Directly observed transmetalation from boron to rhodium. β-aryl elimination from Rh(I) arylboronates and diarylborinates

Article abstract of DOI:10.1021/ja068587q

Transmetalation from boron to rhodium in the absence of basic activators is reported to proceed by β-aryl elimination from a series of triethylphospine-ligated rhodium(I) arylboronates and diarylborinates. [Rh(PEt₃)₃OB(OH)Ar] were prepared by treating {Rh(PEt₃)₂[N(SiMe₃)₂} with the corresponding arylboronic acid, ArB(OH)₂, in the presence of added PEt₃. One example of these complexes was characterized by X-ray diffraction. [Rh(PEt₃)₃OB(mesityl)₂] and [Rh(PEt₃)₂OB(mesityl)₂] were prepared by analogous methods from dimesitylborinic acid in the presence and absence of added PEt₃. Heating of the trisphosphine boronate complexes in cyclohexane generated the rhodium aryl complexes, [(PEt₃)₃RhAr] and boroxin in good to high yields. [Rh(PEt₃)₃OB(mesityl)₂] also underwent aryl migration to form [(PEt₃)₃Rh(mesityl)] and a cyclic boroxine. Kinetic studies showed that migration of more electron-poor aryl groups from the boronate complexes was slightly faster than migration of more electron-poor aryl groups and that migration of the o-anisyl group was particularly fast. Kinetic results are most consistent with a ligand dissociation pathway with a rate-limiting β-aryl elimination from a 14-electron, bis(phosphine) intermediate. Copyright

Full text of DOI:10.1021/ja068587q

Published on Web 01/27/2007
Directly Observed Transmetalation from Boron to Rhodium. â-Aryl
Elimination from Rh(I) Arylboronates and Diarylborinates
Pinjing Zhao, Christopher D. Incarvito, and John F. Hartwig*
Department of Chemistry, Yale UniVersity, P.O. Box 208107 New HaVen, Connecticut 06520-8107, and
Department of Chemistry, UniVersity of Illinois, 600 South Mathews AVenue, Urbana, Illinois 61801
Received December 7, 2006; E-mail: jhartwig@uiuc.edu
Transmetalation from organoboron compounds to late transition
metal complexes is now a common route to catalytically active
metal-hydrocarbyl intermediates.1 Despite the importance of this
transformation, details of its mechanism remain largely unknown.2
A few groups have reported stoichiometric studies of reactions be-
tween arylboronic acids and organometallic complexes to generate
metal aryl species.3 However, the process by which the aryl group is
transferred from boron to the metal is not well defined. Reactions of
metal hydroxo complexes with boronic acids and reactions of hyper-
valent boronates have both been proposed. Reactions of hypervalent
boron species have been studied by computational methods.3c,4,5
We report the isolation of a series of rhodium arylboronate and
diarylborinate complexes that undergo intramolecular transfer of
the aryl group from boron to rhodium by a â-aryl elimination
pathway.6 These studies uncover a new pathway to consider for
the mechanism of transmetalation in several catalytic processes.
Triethylphosphine-ligated rhodium boronate complexes were
prepared by treating the Rh(I) silylamido precursor {(PEt3)2Rh-
[N(SiMe3)2]}7 (1) with arylboronic acids 2a-e and added PEt3 at
room temperature (eq 1).
Figure 1. ORTEP diagram of {Rh(PEt3)3[OB(OH)(p-tolyl)]} (3b). Most
hydrogen atoms are omitted for clarity. Selected bond distances (Å) and
angles (deg): Rh-O(1) ) 2.102(2), O(1)-B ) 1.330(3), B-C(19) ) 1.593-
(4), B-O(2) ) 1.382(3), Rh-P(1) ) 2.336(1), Rh-P(2) ) 2.324(1), Rh-
P(3) ) 2.204(1), P(1)-Rh-P(3) ) 95.96(2), P(2)-Rh-P(3) ) 96.97(2),
O(1)-Rh-P(1) ) 80.21(5), O(1)-Rh-P(2) ) 87.37(5), Rh-O(1)-B )
134.3(2), O(1)-B-C(19) ) 125.3(2), O(1)-B-O(2) ) 121.3(3).
and was insoluble in common solvents, but is likely to be boroxin
oligomers {[OdB(OH)]n}.10 The closest transformations to the
â-aryl eliminations are the reactions of a palladium siloxide
complex11 and reaction of a Pt(II) arylboronate with boronic acid
and silver oxide.9 In contrast to complexes 3a-e, the platinum
boronates were stable in the absence of additives.
The proton exchange occurred smoothly to eliminate HN(SiMe3)2
and form the rhodium boronate complexes 3a-e. The para-
substituted aryl derivatives 3a-d were stable enough to be obtained
as crystalline solids in 45-76% isolated yields and were fully
characterized. The o-anisyl derivative 3e was unstable at room
temperature, but it formed in quantitative yield at lower temperatures
and was characterized in solution by NMR spectroscopic methods.
The structure of boronate complex 3b was determined by X-ray
diffraction (Figure 1). In the solid state, 3b adopts a distorted square-
planar geometry with P-Rh-O(1) angles of 80.21(5), 87.37(5),
and 175.24(5)° for P(1), P(2), and P(3), respectively. The O(1-
2)-B(1)-C(19-25) plane lies approximately perpendicular to the
rhodium coordination plane, and the dihedral angle between these
two planes is 83.4°. The Rh-O distance (2.102(2) Å) is slightly
longer than those in Rh(I) alkoxides (2.05-2.07 Å)8 but is very
close to the Pt-O distance (2.09 Å) in a related Pt(II) boronate.9
Complexes 3a-e underwent â-aryl elimination reactions at
ambient temperatures to afford the corresponding rhodium aryl
complexes 4a-e. These reactions occurred over the course of 0.5-1
h in the absence of added ligand. The rhodium-aryl complexes
were formed in 74-95% yield, as determined by 1H NMR
spectroscopy (eq 2). The boron product precipitated from solution
A moderate electronic effect was observed for the rate of aryl
group migration. The derivatives containing electron-donating groups
(3b, 3c) reacted slightly more slowly than those containing electron
withdrawing groups (3d). However, the ortho-substituted, electron-
rich 3e reacted much faster than the other members of the series.
These migratory aptitudes, including the fast rate for migration of
the o-anisyl group, are comparable to those for â-aryl eliminations
from isoelectronic PEt3-ligated Rh(I) iminyl complexes.12
The mechanism of the â-aryl elimination from p-tolyl derivative
3b in the presence of added PEt3 was investigated by kinetic
methods. Rate constants were measured by 1H NMR spectroscopy
for reactions at 70 °C containing an initial 0.014 M concentration
of 3b in cyclohexane. Reactions were conducted with concentrations
of added PEt3 varying from 0.014 to 0.112 M. A clear exponential
decay of 3b indicated that the reaction was first-order in rhodium.
A plot of 1/kobs versus [PEt3] (Figure S2 in Supporting Information)
9
1876
J. AM. CHEM. SOC. 2007, 129, 1876-1877
10.1021/ja068587q CCC: $37.00 © 2007 American Chemical Society

C O M M U N I C A T I O N S
showed that the reaction was inverse first-order in added PEt3. These
results are most consistent with a pathway that occurs by reversible
dissociation of PEt3 to form a 14-electron intermediate, followed
by â-aryl elimination to cleave the C-B bond. This mechanism
would be analogous to that for â-aryl elimination to cleave the C-N
and C-O bond in Rh(I) iminyl and alkoxo complexes reported
recently.8a,12 This mechanism would also parallel the classic one
for â-hydrogen elimination from square-planar alkoxo complexes.13
The silylamido Rh(I) precursor 1 also underwent reaction with
the diarylborinic acid (2-mesityl)2B(OH) (5) to afford the corre-
sponding bis(phospine) Rh(I) borinate complex, [(PEt3)2Rh[OB-
(Mes)2] (6) in 71% isolated yield (eq 3).14 This complex is unstable
in solution but reacted with 1 equiv of added PEt3 to quantitatively
form a more stable, tris(phospine) Rh(I) borinate complex [(PEt3)3-
Rh[OB(Mes)2] (7). Complex 7 was also prepared directly from
silylamide 1 and boronic acid 5 in the presence of added PEt3 in
82% isolated yield.
Heating of rhodium borinate 7 in cyclohexane at 80 °C led to
â-aryl elimination. The corresponding [(PEt3)3Rh(Mes)] (8) and
cyclic boroxin {[OdB(Mes)]3}15 (9) were formed in 87% and 91%
yields after 4 h (eq 4). Reactions in the presence of 2 equiv of
added PEt3 were much slower, and at higher temperatures the
mesitylrhodium product was unstable. Thus, quantitative rate studies
were not conducted, but these qualitative data suggest that this
reaction also occurs by initial, reversible dissociation of PEt3.
added activators. Kinetic studies are most consistent with â-aryl
elimination from 14-electron boronate and borinate intermediates.
This process appears competent to be a step in rhodium-catalyzed
chemistry of boronic acids and should be considered as a possible
pathway for transmetalation from boron to other late metals. Studies
of transmetalation from boron to palladium by this pathway are
ongoing.
Acknowledgment. Financial support for this work was provided
by NIH (NIGMS Grant GM-58108).
Supporting Information Available: Experimental procedures,
spectral data, and structural data (3b) (CIF and PDF). This material is
available free of charge via the Internet at http://pubs.acs.org.
References
(1) Recent reviews on transition metal-catalyzed organoboron chemistry: (a)
Miyaura, N.; Suzuki, A. Chem. ReV. 1995, 95, 2457. (b) Hayashi, H.;
Yamasaki, K. Chem. ReV. 2003, 103, 2829. (c) Miyaura, N. In Metal-
Catalyzed Cross-Coupling Reactions; Wiley: New York, 2004; p 41.
(2) For recent reviews on the general topic of transmetalations, see: (a)
Osakada, K. Curr. Methods Inorg. Chem. 2003, 3, 233. (b) Espinet, P.;
Echavarren, A. M. Angew. Chem., Int. Ed. 2004, 43, 4704.
(3) (a) Simpson, R. D.; Bergman, R. G. Organometallics 1992, 11, 3980. (b)
Hayashi, H.; Takahashi, M.; Takaya, Y.; Ogasawara, M. J. Am. Chem.
Soc. 2002, 124, 5052. (c) Nishikata, T.; Yamamoto, Y.; Miyaura, N.
Organometallics 2004, 23, 4317. (d) Nishihara, Y.; Onodera, H.; Osakada,
K. Chem. Commun. 2004, 192. (e) Suzaki, Y.; Osakada, K. Organome-
tallics 2006, 25, 3251.
(4) DFT calculations on boron-to-metal transmetalations: (a) Braga, A. A.
C.; Morgon, N. H.; Ujaque, G.; Maseras, F. J. Am. Chem. Soc. 2005,
127, 9298. (b) Goossen, L. J.; Koley, D.; Hermann, H. L.; Thiel, W. J.
Am. Chem. Soc. 2005, 127, 11102. (c) Goossen, L. J.; Koley, D.; Hermann,
H. L.; Thiel, W. Organometallics 2006, 25, 54. (d) Glaser, R.; Knotts, N.
J. Phy. Chem. A 2006, 110, 1295. (e) Braga, A. A. C.; Ujaque, G.; Maseras,
F. Organometallics 2006, 25, 3647.
(5) ESI-MS detection of potential intermediates in B/Pd transmetalations:
Aramend´ıa, M. A.; Lafont, F. J. Org. Chem. 1999, 64, 3592.
(6) An alternative way to isolate the actual aryl migration step would be to
prepare metal-boron complexes that allow intramolecular metal/boron
transmetalation. See the pioneering work by Echavarren and coworkers
on transmetalations of organotin and organosilicon compounds: (a) Mateo,
C.; Ferna´ndez-Rivas, C.; Echavarren, A. M.; Ca´rdenas, D. J. Organome-
tallics, 1997, 16, 1999. (b) Mateo, C.; Ferna´ndez-Rivas, C.; Ca´rdenas, D.
J.; Echavarren, A. M. Organometallics, 1998, 17, 3651.
(7) Zhao, P.; Krug, C.; Hartwig, J. F. J. Am. Chem. Soc. 2005, 127, 12066.
(8) (a) Zhao, P.; Incarvito, C. D.; Hartwig, J. F. J. Am. Chem. Soc. 2006,
128, 3124. (b) Zhao, P.; Incarvito, C. D.; Hartwig, J. F. J. Am. Chem.
Soc. 2006, 128, 9642.
(9) Pantcheva, I.; Nishihara, Y.; Osakada, K. Organometallics 2005, 24, 3815.
(10) 11B NMR spectra that were taken on the aqueous extract of the reaction
mixture showed boric acid B(OH)3 as the hydrolized boron product.
(11) Pd(II) alkenylsiloxide complexes have been proposed to be potential
transmetalation intermediates under fluoride-free conditions: Denmark,
S. E.; Sweis, R. F. J. Am. Chem. Soc. 2004, 126, 4876.
The transmetalation from boron to rhodium is a likely step in
the catalytic asymmetric Michael additions of arylboronic acids.1b,c
These catalytic processes are thought to occur by reaction of the
product enolate with water to form a rhodium hydroxide complex,
followed by transmetalation between the rhodium hydroxide and
the boronic acid.3b To test the competence of rhodium boronates
as intermediates in the transmetalation step, we monitored reactions
of the boronic acid with rhodium hydroxide and enolate complexes.
Treatment of the hydroxorhodium complex [(PEt3)2Rh(µ-OH)]2
(10)16 with boronic acid 2a and borinic acid 5 in the presence of
1
added PEt3 at room temperature eliminated H2O (observed by H
NMR spectroscopy) and formed rhodium boronate and borinate
complexes 3a and 7, respectively, in good yields (eq 5). Under
these conditions, there was no detectable hypervalent boron species,
such as {(PEt3)3Rh[B(Ph)(OH)3]} or {(PEt3)3Rh[B(Mes)2(OH)2]}.
This observation implies that metal-boronates can be intermediates
in the transmetalation of aryl groups to replace hydroxo ligands on
late metals.
In addition, boronic acid 2a reacted with the PEt3-ligated rhodium
enolate 1117 shown in eq 6, in the presence of added PEt3 to form
the same boronate 3a. These data imply that the transmetalation
can occur directly with the enolate complex without the interme-
diacy of the hydroxo complex.
(12) Zhao, P.; Hartwig, J. F. J. Am. Chem. Soc. 2005, 127, 11618.
(13) (a) Bryndza, H. E.; Calabrese, J. C.; Marsi, M.; Roe, D. C.; Tam, W.;
Bercaw, J. E. J. Am. Chem. Soc. 1986, 108, 4805. (b) Zhao, J.; Hesslink,
H.; Hartwig, J. F. J. Am. Chem. Soc. 2001, 123, 7220. (c) Vela, J.; Vaddadi,
S.; Cundari, T. R.; Smith, J. M.; Gregory, E. A.; Lachicotte, R. J.;
Flaschenriem, C. J.; Holland, P. L. Organometallics 2004, 23, 5226.
(14) Studies on metal dimesitylborinate complexes: (a) Weese, K. J.; Bartlett,
R. A.; Murray, B. D.; Olmstead, M. M.; Power, P. P. Inorg. Chem. 1987,
26, 2409. (b) Poulton, J. T.; Sigalas, M. P.; Floting, K.; Streib, W. E.;
Eisenstein, O.; Caulton, K. G. Inorg. Chem. 1994, 33, 1476.
(15) Anulewicz-Ostrowaska, R.; Lulin´ski, S.; Serwatowski, J.; Suwin´ska, K.
Inorg. Chem. 2000, 39, 5763.
(16) Prepared from the known compound [(COD)Rh(µ-OH)]2. See Supporting
Information for details.
In summary, we have isolated a series of tris(phosphine)
rhodium(I) arylboronate and diarylborinate complexes that allow
direct observation of intramolecular transmetalation from boron to
rhodium under mild conditions and without the participation of
(17) Slough, G. A.; Hayashi, R.; Ashbaugh, J. R.; Shamblin, S. L.; Aukamp,
A. M. Organometallics 1994, 13, 890.
JA068587Q
9
J. AM. CHEM. SOC. VOL. 129, NO. 7, 2007 1877