the coordinated aryl
group, showing one C−F resonance at 167.4 ppm and two C−
H resonances at 121.6 and 108.5 ppm. The 31P{1H} NMR
spectrum contains at 43.0 ppm a double triplet with P−Rh and
P−F coupling constants of 159.8 and 3.7 Hz, respectively.
40
Scheme 4
D
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Figure 4. ORTEP diagram of complex 9 (50% probability ellipsoids).
Hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and
angles (deg): Rh−P(1) = 2.2255(9), Rh−P(2) = 2.2432(9), Rh(1)−
O(1) = 2.268(2), Rh−B(1) = 1.981(4); P(1)−Rh(1)−P(2) =
161.98(3), P(1)−Rh−O(1) = 83.07(6), P(2)−Rh−O(1) = 82.98(6),
O(1)−Rh(1)−C(1) = 177.22(14).
atom is almost square-planar with the diphosphine coordinated
in the expected pincer fashion (P(1)−Rh−O(1) = 83.07(6)°,
P(2)−Rh-O(1) = 82.98(6)°, and P(1)−Rh-P(2) = 161.98(3)°)
and the boryl group trans disposed to the oxygen atom of the
diphosphine (B(1)−Rh−O(1) = 177.22(14)°). The Rh−B(1)
bond length is 1.981(4) Å. The 11B{1H} and 31P{1H} NMR
spectra of 9 and 10 are consistent with the reduction of the
metal center as a result of the release of molecular hydrogen
from 7 and 8. Thus, the 11B{1H} NMR spectra contain broad
resonances, at 42 (9) and 49 (10) ppm, which are shifted 9 and
14 ppm toward lower field with regard to the respective signals
corresponding to the rhodium(III) dihydride precursors. The
31P{1H} NMR spectra show, at 51.9 (9) and 55.1 (10) ppm,
doublets with P−Rh coupling constants of 176.0 and 165.3 Hz,
respectively, which are between 46 and 35 Hz higher that these
of 7 and 8.
Figure 5. (a) Stacked 31P{1H} NMR spectra showing the trans-
formation of RhPh{xant(PiPr2)2} (2) into Rh(Bpin){xant(PiPr2)2} (9)
by reaction with B2pin2 (toluene, 60 °C). (b) 11B{1H} NMR spectrum
of the reaction after 24 h at 60 °C. * B2pin3 (decomposition product).
Scheme 5
3. Stoichiometric Formation of Ph−Bpin. The addition
of 1.0 equiv of B2pin2 to toluene solutions of the phenyl
complex 2, at 60 °C, leads to Ph−Bpin and the boryl derivative
9. The formation of these compounds is strongly supported by
the 11B{1H} and 31P{1H} NMR spectra of the mixtures
generated during the first 24 h of reaction (Figure 5). In
benzene, the boryl complex 9 affords Ph−Bpin and the
monohydride 1, which regenerates the phenyl derivative 2 and
releases molecular hydrogen in accordance with Scheme 2.
These elemental reactions can be combined in a cycle (Scheme
5) for the RhH{xant(PiPr2)2}-promoted borylation of benzene
with B2pin2, according to eq 1, where the aryl complex 2 and
the boryl derivative 9 are implied as intermediates.
The phenyl complex 2 also reacts with HBpin, in toluene, at
55 °C. The reaction gives Ph−Bpin and the monohydride 1.
This transformation, which is faster than the reaction between 2
and B2pin2, and the C−H bond activation of benzene promoted
by 1 to afford 2 form an alternative cycle (A in Scheme 6), in
this case, for the RhH{xant(PiPr2)2}-promoted borylation of
benzene with HBpin according to the mass balance shown in
eq 2. Because complex 1 reacts with HBpin to afford molecular
hydrogen and the boryl derivative 9 (Scheme 4) and the latter
gives Ph−Bpin and regenerates 1, in benzene, the reaction
shown in eq 2 can also take place via the cycle B of Scheme 6.
In other words, Scheme 6 suggests that the RhH{xant(PiPr2)2}-
promoted borylation of arenes with HBpin to give aryl-Bpin
and molecular hydrogen could go through two routes; arene
and borane. The first of them, the arene route, should involve
the initial C−H bond activation of the arene followed by the
reaction of the resulting aryl complex with the boron-hydride,
while the second one, the borane route, could proceed through
the initial H−B bond activation of the borane followed by the
reaction of the resulting boryl intermediate with the arene.
2Ph‐H + B2pin2 → 2Ph‐B pin + H2
(1)
Ph‐H + HBpin → Ph‐Bpin + H2
(2)
4. Catalytic Borylation of Arenes. As expected from the
reactions summarized in Schemes 5 and 6, the monohydride
complex 1 is an efficient catalyst for the borylation of benzene
with both B2pin2 and HBpin. The reactions were performed in
the arene as solvent, at 110 °C, and using a Rh/B molar ratio of
E
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Article
the first case and up to 95% in the second case. Because the
borylation with HBpin, in the presence of cyclohexene, appears
to be more efficient than that with B2pin2, we explored the
scope of this arene functionalization under these conditions.
Table 1 collects the arenes investigated and the obtained
results.
Scheme 6
Complex 1 is efficient not only for the benzene borylation
(run 1) but also for the borylation of methyl substituted
benzenes (runs 2 and 3). In contrast to the related precursor
RhCl(PiPr3)2(N2),41 containing the monodentated triisopro-
pylphosphine, the formation of benzylboronate esters is not
observed in our case. This is consistent with the rigidity and
robustness of 1, imposed by the POP diphosphine, which
prevents the formation of η3-benzyl intermediates, the key
species in the benzylic borylation. Toluene (run 2) is
quantitatively transformed into the meta- and para-tolylboro-
nate esters in a 65:35 molar ratio after 48 h. This isomers ratio
agrees well with that observed for the stoichiometric C−H
bond activation of the substrate, according to Scheme 2. This
suggests that under the reaction conditions employed, toluene
as solvent and 110 °C, the arene is the main route (A in
Scheme 6) for the catalysis and that the reactions of the tolyl
complexes 3a and 3b with HBpin are fast. Therefore, the
selectivity of the process is determined by the kinetic of the
toluene C−H bond activations. Also in agreement with Scheme
3, m-xylene (run 3) is quantitatively borylated in position meta
with regard to both substituents.
1:25. After 24 h, under these conditions, the borylation with
B2pin2 (eq 1) affords Ph−Bpin with an isolated yield of 68%,
whereas starting from HBpin (eq 2), the borylation product
was isolated in 66% yield. The addition, to the catalytic
solution, of 1.0 equiv of cyclohexene as hydrogen acceptor per
equiv of boron increases the yield of the reactions up to 89% in
The borylation of fluoroarenes is more complex. Fluo-
robenzene (run 4) and 1,3-difluorobenzene (run 5) yield
mixtures of the three possible isomers, in contrast to the
selectivity observed for the C−H bond activation reactions of
a
Table 1. Borylation of Arenes Catalyzed by RhH{xant(PiPr2)2} (1)
a
b
c
4 mol % 1, 2.06 mmol HBpin, 2.00 mmol cyclohexene, 5 mL of arene, 110 °C. The numbers indicate the ratio of products. Isolated yields are
reported in parentheses.
F
DOI: 10.1021/acs.organomet.5b00176
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Article
the arenes (Scheme 3). It should be even noted that, for 1,3-
difluorobenzene, the borylation at the C−H bond position
between both fluorine substituents is the less favored. These
results are consistent with those obtained for methylbenzenes,
because they also suggest that the selectivity of the catalysis is
governed by the kinetic of the C−H bond activations of the
arene. The borylation of 3-fluorotoluene (run 6) appears to be
run by the methyl susbtituent, which keeps the boryl fragment
away from it.
under argon. Pinacolborane and B2pin2 were purchased from
commercial sources and used without further purification.
Catecholborane was purchased from commercial sources and
1
distilled in a Kugelrohr distillation over. H, 13C{1H}, 31P{1H},
11B{1H}, and 19F NMR spectra were recorded on Bruker 300
ARX, Bruker Avance 300 MHz, Bruker Avance 400 MHz or
Bruker Avance 500 MHz instruments. Chemical shifts (ex-
pressed in parts per million) are referenced to residual solvent
peaks (1H, 13C{1H}), external 85% H3PO4 (31P{1H}), BF3·
OEt2 (11B), or CFCl3 (19F). Coupling constants J and N are
given in hertz. Attenuated total reflection infrared spectra
(ATR-IR) of solid samples were run on a PerkinElmer
Spectrum 100 FT-IR spectrometer. C, H, and N analyses
were carried out in a PerkinElmer 2400 CHNS/O analyzer.
High-resolution electrospray mass spectra were acquired using
a MicroTOF-Q hybrid quadrupole time-of-flight spectrometer
(Bruker Daltonics, Bremen, Germany). RhH{xant(PiPr2)2} (1)
was prepared by the published method.13e
Anisole (run 7) shows a similar behavior to toluene,
suggesting that the oxygen atom of the ether does not play
any significant role in the selectivity of the process.
CONCLUDING REMARKS
■
This study reveals that the square-planar monohydride complex
RhH{xant(PiPr2)2} promotes the C−H bond activation of
arenes, the B−H bond activation of pinacolborane and
catecholborane, and the stoichiometric and catalytic borylation
of arenes.
Reaction of RhH{xant(PiPr2)2} (1) with Benzene:
Preparation of RhPh{xant(PiPr2)2} (2). Complex 1 (200
mg, 0.37 mmol) was dissolved in benzene (5 mL), and the
resulting mixture was stirred during 48 h at 80 °C. After this
time, it was concentrated to dryness to afford a red residue.
Addition of pentane (5 mL) afforded a red solid, which was
further washed with pentane (6 × 1 mL), and lastly, it was
dried in vacuo. Yield: 82 mg (33%). 31P{1H} NMR spectros-
copy shows that the reaction is quantitative, but the isolated
yield is low due to the high solubility of the complex in
pentane. Anal. Calcd for C33H45OP2Rh: C, 63.66; H, 7.28.
Found: C, 64.03; H, 7.47. HRMS (electrospray, m/z): calcd for
C33H45OP2Rh [M]+, 622.1995; found, 622.2037. IR (cm−1):
The C−H bond activation products depend upon the
substituents of the arene. Methyl groups keep the metal
fragment away from them, whereas the metal fragment moves
toward the fluorine substituents. Thus, the observed selectivity
suggests that the activation is thermodynamically controlled.
The B−H bond activation of the boranes is a diaster-
eoselective process with specific B−H bond orientation. The
oxidative addition takes place along the O−Rh−H axis of the
monohydride, with the boron atom toward the hydride, and
selectively leads to trans-dihydride-boryl-rhodium(III) inter-
mediates, which lose molecular hydrogen to afford rare square-
planar rhodium(I) boryl derivatives. The X-ray characterization
of one of them allows us to report the first structure of a
compound of this type.
The stoichiometric borylation of arenes with pinacolborane
can be performed by means of two pathways, arene and borane
routes. The first of them involves the initial C−H bond
activation of the arene followed by the reaction of the resulting
aryl intermediate with the borane, while the borane route
involves the initial B−H bond activation of the borane and the
subsequent reaction of the resulting boryl intermediate with the
arene. In spite of this, the comparison between the selectivities
observed in the stoichiometric arene C−H bond activation and
the catalytic arene borylation suggests that, under the
experimental conditions employed for the catalysis, the arene
route is the main pathway to the formation of the borylation
products and that the selectivity of the process is governed by
the kinetic of the C−H bond activation of the arenes.
In conclusion, the characteristic of rigidity and robustness
provided by the POP diphosphine 9,9-dimethyl-4,5-bis-
(diisopropylphosphino)xanthene, along with the hemilability
of its oxygen atom, give to the square-planar monohydride
RhH{xant(PiPr2)2} the capacity of promoting the arene
borylation, of serving as model to study the stoichiometric
steps of the process, and to be the starting material to isolate
the key intermediates.
1
ν(CC) 1559 (w), ν(C−O−C) 1099 (m). H NMR (300.13
MHz, C6D6, 298 K): δ 8.06 (d, JH−H = 7.2, 2H, o-CH Ph), 7.27
(m, 2H, CH-arom POP), 7.21 (t, JH−H = 7.2, 1H, m-CH Ph),
7.04 (dd, JH−H = 7.7, JH−H = 1.6, 2H, CH-arom POP), 6.97 (t,
JH−H = 7.2, 1H, p-CH Ph), 6.86 (t, JH−H = 7.5, 2H, CH-arom
POP), 2.40 (m, 4H, PCH(CH3)2), 1.24 (s, 6H, CH3), 1.23
(dvt, JH−H = 7.2, N = 15.7, 12H, PCH(CH3)2), 1.18 (dvt, JH−H
= 7.0, N = 13.3, 12H, PCH(CH3)2). 13C{1H} NMR (75.47
MHz, C6D6, 298 K): δ 162.0 (dt, JC−Rh = 41.2, JC−P = 12.2, Rh−
C), 156.2 (dvt, JC−Rh = 0.9, N = 16.0, Carom POP), 139.9 (t,
J
C−P = 3.1, o-CH Ph), 131.3 (s, CH arom POP), 130.7 (vt, N =
6, Carom POP) 127.7 (s, CH-arom POP), 126.0 (vt, N = 21.7,
Carom POP), 125.6 (dt, JC−Rh = 2.3, JC−P = 1.0, m-CH Ph),
124.0 (vt, N = 4.0, CH-arom POP), 118.4 (t, JC−P = 1.6, p-CH
Ph), 34.1 (s, C(CH3)2), 33.0 (s, C(CH3)2), 25.3 (dvt, JC−Rh
=
2.9, N = 17.5, PCH(CH3)2), 19.4 (vt, N = 8.4, PCH(CH3)2),
18.7 (vt, N = 3.0, PCH(CH3)2). 31P{1H} NMR (121.49 MHz,
C6D6, 298 K): δ 36.4 (d, JP−Rh = 177.1).
Reaction of RhH{xant(PiPr2)2} (1) with Toluene:
Preparation of Rh(m-tolyl){xant(PiPr2)2} (3a) and Rh(p-
tolyl){xant(PiPr2)2} (3b). Complex 1 (200 mg, 0.37 mmol)
was dissolved in toluene (5 mL), and the resulting mixture was
stirred during 24 h at 80 °C. After this time, it was concentrated
to dryness to afford a red residue. Addition of pentane (5 mL)
afforded a red solid, which was further washed with pentane
(15 × 1 mL), and lastly, it was dried in vacuo. Yield: 52 mg
(22%). 31P{1H} NMR spectroscopy shows that the reaction is
quantitative, but the isolated yield is low due to the high
EXPERIMENTAL SECTION
■
General Information. All reactions were carried out with
rigorous exclusion of air using Schlenk-tube techniques or in a
drybox. Pentane was obtained oxygen- and water-free from an
MBraun solvent purification apparatus and was stored over
P2O5 in the drybox, while all the arenes were dried and distilled
1
solubility of the mixture in pentane. H and 31P{1H} NMR
spectra show a mixture of 3a and 3b in a ratio of 78:22. Anal.
Calcd for C34H47OP2Rh: C, 64.15; H, 7.44. Found: C, 63.80;
G
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H, 7.08. IR (cm−1): ν(CC) 1556 (w), ν(C−O−C) 1098
(s, C(CH3)2), 25.5 (dvt, JC−Rh = 3.0, N = 17.2, PCH(CH3)2),
19.5 (vt, N = 8.5, PCH(CH3)2), 18.7 (s, PCH(CH3)2), 14.3 (s,
Ph-CH3). 31P{1H} NMR (121.49 MHz, C6D6, 298 K): δ 35.6
(d, JP−Rh = 178.3).
(m).
1
Spectroscopic data for Rh(m-tolyl){xant(PiPr2)2} (3a): H
NMR (500.13 MHz, C6D6, 298 K): δ 7.94 (s, 1H, o−CH Ph),
Reaction of RhH{xant(PiPr2)2} (1) with Fluorobenzene:
Preparation of Rh(C6H4-2-F){xant(PiPr2)2} (5). Complex 1
(200 mg, 0.366 mmol) was dissolved in fluorobenzene (2 mL),
and the resulting mixture was stirred at room temperature for 3
h. After this time, the solvent was removed under vacuum,
affording a orange residue. Addition of pentane (2 mL)
afforded an orange solid, which was further washed with
pentane (2 × 1 mL), and lastly, it was dried in vacuo. Yield:
210.2 mg (91%). Anal. Calcd for C33H44FOP2Rh·C5H12: C,
61.88; H, 6.92. Found: C, 61.30; H, 6.65. IR (cm−1): ν(CC)
7.88 (d, 1H, JH−H = 7.3, o−CH Ph), 7.29 (m, 2H, CH-arom
POP), 7.16 (t, JH−H = 7.3, 1H, m−CH Ph), 7.05 (dd, JH−H
=
6.5, JH−H = 1.5, 2H, CH-arom POP), 6.86 (t, JH−H = 7.5, 2H,
CH-arom POP), 6.78 (d, JH−H = 7.3, 1H, p−CH Ph), 2.46 (s,
3H, CH3Ph), 2.42 (m, 4H, PCH(CH3)2), 1.26 (dvt, JH−H = 7.0,
N = 16.1, 12H, PCH(CH3)2), 1.24 (s, 6H, CH3), 1.20 (dvt,
JH−H = 6.8, N = 13.7, 12H, PCH(CH3)2). 13C{1H} NMR
(75.47 MHz, C6D6, 298 K): δ 161.6 (dt, JC−Rh = 40.5, JC−P
=
12.6, Rh−C), 156.2 (vt, N = 16.3, Carom POP), 140.6 (t, JC−P
= 2.9, o-CH Ph), 136.9 (t, JC−P = 2.9, o-CH Ph), 131.3 (s, CH
arom POP), 130.8 (vt, N = 5.4, Carom POP), 128.0
(overlapping with C6D6, Carom POP), 127.6 (s, CH-arom
POP), 126.0 (t, JC−P = 7.1, m-C Ph), 125.2 (s, m-CH Ph), 124.0
(s, CH-arom POP), 119.5 (s, p-CH Ph), 34.1 (s, C(CH3)2),
33.0 (s, C(CH3)2), 25.3 (dvt, JC−Rh = 2.8, N = 17.4,
PCH(CH3)2), 22.4 (s, Ph-CH3), 19.5 (vt, N = 8.5, PCH-
(CH3)2), 18.7 (s, PCH(CH3)2). 31P{1H} NMR (121.49 MHz,
C6D6, 298 K): δ 35.9 (d, JP−Rh = 177.8).
1
1573 (w), ν(C−O−C) 1101 (m). H NMR (300.13 MHz,
C6D6, 298 K): δ 8.08 (m, 1H, CH C6H4-2-F), 7.24 (m, 2H,
CH-arom POP), 7.05 (dd, JH−H = 7.9, JH−H = 1.5, 2H, CH-
arom POP), 7.03−6.91 (m, 3H, CH C6H4-2-F), 6.85 (t, JH−H
=
7.5, 2H, CH-arom POP), 2.38 (m, 4H, PCH(CH3)2), 1.35−
1.10 (m, 30H, C(CH3)2 + PCH(CH3)2). 13C{1H} NMR (75.47
MHz, C6D6, 298 K): δ 167.4 (ddt, JC−F = 222.8, JC−Rh = 2.5,
JC−P = 2.5, C-F C6H4F), 156.4 (vt, N = 15.8, C-arom POP),
143.1 (ddt, JC−Rh = 44.3, JC−F = 42.6, JC−P = 13.5, Rh-C C6H4F),
141.5 (dt, JC−F = 21.4, JC−P = 2.6, CH C6H4F), 131.2 (s, CH-
arom POP), 130.8 (vt, N = 5.5, C-arom POP), 127.9 (s, CH-
arom POP), 125.7 (dvt, JC−Rh = 1.8, N = 14.6, C-arom POP),
124.1 (vt, N = 4.0, CH-arom POP), 122.0 (m, CH C6H4F),
1
Spectroscopic data for Rh(p-tolyl){xant(PiPr2)2} (3b): H
NMR (500.13 MHz, C6D6, 298 K): δ 7.96 (dd, JH−H = 8.0,
JH−Rh = 2.3, 2H, o−CH Ph), 7.24 (m, 2H, CH-arom POP), 7.09
(d, JH−H = 7.7, 2H, m−CH Ph), 7.05 (d, JH−H = 6.5, 2H, CH-
arom POP), 6.85 (t, JH−H = 7.5, 2H, CH-arom POP), 2.42 (m,
4H, PCH(CH3)2), 2.38 (s, 3H, CH3Ph), 1.27 (dvt, JH−H = 7.7,
N = 18.2, 12H, PCH(CH3)2), 1.24 (s, 6H, CH3), 1.20 (dvt,
JH−H = 7.0, N = 14.1, 12H, PCH(CH3)2). 13C{1H} NMR
120.1 (dt, JC−F = 7.1, JC−P = 1.5, CH C6H4F), 111.9 (ddt, JC−F
=
30.6, JC−Rh = 1.3, JC−P = 1.3, CH C6H4F), 34.0 (s, C(CH3)2),
33.5, 32.6 (both br, C(CH3)2), 26.5, 25.0 (both br, PCH-
(CH3)2), 19.3 (vt, N = 8.4, PCH(CH3)2), 18.6 (s, PCH-
(CH3)2). 31P{1H} NMR (121.49 MHz, C6D6, 298 K): δ 40.0
(dd, JP−Rh = 167.6, JP−F = 4.2). 19F{1H} NMR (282.33 MHz,
C6D6, 298 K): δ −85.4 (dt, JF−Rh = 19.8, JF−P = 4.1).
(75.47 MHz, C6D6, 298 K): δ 161.6 (dt, JC−Rh = 40.5, JC−P
=
12.6, Rh−C), 156.7 (vt, N = 25.8, Carom POP), 139.5 (t, JC−P
= 2.9, o-CH Ph), 131.0 (s, CH arom POP), 130.7 (vt, N = 5.4,
Carom POP), 128.0 (overlapping with C6D6, Carom POP),
127.4 (s, CH-arom POP), 126.8 (s, m-CH Ph), 125.6 (t, JC−P
=
Reaction of RhH{xant(PiPr2)2} (1) with 1,3-Difluoro-
benzene: Preparation of Rh(C6H3-2,6-F2){xant(PiPr2)2} (6).
Complex 1 (200 mg, 0.366 mmol) was dissolved in 1,3-
difluorobenzene (5 mL), and the resulting mixture was stirred
at room temperature for 5 min, getting a reddish solution. After
this time, the solvent was removed under vacuum, affording a
red residue. Addition of pentane (3 mL) afforded an orange
solid, which was further washed with pentane (2 × 1 mL), and
lastly, it was dried in vacuo. Yield: 175.2 mg (73%). Anal. Calcd
for C33H43F2OP2Rh·C5H12: C, 62.29; H, 7.56. Found: C, 62.01;
H, 7.74. IR (cm−1): ν(CC) 1573 (w), ν(C−O−C) 1036
7.2, p-C Ph), 124.0 (s, CH-arom POP), 34.1 (s, C(CH3)2), 33.0
(s, C(CH3)2), 24.5 (dvt, JC−Rh= 3.6, N = 18.0, PCH(CH3)2),
21.5 (s, Ph-CH3), 19.4 (vt, N = 8.6, PCH(CH3)2), 18.0 (s,
PCH(CH3)2). 31P{1H} NMR (121.49 MHz, C6D6, 298 K): δ
35.6 (d, JP−Rh = 178.2).
Reaction of RhH{xant(PiPr2)2} (1) with m-Xylene:
Preparation of Rh(C6H3-3,5-Me2){xant(PiPr2)2} (4). Com-
plex 1 (200 mg, 0.37 mmol) was dissolved in m-xylene (5 mL),
and the resulting mixture was stirred during 24 h at 80 °C. After
this time, it was concentrated to dryness to afford a red residue.
Addition of pentane (5 mL) afforded a red solid, which was
further washed with pentane (8 × 1 mL), and lastly, it was
dried in vacuo. Yield: 102.3 mg (42%). Anal. Calcd for
C35H49OP2Rh: C, 64.61; H, 7.65. Found: C, 64.30; H, 7.35. IR
1
(m). H NMR (300.13 MHz, C6D6, 298 K): δ 7.21 (m, 2H,
CH-arom POP), 7.08 (d, JH−H = 7.1, 2H, CH-arom POP),
6.78−6.68 (m, 5H, CH-arom POP + C6H3F2), 2.36 (m, 4H,
PCH(CH3)2), 1.30−1.10 (m, 30H, C(CH3)2 + PCH(CH3)2).
1
(cm−1): ν(CC) 1556 (w), ν(C−O−C) 1099 (m). H NMR
13C{1H} NMR (75.47 MHz, C6D6, 298 K): δ 167.4 (ddt, JC−F
=
(300.13 MHz, C6D6, 298 K): δ 7.73 (s, 2H, o−CH Ph), 7.29
(m, 2H, CH-arom POP), 7.05 (dd, JH−H = 7.7, JH−H = 1.6, 2H,
CH-arom POP), 6.86 (t, JH−H = 7.7, 2H, CH-arom POP), 6.55
(s, 1H, p−CH Ph), 2.45 (s, 6H, CH3Ph), 2.42 (m, 4H,
PCH(CH3)2), 1.24 (s, 6H, CH3), 1.28 (dvt, JH−H = 7.2, N =
16.0, 12H, PCH(CH3)2), 1.20 (dvt, JH−H = 7.1, N = 13.2, 12H,
PCH(CH3)2). 13C{1H} NMR (75.47 MHz, C6D6, 298 K): δ
161.1 (dt, JC−Rh = 40.2, JC−P = 12.4, Rh−C), 156.3 (vt, N =
15.9, Carom POP), 138.6 (t, JC−P = 2.8, o-CH Ph), 131.3 (s,
CH arom POP), 130.8 (vt, N = 5.2, Carom POP), 128.0
(overlapping with C6D6, Carom POP), 127.4 (s, CH-arom
POP), 126.2 (td, JC−P = 7.2, JC−Rh = 1.6, m-C Ph), 123.9 (s,
CH-arom POP), 120.8 (s, p-CH Ph), 34.5 (s, C(CH3)2), 32.9
224.4, JC−Rh = 24.2, JC−P = 2.4, C-F C6H3F2), 156.4 (vt, N =
16.4, C-arom POP), 131.1 (s, CH-arom POP), 130.7 (vt, N =
5.6, C-arom POP), 128.0 (s, CH-arom POP, inferred from the
HSQC spectrum), 125.4 (dvt, JC−Rh = 1.9, N = 15.2, C-arom
POP), 124.2 (vt, N = 3.9, CH-arom POP), 121.6 (t, JC−F = 8.2,
CH C6H3F2), 108.5 (d, JC−F = 31.2, CH C6H3F2), 33.9 (s,
C(CH3)2), 33.2 (s, C(CH3)2), 26.0 (dvt, JC−Rh = 2.7, N = 18.7,
PCH(CH3)2), 19.1 (vt, N = 8.3, PCH(CH3)2), 18.4 (s,
PCH(CH3)2), the signal for the Rh−C atom was not observed.
31P{1H} NMR (121.49 MHz, C6D6, 298 K): δ 43.0 (dt, JP−Rh
=
159.8, JP−F = 3.6). 19F{1H} NMR (282.33 MHz, C6D6, 298 K):
δ −80.8 (dt, JF−Rh = 22.1, JF−P = 3.7).
H
DOI: 10.1021/acs.organomet.5b00176
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Organometallics
Article
Reaction of RhH{xant(PiPr2)2} (1) with Pinacolborane
at Low Temperature: Spectroscopic Detection of
RhH2(Bpin){xant(PiPr2)2} (7). A screw-top NMR tube
containing a solution of 1 (23.2 mg, 0.04 mmol) in toluene-
d8 (0.4 mL) and cooled at 195 K was treated with HBpin (6.2
μL, 0.04 mmol). Immediately the NMR tube was introduced in
a NMR probe precooled at 258 K. The immediate and
2H, CH-arom POP), 2.47 (m, 2H, PCH(CH3)2), 1.59 (dvt,
JH−H = 7.1, N = 16.5, 12H, PCH(CH3)2), 1.38 (s, 12H, CH3
Bpin), 1.28 (s, 6H, CH3), 1.20 (dvt, JH−H = 7.1, N = 14.2, 12H,
PCH(CH3)2). 13C{1H} NMR (100.62 MHz, C6D6, 298 K): δ
155.5 (dvt, JC−Rh = 0.9, N = 16.3, C-arom POP), 131.2 (s, CH-
arom POP), 131.1 (vt, N = 5.2, C-arom POP), 127.7 (vt, N =
25.0, C-arom POP), 127.2 (s, CH-arom POP), 124.0 (vt, N =
3.7, CH-arom POP), 79.5 (d, JC−Rh = 1.4, C Bpin), 34.4 (s,
C(CH3)2), 32.2 (s, C(CH3)2), 27.6 (dvt, JC−Rh = 3.8, N = 19.3,
PCH(CH3)2), 26.5 (s, CH3 Bpin), 20.8 (dvt, JC−Rh = 0.8, N =
10.5, PCH(CH3)2), 19.8 (dvt, JC−Rh = 2.1, N = 3.6,
PCH(CH3)2). 31P{1H} NMR (121.49 MHz, C6D6, 298 K): δ
51.9 (d, JP−Rh = 176.0). 11B NMR (96.29 MHz, C6D6, 298 K): δ
41.9 (br).
1
quantitative conversion to 7 was observed by H and 31P{1H}
NMR spectroscopies (in solution at this temperature 9 was
1
observed as a minor product with time). H NMR (400.13
MHz, C7D8, 258 K): δ 7.21 (m, 2H, CH-arom POP), 6.97 (dd,
JH−H = 7.5, JH−H = 1.3, 2H, CH-arom POP), 6.89 (t, JH−H = 7.5,
2H, CH-arom POP), 2.61 (m, 4H, PCH(CH3)2), 1.56 (dvt,
JH−H = 7.8, N = 15.9, 12H, PCH(CH3)2), 1.23 (s, 12H, CH3
Bpin), 1.22 (dvt, JH−H = 7.3, N = 14.2, 12H, PCH(CH3)2), 1.16
(s, 6H, CH3), −5.94 (dt, JH−Rh = 23.4, JH−P = 15.9, 2H, RhH2).
13C{1H} NMR (75.47 MHz, C7D8, 258 K): δ 155.7 (vt, N =
12.4, C-arom POP), 132.3 (vt, N = 4.5, C-arom POP), 130.2 (s,
CH-arom POP), 126.3 (vt, N = 23.0, C-arom POP), 126.1 (s,
CH-arom POP), 123.7 (vt, N = 4.2, CH-arom POP), 80.7 (s, C
Bpin), 34.8 (s, C(CH3)2), 29.7 (s, C(CH3)2), 26.6 (vt, N =
24.0, PCH(CH3)2), 25.1 (s, CH3 Bpin), 20.1 (vt, N = 8.3,
PCH(CH3)2), 19.0 (s, PCH(CH3)2). 31P{1H} NMR (161.98
MHz, C7D8, 258 K): δ 68.3 (d, JP−Rh = 131.0). 11B{1H} NMR
(128.38 MHz, C7D8, 258 K): δ 33.3 (br).
Reaction of RhH{xant(PiPr2)2} (1) with Catecholborane
at Room Temperature: Preparation of Rh(Bcat){xant-
(PiPr2)2} (10). HBcat (11.5 μL, 0.11 mmol) was added to a
solution of 1 (59.0 mg, 0.11 mmol) in toluene (3 mL) cooled at
195 K. After stirring for 5 min at this temperature, it was slowly
heated at room temperature, affording a dark red solution. This
solution was evaporated to dryness to afford a red residue.
Addition of pentane afforded a red solid that was washed with
pentane (2 × 0.5 mL) and dried in vacuo. Yield: 50 mg (70%).
Anal. Calcd for C33H44BO3P2Rh: C, 59.66; H, 6.68. Found: C,
59.90; H, 6.20. HRMS (electrospray, m/z): calcd. for
C33H44BO3P2Rh [M]+: 661.2601; found: 661.2612. IR
(cm−1): ν(C−O−C) 1102 (m). 1H NMR (300.13 MHz,
C6D6, 298 K): δ 7.32 (m, 2H, Bcat), 7.22 (m, 2H, CH-arom
POP), 7.09 (dd, JH−H = 7.7, JH−H = 1.4, 2H, CH-arom POP),
6.92−6.85 (m, 4H, 2H CH-arom POP + 2H Bcat), 2.35 (m,
2H, PCH(CH3)2), 1.33 (dvt, JH−H = 7.5, N = 16.9, 12H,
PCH(CH3)2), 1.27 (s, 6H, CH3), 1.10 (dvt, JH−H = 7.1, N =
14.3, 12H, PCH(CH3)2). 13C{1H} NMR (100.62 MHz, C6D6,
298 K): δ 155.7 (vt, N = 12.3, Carom POP), 151.6 (s, C-O
Bcat), 131.3 (s, CH-arom POP), 131.2 (vt, N = 5.4, Carom
POP), 127.6 (s, CH-arom POP), 128.3 (vt, N = 25.0, C-arom
POP), 124.2 (vt, N = 3.9, CH-arom POP), 120.3, 110.5 (both s,
CH Bcat), 34.5 (s, C(CH3)2), 32.2 (s, C(CH3)2), 26.7 (dvt,
Reaction of RhH{xant(PiPr2)2} (1) with Catecholborane
at Low Temperature: Spectroscopic Detection of
RhH2(Bcat){xant(PiPr2)2} (8). A screw-top NMR tube
containing a solution of 1 (23.0 mg, 0.04 mmol) in toluene-
d8 (0.4 mL) and cooled at 195 K was treated with HBcat (4.5
μL, 0.04 mmol). Immediately the NMR tube was introduced in
a NMR probe precooled at 258 K. The immediate and
1
quantitative conversion to 8 was observed by H and 31P{1H}
NMR spectroscopies (in solution at this temperature 10 was
1
observed as a minor product with time). H NMR (400.13
MHz, C7D8, 258 K): δ 7.11 (m, 2H, CH-arom POP), 7.06 (m,
2H, Bcat), 6.98 (m, 2H, CH-arom POP), 6.89 (t, JH−H = 7.5,
2H, CH-arom POP), 6.85 (m, 2H, Bcat), 2.67 (m, 4H,
PCH(CH3)2), 1.42 (dvt, JH−H = 7.9, N = 16.1, 12H,
PCH(CH3)2), 1.17 (s, 6H, CH3), 1.13 (dvt, JH−H = 6.8, N =
13.9, 12H, PCH(CH3)2), −6.04 (dt, JH−Rh = 23.9, JH−P = 13.5,
2H, RhH2). 13C{1H} NMR (100.62 MHz, C7D8, 258 K): δ
156.6 (vt, N = 12.3, Carom POP), 151.7 (s, C-O Bcat), 133.4
(vt, N = 4.7, Carom POP), 130.0 (s, CH-arom POP), 125.9 (s,
CH-arom POP), 123.7 (br, CH-arom POP), 120.2, 110.2 (both
s, CH Bcat), 35.1 (s, C(CH3)2), 28.3 (s, C(CH3)2), 25.7 (vt, N
= 24.5, PCH(CH3)2), 19.4 (vt, N = 8.1, PCH(CH3)2), 18.4 (s,
PCH(CH3)2). 31P{1H} NMR (161.98 MHz, C7D8, 258 K): δ
63.8 (d, JP−Rh = 132.0). 11B{1H} NMR (128.8 MHz, C7D8, 258
K): δ 34.7 (br).
J
C−Rh = 3.7, N = 21.2, PCH(CH3)2), 20.3 (dvt, JC−Rh = 1.0, N =
9.9, PCH(CH3)2), 19.3 (vt, N = 4.2, PCH(CH3)2). 31P{1H}
NMR (121.49 MHz, C6D6, 298 K): δ 55.1 (d, JP−Rh = 165.3).
11B{1H} NMR (96.29 MHz, C6D6, 298 K): δ 48.7 (br).
Reaction of RhH{xant(PiPr2)2} (1) with Bis(pinacolato)-
diboron. A solution of 1 (20 mg, 0.036 mmol) in C6D6 (0.5
mL) in an NMR tube was treated with the stoichiometric
amount of B2pin2 (9.3 mg, 0.036 mmol) at room temperature.
1H, 31P{1H} and 11B NMR spectroscopies show the quantitative
and immediate formation of Rh(Bpin){xant(PiPr2)2} (9) and
HBpin.
Reaction of RhPh{xant(PiPr2)2} (2) with Bis-
(pinacolato)diboron. A solution of 2 (20 mg, 0.032 mmol)
in toluene (0.5 mL) in an NMR tube was treated with the
stoichiometric amount of B2pin2 (8.1 mg, 0.032 mmol), and the
resulting solution was heated at 60 °C in an oil bath. The
reaction was periodically checked by 31P{1H} NMR spectros-
copy. After 24 h, the 31P{1H} NMR spectrum shows the
quantitative conversion of 2 and the formation of Rh(Bpin)-
{xant(PiPr2)2} (9). In addition to the formation of 9 (br, δ
42.9), the 11B{1H} NMR spectrum shows the formation of Ph-
Bpin (br, δ 31.4)
Reaction of RhH{xant(PiPr2)2} (1) with Pinacolborane
at Room Temperature: Preparation of Rh(Bpin){xant-
(PiPr2)2} (9). HBpin (110 μL, 0.76 mmol) was added to a
solution of 1 (400 mg, 0.73 mmol) in pentane (10 mL). After
stirring for 3 min, a dark red solution is obtained. This solution
was evaporated to dryness to afford a red residue, which was
further washed with pentane (3 × 3 mL) and dried in vacuo.
Yield: 458.2 mg (93%). Anal. Calcd for C33H52BO3P2Rh: C,
58.94; H, 7.79. Found: C, 58.90; H, 8.20. HRMS (electrospray,
m/z): calcd for C33H53BO3P2Rh [M + H]+ 673.2618; found,
673.2629. IR (cm−1): ν(C−O−C) 1102 (m). 1H NMR (300.13
MHz, C6D6, 298 K): δ 7.36 (m, 2H, CH-arom POP), 7.10 (dd,
Reaction of RhPh{xant(PiPr2)2} (2) with HBpin. A
solution of 2 (21.4 mg, 0.034 mmol) in toluene (0.5 mL) in
an NMR tube was treated with HBpin (5.0 μL, 0.034 mmol),
JH−H = 7.7, JH−H = 1.6, 2H, CH-arom POP), 6.91 (t, JH−H = 7.7,
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and the resulting solution was heated at 55 °C in an oil bath.
The NMR tube was periodically checked by 31P{1H} NMR
spectroscopy.
borylation product was obtained in 100% yield (isolated 98%)
after 48 h as a mixture of two isomers in a ratio 65 (meta): 35
(para).
Reaction of Rh(Bpin){xant(PiPr2)2} (9) with Benzene. A
solution of 9 (20 mg, 0.030 mmol) in benzene (0.5 mL) in an
NMR tube was heated at 65 °C in an oil bath. The NMR tube
was periodically checked by 31P{1H} NMR spectroscopy. After
2.5 h the 31P{1H} NMR spectrum shows signals corresponding
to Rh(Bpin){xant(PiPr2)2} (9), RhH{xant(PiPr2)2} (1) and
Rh(C6H5){xant(PiPr2)2} (2) in a ratio of 28:28:44, together
with a small signal of an unidentified species.
NMR data for 3-methylphenyl boronic acid pinacol ester: 1H
NMR (400 MHz, CDCl3, 298 K): δ 7.63 (d, JH−H = 0.8, 1H,
CH), 7.60 (t, JH−H = 4.6, 1H, CH), 7.25 (dd, JH−H = 5.0, JH−H
=
1.1, 1H, CH), 7.25 (dd, JH−H = 5.0, JH−H = 1.1, 1H, CH), 2.34
(s, 3H, CH3), 1.33 (s, 12H, CH3). 13C{1H}-APT NMR (100.5
MHz, CDCl3, 298 K): δ 137.2 (s, C-CH3), 135.5 (s, CH), 132.2
(s, CH), 131.9 (s, CH), 127.8 (s, CH), 83.8 (s, C), 25.0 (s,
1
CH3), 21.4 (s, CH3). H and 13C{1H} NMR data agree with
Borylation of Benzene with B2pin2 Catalyzed by
RhH{xant(PiPr2)2} (1). In an argon-filled glovebox, an Ace
pressure tube was charged with 1 (43.7 mg, 0.08 mmol), B2pin2
(254 mg, 1 mmol), and 5 mL of benzene. The resulting mixture
was stirred at 110 °C for 24 h. After this time, the arene was
evaporated under reduced pressure to afford a crude reaction
mixture. After purification of the crude reaction mixture by flash
chromatography over silica gel using diethyl ether as the
eluyent, phenylboronic acid pinacol ester was isolated in a 68%
yield.
Borylation of Benzene with HBpin Catalyzed by
RhH{xant(PiPr2)2} (1). This reaction was performed analo-
gously as described for the borylation of benzene with B2pin2,
starting from 1 (43.7 mg, 0.08 mmol), HBpin (300 μL, 2.06
mmol), and 5 mL of benzene. Isolated yield: 66%.
Borylation of Benzene with B2pin2 Catalyzed by
RhH{xant(PiPr2)2} (1) in the presence of cyclohexene.
This reaction was performed analogously as described for the
borylation of benzene with B2pin2, adding cyclohexene (200
μL, 2.00 mmol). Isolated yield: 89%.
Borylation of Benzene with HBpin Catalyzed by
RhH{xant(PiPr2)2} (1) in the Presence of Cyclohexene.
This reaction was performed analogously as described for the
borylation of benzene with HBpin, adding cyclohexene (200
μL, 2.00 mmol). Isolated yield: 95%.
previously reported data.42
NMR data for 4-methylphenyl boronic acid pinacol ester: 1H
NMR (400 MHz, CDCl3, 298 K): δ 7.70 (d, JH−H = 7.9, 2H,
CH), 7.17 (d, JH−H = 7.5, 2H, CH), 2.35 (s, 3H, CH3), 1.32 (s,
12H, CH3). 13C{1H}-APT NMR (100.5 MHz, CDCl3, 298 K):
δ 141.5 (s, C-CH3), 134.9 (s, CH), 128.6 (s, CH), 83.7 (s, C),
25.0 (s, CH3), 21.8 (s, CH3). 1H and 13C{1H} NMR data agree
with previously reported data.42
Borylation of 1,3-Dimethylbenzene: Preparation of
3,5-Dimethylphenylboronic Acid Pinacol Ester (Run 3).
The reaction was performed using the general procedure. The
title compound was obtained in 100% yield (isolated 99%) after
48 h. 1H NMR (400 MHz, CDCl3, 298 K): δ 7.44 (s, 2H, CH),
7.10 (s, 1H, CH), 2.32 (s, 6H, CH3), 1.34 (s, 12H, CH3).
13C{1H}-APT NMR (100.5 MHz, CDCl3, 298 K): δ 137.3 (s,
C), 133.1 (s, CH), 132.5 (s, CH), 83.8 (s, C), 25.0 (s, CH3),
21.3 (s, CH3). 1H and 13C{1H} NMR data agree with
previously reported data.43
Borylation of Fluorobenzene: Preparation of 2-, 3-
and 4-Fluorophenyl Boronic Acid Pinacol Ester (Run 4).
The reaction was performed using the general procedure. The
borylation product was obtained in 100% yield (isolated 99%)
after 24 h as a mixture of the three possible isomers in a ratio of
43 (ortho): 38 (meta): 19 (para).
1
NMR data for 2-fluorophenyl boronic acid pinacol ester: H
General Procedure for the Borylation Reactions. In an
argon-filled glovebox an Ace pressure tube was charged with
RhH{xant(PiPr2)2} (43.7 mg, 0.08 mmol), HBpin (300 μL,
2.06 mmol), cyclohexene (200 μL, 2.00 mmol), and 5 mL of
the arene. The resulting mixture was stirred at 110 °C for 24 or
48 h. After this time the arene was evaporated under reduced
pressure to afford a crude reaction mixture. The yield of the
NMR (400 MHz, CDCl3, 298 K): δ 7.77 (dd, JH−F = 6.1, JH−H
= 7.7, JH−H = 1.9, 1H, CH), 7.40 (dddd, JH−F = 6.0, JH−H = 8.3,
JH−H = 7.3, JH−H = 1.9, 1H, CH), 7.11 (m, 1H, CH), 7.01 (ddd,
JH−F = 9.0, JH−H = 8.3, JH−H = 0.9, 1H, CH), 1.35 (s, 12H,
CH3). 13C{1H}-APT NMR (100.5 MHz, CDCl3, 298 K): δ
167.2 (d, JC−F = 249.4, C−F), 136.9 (d, JC−F = 7.9, CH), 133.3
(d, JC−F = 8.7, CH), 123.6 (d, JC−F = 3.3, CH), 114.8 (d, JC−F
20.1, CH), 83.8 (s, C), 24.8 (s, CH3). 19F NMR (376.49 MHz,
CDCl3, 298 K): δ −102.3 (dtd, JF−H = 9.0, JF−H = 5.8, JF−H
=
1
borylation reaction was determined by H NMR spectroscopy
by dissolving the crude reaction mixture in CDCl3 and adding
50 μL of 1,2-dichloroethane, which was used as internal
standard. In order to ensure accurate integration of the signals,
the spectra were recorded using eight scans and a 5 s delay. The
isolated yields were calculated after purification of the crude
reaction mixture by flash chromatography over silica gel using
diethyl ether as the eluent and by evaporation to dryness.
Borylation of Benzene: Preparation of Phenylboronic
Acid Pinacol Ester (Run 1). The reaction was performed
using the general procedure. The title compound was obtained
=
44
1
2.5). H NMR data agree with previously reported data.
1
NMR data for 3-fluorophenyl boronic acid pinacol ester: H
NMR (400 MHz, CDCl3, 298 K): δ 7.59 (d, JH−F = 7.3, 1H,
CH), 7.51 (dd, JH−H = 9.1, JH−F = 2.5, 2H, CH), 7.32 (ddd,
JH−H = 8.2, JH−H = 7.3, JH−F = 5.4, 1H, CH), 7.13 (m, 1H, CH),
1.32 (s, 12H, CH3). 13C{1H}-APT NMR (100.5 MHz, CDCl3,
298 K): δ 162.6 (d, JC−F = 256.5, C-F), 130.4 (d, JC−F = 3.0,
CH), 129.5 (d, JC−F = 7.1, CH), 121.0 (d, JC−F = 19.2, CH),
118.1 (d, JC−F = 21.1, CH), 83.8 (s, C), 24.8 (s, CH3). 19F
NMR (376.49 MHz, CDCl3, 298 K): δ −114.00 (td, JF−H = 9.0,
1
in 100% yield (isolated 95%) after 24 h. H NMR (400 MHz,
1
CDCl3, 298 K): δ 7.78 (m, 1H, CH), 7.37 (m, 1H, CH), 7.30
(m, 1H, CH), 1.27 (s, 12H, CH3). 13C{1H}-APT NMR (100.5
MHz, CDCl3, 298 K): δ 134.8 (s, CH), 131.2 (s, CH), 127.7 (s,
JF−H = 5.4). H and 13C{1H} NMR data agree with previously
reported data.45
NMR data for 4-fluorophenyl boronic acid pinacol ester: H
1
1
CH), 83.7 (s, C), 24.9 (s, CH3). H and 13C{1H} NMR data
NMR (400 MHz, CDCl3, 298 K): δ 7.82 (dd, JH−F = 6.3, JH−H
= 8.4, 1H, CH), 7.04 (dd, JH−F = 6.7, JH−H = 8.5, 1H, CH), 1.33
(s, 6H, CH3). 13C{1H}-APT NMR (100.5 MHz, CDCl3, 298
K): δ 165.1 (d, JC−F = 260.4, C-F), 137.1 (d, JC−F = 8.1, CH),
115.2 (d, JC−F = 23.8, CH), 83.8 (s, C), 24.8 (s, CH3). 19F
agree with previously reported data.42
Borylation of Toluene: Preparation of 3- and 4-
Methylphenyl Boronic Acid Pinacol Ester (Run 2). The
reaction was performed using the general procedure. The
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NMR (376.49 MHz, CDCl3, 298 K): δ −108.2 (tt, JF−H = 9.0,
CH), 83.8 (s, C), 24.9 (s, CH3), 21.5 (d, JC−F = 1.7, CH3). 19
F
=
1
JF−H = 6.2). H and 13C{1H} NMR data agree with previously
NMR (376.49 MHz, CDCl3, 298 K): δ −103.7 (dd, JF−H
reported data.46
1
10.3, JF−H = 6.5). H, 13C{1H} and 19F NMR data agree with
previously reported data.48
Borylation of 1,3-Difluorobenzene: Preparation of
2,4-, 3,5- and 2,6-Difluoro-Phenylboronic Acid Pinacol
Ester (Run 5). The reaction was performed using the general
procedure. The borylation product was obtained in 100% yield
(isolated 99%) after 24 h as a mixture of 2,4-difluoro-
phenylboronic acid pinacol ester, 3,5-difluoro-phenylboronic
acid pinacol ester, and 2,6-difluoro-phenylboronic acid pinacol
ester in a ratio of 44:40:16.
Borylation of Anisole: Preparation of 3- and 4-
Methoxyphenyl Boronic Acid Pinacol Ester (Run 7).
The reaction was performed using the general procedure. The
borylation product was obtained in 67% yield (isolated 65%)
after 24 h as a mixture of two isomers in a ratio of 62 (meta): 38
(para).
NMR data for 3-methoxyphenyl boronic acid pinacol ester:
1H NMR (400 MHz, CDCl3, 298 K): δ 7.38 (dt, JH−H = 7.3,
JH−H = 1.0, 1H, CH), 7.30 (dd, JH−H = 2.8, JH−H = 1.0, 1H,
CH), 7.24 (dd, JH−H = 8.2, JH−H = 7.3, 1H, CH), 6.96 (ddd,
JH−H = 8.2, JH−H = 2.8, JH−H = 1.1, 1H, CH), 3.83 (s, 3H,
OCH3), 1.29 (s, 12H, CH3). 13C{1H}-APT NMR (100.5 MHz,
CDCl3, 298 K): δ 159.0 (s, C-OCH3), 128.8 (s, CH), 127.1 (s,
CH), 118.8 (s, CH), 117.7(s, CH), 83.7 (s, C), 55.3 (s, OCH3),
24.9 (s, CH3). 1H and 13C{1H} NMR data agree with
previously reported data.5
NMR data for 2,4-difluoro-phenylboronic acid pinacol ester:
1H NMR (400 MHz, CDCl3, 298 K): δ 7.62 (dt, JH−F = 8.4,
JH−H = 7.1, 1H, CH), 6.75 (m, 1H, CH), 6.64 (td, JH−F = 9.4,
J
H−H = 2.3, 1H, CH), 1.29 (s, 12H, CH3). 13C{1H}-APT NMR
(100.5 MHz, CDCl3, 298 K): δ 168.0 (dd, JC−F = 234.7, JC−F
12.2, C-F), 165.5 (dd, JC−F = 233.5, JC−F = 12.1, C-F), 138.3 (t,
C−F = 10.0, CH), 111.1 (dd, JC−F = 20.1, JC−F = 3.6, CH), 103.6
=
J
(dd, JC−F = 27.9, JC−F = 24.3, CH), 84.0 (s, C), 24.8 (s, CH3).
19F{1H} NMR (376.49 MHz, CDCl3, 298 K): δ −105.2 (d, JF−F
1
= 10.8), −98.8 (d, JF−F = 10.8). H and 13C{1H} NMR data
NMR data for 4-methoxyphenyl boronic acid pinacol ester:
1H NMR (400 MHz, CDCl3, 298 K): δ 7.72 (d, JH−H = 8.6, 2H,
CH), 6.85 (d, JH−H = 8.6, 2H, CH), 3.70 (s, 3H, OCH3), 1.28
(s, 12H, CH3). 13C{1H}-APT NMR (100.5 MHz, CDCl3, 298
K): δ 162.1 (s, C-OCH3), 136.4 (s, CH), 113.2 (s, CH), 83.5
agree with previously reported data.47
NMR data for 3,5-difluoro-phenylboronic acid pinacol ester:
1H NMR (400 MHz, CDCl3, 298 K): δ 7.25 (m, 2H, CH), 6.85
(m, 1H, CH), 1.30 (s, 12H, CH3). 13C{1H}-APT NMR (100.5
MHz, CDCl3, 298 K): δ 162.8 (dd, JC−F = 249.7, JC−F = 11.0, C-
F), 116.8 (m, CH), 106.5 (t, JC−F = 25.1, CH), 84.5 (s, C), 24.8
(s, CH3). 19F{1H} NMR (376.49 MHz, CDCl3, 298 K): δ
1
(s, C), 54.9 (s, OCH3), 24.9 (s, CH3). H and 13C{1H} NMR
data agree with previously reported data.42
Structural Analysis of Complexes 2, 3, 5, 6, and 9.
Crystals suitable for the X-ray diffraction were obtained by slow
evaporation of pentane (2, 3, 9) or by diffusion of pentane into
solutions of 5 and 6 in benzene. X-ray data were collected on a
Bruker Smart APEX difractometer equipped with a normal
focus, 2.4 kW sealed tube source (Mo radiation, λ = 0.71073 Å)
operating at 50 kV and 30 (6) or 40 (2, 3, 5, 9) mA. Data were
collected over the complete sphere by a combination of four
sets. Each frame exposure time was 10 s (2, 6), 20 s (3), 30 s
(5, 9) covering 0.3° in ω. Data were corrected for absorption
by using a multiscan method applied with the SADABS
program.49 The structures were solved by the Patterson (Rh
atoms) or direct methods and conventional Fourier techniques
and refined by full-matrix least-squares on F2 with
SHELXL97.50 Anisotropic parameters were used in the last
cycles of refinement for all non-hydrogen atoms. The hydrogen
atoms were observed or calculated and refined freely or using a
restricted riding model. Complexes 3a and 3b cocrystallize (3)
in a ratio of 71.3:28.7. The atoms of the tolyl groups were
refined with restrained geometry and thermal parameters. The
fluorine atom of 5 is disordered (50/50) between the atoms
C(2) and C(6) of the aryl moiety. The boryl ligand of 9 is
disordered between two orientations (0.8/0.2) by a 68°
rotation around the Rh−B bond. The disordered groups were
refined with two moieties, complementary occupancy factors,
and isotropic thermal parameters. Complexes 5 and 6
crystallize with two molecules of benzene each, one of them
disordered. These disordered solvent molecules were refined
isotropically with restrained geometry. For all structures, the
highest electronic residuals were observed in the close
proximity of the metal centers and make no chemical sense.
Crystal data for 2: C33H45OP2Rh, MW 622.54, red, prism
(0.22 × 0.12 × 0.09), triclinic, space group P-1, a: 12.2682(9)
Å, b: 13.4969(10) Å, c: 19.9489(15) Å, α = 91.5600(10)°, β =
107.3610(10)°, γ = 104.3260(10)°, V = 3036.4(4) Å3, Z = 2,
1
−110.7 (s). H and 13C{1H} NMR data agree with previously
reported data.47
NMR data for 2,6-difluoro-phenylboronic acid pinacol ester:
1H NMR (400 MHz, CDCl3, 298 K): δ 7.30 (m, 1H, CH), 6.82
(m, 2H, CH), 1.34 (s, 12H, CH3). 13C{1H}-APT NMR (100.5
MHz, CDCl3, 298 K): δ 166.6 (dd, JC−F = 250.5, JC−F = 12.8, C-
F), 133.1 (t, JC−F = 10.6, CH), 111.0 (m, CH), 84.2 (s, C), 24.7
(s, CH3). 19F{1H} NMR (376.49 MHz, CDCl3, 298 K): δ
1
−100.5 (s). H and 13C{1H} NMR data agree with previously
reported data.47
Borylation of 1-Fluoro-3-methylbenzene: Preparation
of 3-Fluoro-5-methylphenylboronic Acid Pinacol Ester
and 2-Fluoro-4-methylphenylboronic Acid Pinacol Ester
(Run 6). The reaction was performed using the general
procedure. The borylation product was obtained in 74% yield
(isolated 73%) after 24 h as a mixture of 3-fluoro-5-
methylphenylboronic acid pinacol ester and 2-fluoro-4-
methylphenylboronic acid pinacol ester in a ratio of 58:42.
NMR data for 3-fluoro-5-methylphenylboronic acid pinacol
ester. 1H NMR (400 MHz, CDCl3, 298 K): δ 7.37 (s, 1H, CH),
7.26 (dd, JH−F = 8.8, JH−H = 2.5, 1H, CH), 6.92 (m, 1H, CH),
2.32 (s, 3H, CH3), 1.32 (s, 12H, CH3). 13C{1H}-APT NMR
(100.5 MHz, CDCl3, 298 K): δ 162.7(d, JC−F = 246.0, C-F),
139.9 (d, JC−F = 7.0, C-CH3), 131.1 (d, JC−F = 2.5, CH), 118.9
(d, JC−F = 20.9, CH), 117.9 (d, JC−F = 19.3, CH), 84.1 (s, C),
24.9 (s, CH3), 21.1 (d, JC−F = 1.7, CH3).19F NMR (376.49
MHz, CDCl3, 298 K): δ −115.2 (t, JF−H = 9.3).
NMR data for 2-fluoro-4-methylphenylboronic acid pinacol
ester. 1H NMR (400 MHz, CDCl3, 298 K): δ 7.59 (dd, JH−F
7.6, JH−H = 7.6, 1H, CH), 6.91 (m, 1H, CH), 6.82 (d, JH−F
=
=
10.3, 1H, CH), 2.32 (s, 3H, CH3), 1.33 (s, 12H, CH3).
13C{1H}-APT NMR (100.5 MHz, CDCl3, 298 K): δ 167.5 (d,
JC−F = 250.5, C-F), 144.5 (d, JC−F = 8.7, C-CH3), 136.7 (d, JC−F
= 8.6, CH), 124.6 (d, JC−F = 2.7, CH), 115.9 (d, JC−F = 23.7,
D
calc: 1.362 g cm−3, F(000): 1304, T = 100(2) K, μ 0.692
K
DOI: 10.1021/acs.organomet.5b00176
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
mm−1. 28048 measured reflections (2θ: 2−57°, ω scans 0.3°),
13 844 unique (Rint = 0.0512); minimum/maximum trans-
mission factors 0.733/0.862. Final agreement factors were R1 =
0.0593 (9942 observed reflections, I > 2σ(I)) and wR2 =
0.1146; data/restraints/parameters 13 844/0/687; GoF =
1.072. Largest peak and hole 1.063 and −1.405 e/Å3.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
Financial support from the MINECO of Spain (Projects
CTQ2014-52799-P and CTQ2014-51912-REDC), the Diputa-
■
Crystal data for 3: C34H47OP2Rh, MW 636.57, red, prism
(0.30 × 0.21 × 0.13), orthorhombic, space group Pbca, a:
14.8931(19) Å, b: 20.025(3)Å, c: 21.472(3) Å, V = 6403.8(14)
Å3, Z = 8, Dcalc: 1.321 g cm−3, F(000): 267, T = 100(2) K, μ
0.657 mm−1. 49325 measured reflections (2θ: 3−60°, ω scans
0.3°), 9226 unique (Rint = 0.0701); minimum/maximum
transmission factors 0.708/0.900. Final agreement factors
were R1 = 0.0398 (5052 observed reflections, I > 2 σ(I)) and
wR2 = 0.0948; data/restraints/parameters 9226/5/326; GoF =
0.861. Largest peak and hole 1.078 and −0.959 e/Å3.
cion
́ ́
General de Aragon (E-35), FEDER, and the European
Social Fund is acknowledged. We are very grateful to Dr.
Enrique Onate for collecting the X-ray diffraction data.
̃
REFERENCES
■
(1) (a) Davies, H. M. L.; Morton, D. Chem. Soc. Rev. 2011, 40, 1857−
1869. (b) Borovik, A. S. Chem. Soc. Rev. 2011, 40, 1870−1874.
(c) Zhou, M.; Crabtree, R. H. Chem. Soc. Rev. 2011, 40, 1875−1884.
(d) Lu, H.; Zhang, X. P. Chem. Soc. Rev. 2011, 40, 1899−1909.
(e) Lewis, J. C.; Coelho, P. S.; Arnold, F. H. Chem. Soc. Rev. 2011, 40,
2003−2021. (f) Webb, J. R.; Bolano, T.; Gunnoe, T. B. ChemSusChem
̃
Crystal data for 5: C33H44FOP2Rh·2C6H6, MW 796.75,
orange, irregular block (0.13 × 0.12 × 0.10), monoclinic,
space group P2(1)/m, a: 11.8790(17) Å, b: 14.547(2) Å, c:
2011, 4, 37−49.
(2) (a) Mkhalid, I. A. I.; Barnard, J. H.; Marder, T. B.; Murphy, J. M.;
Hartwig, J. F. Chem. Rev. 2010, 110, 890−931. (b) Hartwig, J. F. Acc.
12.9966(18) Å, β = 114.323(2)°, V = 2046.6(5) Å3, Z = 2, Dcalc
:
́
Chem. Res. 2012, 45, 864−873. (c) Ros, A.; Fernandez, R.; Lassaletta,
1.293 g cm−3, F(000): 836, T = 100(2) K, μ 0.532 mm−1.
22891 measured reflections (2θ: 3−57°, ω scans 0.3°), 5112
unique (Rint = 0.0387); minimum/maximum transmission
J. M. Chem. Soc. Rev. 2014, 43, 3229−3243.
(3) Boronic Acids: Preparation and Applications in Organic Synthesis,
Medicine and Materials, 2nd ed.; Hall, D. G., Ed.; Wiley-VCH:
Weinheim, 2011.
factors 0.738/0.862. Final agreement factors were R1
=
0.0463 (4595 observed reflections, I > 2σ(I)) and wR2 =
0.1179; data/restraints/parameters 5112/0/250; GoF = 1.048.
Largest peak and hole 2.248 and −0.814 e/Å3.
(4) Hartwig, J. F. Chem. Soc. Rev. 2011, 40, 1992−2002.
(5) Yan, G.; Jiang, Y.; Kuang, C.; Wang, S.; Liu, H.; Zhang, Y.; Wang,
J. Chem. Commun. 2010, 46, 3170−3172.
(6) Obligacion, J. V.; Semproni, S. P.; Chirik, P. J. J. Am. Chem. Soc.
2014, 136, 4133−4136.
(7) (a) Chen, H.; Schlecht, S.; Semple, T. C.; Hartwig, J. F. Science
2000, 287, 1995−1997. (b) Cho, J.-Y.; Iverson, C. N.; Smith, M. R., III
J. Am. Chem. Soc. 2000, 122, 12868−12869. (c) Tse, M. K.; Cho, J.-Y.;
Smith, M. R., III Org. Lett. 2001, 3, 2831−2833.
(8) (a) Cho, J.-Y.; Tse, M. K.; Holmes, D.; Maleczka, R. E., Jr.; Smith,
M. R., III Science 2002, 295, 305−308. (b) Ishiyama, T.; Takagi, J.;
Ishida, K.; Miyaura, N.; Anastasi, N. R.; Hartwig, J. F. J. Am. Chem. Soc.
2002, 124, 390−391. (c) Boller, T. M.; Murphy, J. M.; Hapke, M.;
Ishiyama, T.; Miyaura, N.; Hartwig, J. F. J. Am. Chem. Soc. 2005, 127,
Crystal data for 6: C33H53F2OP2Rh·2C6H6, MW 814.74,
orange, irregular block (0.24 × 0.20 × 0.16), monoclinic, space
group P2(1)/m, a: 11.8677(4) Å, b: 14.5318(5) Å, c:
13.0100(5) Å, β = 114.51°, V = 2041.44(13) Å3, Z = 2, Dcalc
:
1.325 g cm−3, F(000): 852, T = 100(2) K, μ 0.539 mm−1.
24908 measured reflections (2θ: 3−57°, ω scans 0.3°), 5113
unique (Rint = 0.0249); minimum/maximum transmission
factors 0.822/0.922. Final agreement factors were R1
=
0.0230 (4726 observed reflections, I > 2σ(I)) and wR2 =
0.0578; data/restraints/parameters 5113/60/290; GoF = 1.025.
Largest peak and hole 0.605 and −0.329 e/Å3.
14263−14278. (d) Nguyen, D. H.; Per
Jimenez, M. V.; Lahoz, F. J.; Oro, L. A. Dalton Trans. 2011, 40, 8429−
8435. (e) Nguyen, D. H.; Perez-Torrente, J.; Jimenez, M. V.; Modrego,
F. J.; Gomez-Bautista, D.; Lahoz, F. J.; Oro, L. A. Organometallics
́
ez-Torrente, J.; Lomba, L.;
́
Crystal data for 9: C33H52BO3P2Rh, MW 672.41, red, irregular
block (0.12 × 0.08 × 0.07), monoclinic, space group P2(1)/n,
a: 9.6438(4) Å, b: 18.7522(8) Å, c: 18.5770(8) Å, β =
96.2620(10)°, V = 3339.5(2)Å3, Z = 4, Dcalc: 1.337 g cm−3,
F(000): 1416, T = 100(2) K, μ 0.638 mm−1. 38723 measured
́
́
́
2013, 32, 6918−6930. (f) Preshlock, S. M.; Ghaffari, B.; Maligres, P.
E.; Krska, S. W.; Maleczka, R. E., Jr.; Smith, M. R., III J. Am. Chem. Soc.
2013, 135, 7572−7582.
(9) (a) Shilov, A. E.; Shul’pin, G. B. Chem. Rev. 1997, 97, 2879−
2932. (b) Labinger, J. A.; Bercaw, J. E. Nature 2002, 417, 507−514.
(c) Lersch, M.; Tilset, M. Chem. Rev. 2005, 105, 2471−2526.
(d) Balcells, D.; Clot, E.; Eisenstein, O. Chem. Rev. 2010, 110, 749−
823.
(10) (a) Irvine, G. J.; Lesley, M. J. G.; Marder, T. B.; Norman, N. C.;
Rice, C. R.; Robins, E. G.; Roper, W. R.; Whittell, G. R.; Wright, L. J.
Chem. Rev. 1998, 98, 2685−2722. (b) Braunschweig, H.; Colling, M.
Coord. Chem. Rev. 2001, 223, 1−51. (c) Braunschweig, H.; Kollann, C.;
Rais, D. Angew. Chem., Int. Ed. 2006, 45, 5254−5274. (d) Braunsch-
weig, H.; Dewhurst, R. D.; Schneider, A. Chem. Rev. 2010, 110, 3924−
3957.
(11) (a) Albrecht, M.; van Koten, G. Angew. Chem., Int. Ed. 2001, 40,
3750−3781. (b) Benito-Garagorri, D.; Kirchner, K. Acc. Chem. Res.
2008, 41, 201−213. (c) Whited, M. T.; Grubbs, R. H. Acc. Chem. Res.
2009, 42, 1607−1616.
reflections (2θ: 3−57°, ω scans 0.3°), 8089 unique (Rint
=
0.0603); minimum/maximum transmission factors 0.843/
0.957. Final agreement factors were R1 = 0.0543 (6758
observed reflections, I > 2σ(I)) and wR2 = 0.0930; data/
restraints/parameters 8089/0/371; GoF = 1.173. Largest peak
and hole 0.774 and −0.688 e/Å3.
ASSOCIATED CONTENT
* Supporting Information
■
S
Molecular diagram of cocrystrallized 3a and 3b, NMR spectra
of complexes 7 and 8 and of all borylated arenes. CIF files
giving positional and displacement parameters, crystallographic
data, and bond lengths and angles of compounds 2, 3, 5, 6, and
9. The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.5b00176.
(12) (a) Zuideveld, M. A.; Swennenhuis, B. H. G.; Boele, M. D. K.;
Guari, Y.; van Strijdonck, G. P. F.; Reek, J. N. H.; Kamer, P. C. J.;
Goubitz, K.; Fraanje, J.; Lutz, M.; Spek, A. L.; van Leeuwen, P. W. N.
M. J. Chem. Soc., Dalton Trans. 2002, 2308−2317. (b) van der Vlugt, J.
I.; Sablong, R.; Mills, A. M.; Kooijman, H.; Spek, A. L.; Meetsma, A.;
Vogt, D. Dalton Trans. 2003, 4690−4699. (c) Fox, D. J.; Duckett, S.
AUTHOR INFORMATION
Corresponding Author
*E-mail: maester@unizar.es.
■
L
DOI: 10.1021/acs.organomet.5b00176
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
B.; Flaschenriem, C.; Brennessel, W. W.; Schneider, J.; Gunay, A.;
Eisenberg, R. Inorg. Chem. 2006, 45, 7197−7209. (d) Grushin, V. V.;
Marshall, W. J. J. Am. Chem. Soc. 2006, 128, 12644−12645. (e) Deb,
B.; Borah, B. J.; Sarmah, B. J.; Das, B.; Dutta, D. K. Inorg. Chem.
Commun. 2009, 12, 868−871. (f) Ledger, A. E. W.; Slatford, P. A.;
Lowe, J. P.; Mahon, M. F.; Whittlesey, M. K.; Williams, J. M. J. Dalton
Trans. 2009, 716−722. (g) Pontiggia, A. J.; Chaplin, A. B.; Weller, A.
S. J. Organomet. Chem. 2011, 696, 2870−2876. (h) Guard, L. M.;
Ledger, A. E. W.; Reade, S. P.; Ellul, C. E.; Mahon, M. F.; Whittlesey,
M. K. J. Organomet. Chem. 2011, 696, 780−786. (i) Dallanegra, R.;
Chaplin, A. B.; Weller, A. S. Organometallics 2012, 31, 2720−2728.
(13) For group 8 metals, see: (a) Asensio, G.; Cuenca, A. B.;
T.; Otsuka, S.; Ibers, J. A. J. Am. Chem. Soc. 1980, 102, 6451−6457.
(c) Burgess, K.; van der Donk, W. A.; Westcott, S. A.; Marder, T. B.;
Baker, R. T.; Calabrese, J. C. J. Am. Chem. Soc. 1992, 114, 9350−9359.
(d) Goikhman, R.; Aizenberg, M.; Ben-David, Y.; Shimon, L. J. W.;
Milstein, D. Organometallics 2002, 21, 5060−5065. (e) Esteruelas, M.
́
A.; Herrero, J.; Olivan, M. Organometallics 2004, 23, 3891−3897.
(f) Teltewskoi, M.; Panetier, J. A.; Mcgregor, S. A.; Braun, T. Angew.
Chem., Int. Ed. 2010, 49, 3947−3951. (g) Shaw, B. K.; Patrick, B. O.;
Fryzuk, M. D. Organometallics 2012, 31, 783−786. (h) Segarra, C.;
́
Mas-Marza, E.; Lowe, J. P.; Mahon, M. F.; Poulten, R. C.; Whittlesey,
M. K. Organometallics 2012, 31, 8584−8590.
(25) (a) Darensbourg, D. J.; Grotsch, G.; Wiegreffe, P.; Rheingold, A.
̈
Esteruelas, M. A.; Medio-Simon
Chem. 2010, 49, 8665−8667. (b) Esteruelas, M. A.; Honczek, N.;
Olivan, M.; Onate, E.; Valencia, M. Organometallics 2011, 30, 2468−
2471. (c) Alos
Valencia, M. Inorg. Chem. 2013, 52, 6199−6213. (d) Alos
T.; Esteruelas, M. A.; Olivan, M.; Onate, E.; Valencia, M. Inorg. Chem.
2014, 53, 1195−1209. For group 9 metals, see: (e) Esteruelas, M. A.;
Olivan, M.; Velez, A. Inorg. Chem. 2013, 52, 5339−5349. (f) Esteruelas,
M. A.; Olivan, M.; Vel
́
, M.; Olivan
́
, M.; Valencia, M. Inorg.
L. Inorg. Chem. 1987, 26, 3827−3830. (b) Boyd, S. E.; Field, L. D.;
Hambley, T. W.; Partridge, M. G. Organometallics 1993, 12, 1720−
1724. (c) Krug, C.; Hartwig, J. F. J. Am. Chem. Soc. 2002, 124, 1674−
1679. (d) Krug, C.; Hartwig, J. F. J. Am. Chem. Soc. 2004, 126, 2694−
2695. (e) Mcgregor, S. A.; Roe, D. C.; Marshall, W. J.; Bloch, K. M.;
Bakhmutov, V. I.; Grushin, V. V. J. Am. Chem. Soc. 2005, 127, 15304−
15321. (f) Sun, Z.-M.; Zhao, P. Angew. Chem., Int. Ed. 2009, 48, 6726−
6730. (g) Truscott, B. J.; Fortman, G. C.; Slawin, A. M. Z.; Nolan, S. P.
Org. Biomol. Chem. 2011, 9, 7038−7041.
́
̃
́
́
, J.; Bolano, T.; Esteruelas, M. A.; Olivan, M.; Onate, E.;
̃ ̃
́
, J.; Bolano,
̃
́
̃
́
́
́
́
ez, A. Inorg. Chem. 2013, 52, 12108−12119.
(14) (a) Werner, H.; Wolf, J.; Hohn, A. J. Organomet. Chem. 1985,
287, 395−407. (b) Schneider, D.; Werner, H. Angew. Chem., Int. Ed.
1991, 30, 700−702.
(26) (a) Adams, C. S.; Legzdins, P.; Tran, E. J. Am. Chem. Soc. 2001,
123, 612−624. (b) Adams, C. S.; Legzdins, P.; Tran, E. Organometallics
2002, 21, 1474−1486. (c) Butschke, B.; Schwarz, H. Organometallics
2011, 30, 1588−1598.
̈
(15) (a) van der Boom, M. E.; Milstein, D. Chem. Rev. 2003, 103,
1759−1792. (b) Choi, J.; McArthur, A. H. R.; Brookhart, M.;
Goldman, A. S. Chem. Rev. 2011, 111, 1761−1779. (c) Haibach, M. C.;
Kundu, S.; Brookhart, M.; Goldman, A. S. Acc. Chem. Res. 2012, 45,
947−958. (d) Gunanattan, C.; Milstein, D. Chem. Rev. 2014, 114,
12024−12087.
(16) (a) Moxham, G. L.; Randell-Sly, H. E.; Brayshaw, S. K.;
Woodward, R. L.; Weller, A. S.; Willis, M. C. Angew. Chem., Int. Ed.
2006, 45, 7618−7622. (b) Moxham, G. L.; Randell-Sly, H. E.;
Brayshaw, S. K.; Weller, A. S.; Willis, M. C. Chem.Eur. J. 2008, 14,
8383−8397. (c) Pawley, R. J.; Moxham, G. L.; Dallanegra, R.; Chaplin,
A. B.; Brayshaw, S. K.; Weller, A. S.; Willis, M. C. Organometallics
2010, 29, 1717−1728. (d) Pike, S. D.; Pawley, R. J.; Chaplin, A. B.;
Thompson, A. L.; Hooper, J. A.; Willis, M. C.; Weller, A. S. Eur. J.
Inorg. Chem. 2011, 5558−5565. (e) Dallanegra, R.; Chaplin, A. B.;
Weller, A. S. Organometallics 2012, 31, 2720−2728. (f) Pawley, R. J.;
Huertos, M. A.; Lloyd-Jones, G. C.; Weller, A. S.; Willis, M. C.
Organometallics 2012, 31, 5650−5659.
(17) (a) Kranenburg, M.; van der Burgt, Y. E. M.; Kamer, P. C. J.;
van Leeuwen, P. W. N. M.; Goubitz, K.; Fraanje, J. Organometallics
1995, 14, 3081−3089. (b) van der Veen, L. A.; Boele, M. D. K.;
Bregman, F. R.; Kamer, P. C. J.; van Leeuwen, P. W. N. M.; Goubitz,
K.; Fraanje, J.; Schenk, H.; Bo, C. J. Am. Chem. Soc. 1998, 120, 11616−
11626. (c) van der Veen, L. A.; Keeven, P. H.; Shoemaker, G. C.;
Reek, J. N. H.; Kamer, P. C. J.; van Leeuwen, P. W. N. M.; Lutz, M.;
Spek, A. L. Organometallics 2000, 19, 872−883. (d) van der Vlugt, J. I.;
Sablong, R.; Magusin, P. C. M. M.; Mills, A. M.; Spek, A. L.; Vogt, D.
Organometallics 2004, 23, 3177−3183.
(27) (a) Reinartz, S.; White, P. S.; Brookhart, M.; Templeton, J. L.
Organometallics 2001, 20, 1709−1712. (b) Johansson, L.; Ryan, O. B.;
Rømming, C.; Tilset, M. J. Am. Chem. Soc. 2001, 123, 6579−6590.
(c) Ito, J.; Nishiyama, H. Eur. J. Inorg. Chem. 2007, 1114−1119.
(d) Ito, J.; Kaneda, T.; Nishiyama, H. Organometallics 2012, 31, 4442−
4449. (e) Rivada-Wheelaghan; Ortuno, M. A.; Díez, J.; Lledos, A.;
́
̃
Conejero, S. Angew. Chem., Int. Ed. 2012, 51, 3936−3939.
(28) (a) Burger, P.; Bergman, R. G. J. Am. Chem. Soc. 1993, 115,
10462−10463. (b) Esteruelas, M. A.; García-Raboso, J.; Olivan
́
, M.
Organometallics 2011, 30, 3844−3852.
(29) Zhang, F.; Kirby, C. W.; Hairsine, D. W.; Jennings, M. C.;
Puddephatt, R. J. J. Am. Chem. Soc. 2005, 127, 14196−14197.
(30) C−H bond activation products are particularly preferred for aryl
fluorides, which rarely undergo C−F cleavage. For some relevant
examples of the latter, see: (a) Barrio, P.; Castarlenas, R.; Esteruelas,
M. A.; Lledos, A.; Maseras, F.; Onate, E.; Tomas, J. Organometallics
́
̀
̃
2001, 20, 442−452. (b) Liu, W.; Welch, K.; Trindle, C. O.; Sabat, M.;
Myers, W. H.; Harman, W. D. Organometallics 2007, 26, 2589−2597.
(c) Schaub, T.; Fischer, P.; Steffen, A.; Braun, T.; Radius, U.; Mix, A. J.
Am. Chem. Soc. 2008, 130, 9304−9317. (d) Johnson, S. A.; Huff, C.
W.; Mustafa, F.; Saliba, M. J. Am. Chem. Soc. 2008, 130, 17278−17280.
(e) Amii, H.; Uneyama, K. Chem. Rev. 2009, 109, 2119−2183.
(f) Clot, E.; Eisenstein, O.; Jasim, N.; Macgregor, S. A.; McGrady, J. E.;
Perutz, R. N. Acc. Chem. Res. 2011, 44, 333−348. (g) Johnson, S. A.;
Mroz, N. M.; Valdizon, R.; Murray, S. Organometallics 2011, 30, 441−
457. (h) Li, B. Z.; Qian, Y. Y.; Liu, J.; Chan, K. S. Organometallics
2014, 33, 7059−7068.
(18) Williams, G. L.; Parks, C. M.; Smith, C. R.; Adams, H.; Haynes,
A.; Meijer, A. J. H. M.; Sunley, G. J.; Gaemers, S. Organometallics 2011,
30, 6166−6179.
(19) Julian, L. D.; Hartwig, J. F. J. Am. Chem. Soc. 2010, 132, 13813−
13822.
(31) (a) Evans, M. E.; Burke, C. L.; Yaibuathes, S.; Clot, E.;
Eisenstein, O.; Jones, W. D. J. Am. Chem. Soc. 2009, 131, 13464−
́
13473. (b) Clot, E.; Megret, C.; Eisenstein, O.; Perutz, R. N. J. Am.
Chem. Soc. 2009, 131, 7817−7827. (c) Tanabe, T.; Brennessel, W. W.;
Clot, E.; Eisenstein, O.; Jones, W. D. Dalton Trans. 2010, 39, 10495−
10509.
(20) (a) Arambasic, M.; Hooper, J. F.; Willis, M. C. Org. Lett. 2013,
15, 5162−5165. (b) Ren, P.; Pike, S. D.; Pernik, I.; Weller, A. S.; Willis,
M. C. Organometallics 2015, 34, 711−723.
(32) Kallane, S. I.; Teltewskoi, M.; Braun, T.; Braun, B. Organo-
̈
metallics 2015, 34, 1156−1169.
(21) Haibach, M. C.; Wang, D. Y.; Emge, T. J.; Krogh-Jespersen, K.;
Goldman, A. S. Chem. Sci. 2013, 4, 3683−3692.
(33) Bajo, S.; Esteruelas, M. A.; Lo
Organometallics 2014, 33, 1851−1858.
(34) Bajo, S.; Esteruelas, M. A.; Lo
Organometallics 2011, 30, 5710−5715.
́
́
pez, A. M.; Onate, E.
̃
(22) Johnson, H. C.; Leitao, E. M.; Whittell, G. R.; Manners, I.;
Lloyd-Jones, G. C.; Weller, A. S. J. Am. Chem. Soc. 2014, 136, 9078−
9093.
pez, A. M.; Onate, E.
̃
(35) For example, see: Buil, M. L.; Esteruelas, M. A.; Fernan
́
dez, I.;
(23) Johnson, H. C.; Torry-Harris, R.; Ortega, L.; Theron, R.;
McIndoe, J. S.; Weller, A. S. Catal. Sci. Technol. 2014, 4, 3486−3494.
(24) (a) Strauss, S. H.; Diamond, S. E.; Mares, F.; Shriver, D. F. Inorg.
Chem. 1978, 17, 3064−3068. (b) Yoshida, T.; Thorn, D. L.; Okano,
Izquierdo, S.; Onate, E. Organometallics 2013, 32, 2744−2752.
̃
(36) (a) Johnson, C. E.; Eisenberg, R. J. Am. Chem. Soc. 1985, 107,
, M.; Onate, E.;
6531−6540. (b) Esteruelas, M. A.; Lahoz, F. J.; Olivan
́
̃
Oro, L. A. Organometallics 1995, 14, 3486−3496. (c) Esteruelas, M. A.;
M
DOI: 10.1021/acs.organomet.5b00176
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
́
Olivan, M.; Oro, L. A. Organometallics 1996, 15, 814−822.
(d) Esteruelas, M. A.; Oro, L. A. Coord. Chem. Rev. 1999, 183−195,
557−618.
(37) Bolano, T.; Castarlenas, R.; Esteruelas, M. A.; Onate, E. J. Am.
̃
̃
Chem. Soc. 2007, 129, 8850−8859.
(38) (a) Dai, C.; Stringer, G.; Marder, T. B.; Scott, A. J.; Clegg, W.;
Norman, N. C. Inorg. Chem. 1997, 36, 272−273. (b) Hasegawa, M.;
Segawa, Y.; Yamashita, M.; Nozaki, K. Angew. Chem., Int. Ed. 2012, 51,
6956−6960. (c) Masuda, Y.; Hasegawa, M.; Yamashita, M.; Nozaki, K.;
Ishida, N.; Murakami, M. J. Am. Chem. Soc. 2013, 135, 7142−7145.
(39) (b) Teltewskoi, M.; Kallane, S. I.; Braun, T.; Herrmann, R. Eur.
̈
J. Inorg. Chem. 2013, 5762−5768. (b) Kallane, S. I.; Braun, T.; Braun,
̈
B.; Mebs, S. Dalton. Trans. 2014, 43, 6786−6801.
(40) Schmid, G. Chem. Ber. 1969, 102, 191−195.
(41) Shimada, S.; Batsanov, A. S.; Howard, J. A. K.; Marder, T. B.
Angew. Chem., Int. Ed. 2001, 40, 2168−2171.
(42) Clary, J. W.; Rettenmaier, T. J.; Snelling, R.; Bryks, W.; Banwell,
J.; Wipke, W. T.; Singaram, B. J. Org. Chem. 2011, 76, 9602−9610.
(43) Harrisson, P.; Morris, J.; Marder, T. B.; Steel, P. G. Org. Lett.
2009, 11, 3586−3589.
(44) Zhu, W.; Ma, D. Org. Lett. 2006, 8, 261−263.
(45) Kianmehr, E.; Yahyaee, M.; Tabatabai, K. Tetrahedron Lett.
2007, 48, 2713−2715.
(46) Browne, D. L.; Baumann, M.; Harji, B. H.; Baxendale, I. R.; Ley,
S. V. Org. Lett. 2011, 13, 3312−3315.
(47) Chotana, G. A.; Rak, M. A.; Smith, M. R., III J. Am. Chem. Soc.
2005, 127, 10539−10544.
(48) Jayasundara, C. R. K.; Unold, J. M.; Oppenheimer, J.; Smith, M.
R., III; Maleczka, R. E., Jr. Org. Lett. 2014, 16, 6072−6075.
(49) Blessing, R. H. Acta Crystallogr. 1995, A51, 33−38. SADABS:
Area-detector absorption correction; Bruker-AXS: Madison, WI, 1996.
(50) SHELXTL Package, v. 6.10; Bruker-AXS: Madison, WI, 2000.
Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112−122.
N
DOI: 10.1021/acs.organomet.5b00176
Organometallics XXXX, XXX, XXX−XXX