Dimetallic dioxygen activation leading to a doubly oxygen-bridged dirhodium complex

Article abstract of DOI:10.1002/anie.200463073

Ready cleavage of dioxygen and its selective insertion into Rh-alkene bonds occurs in the presence of [{Rh(PhN₃Ph)-(C₈H ₁₂)}_n] (n = 1 and 2). The structure of the resulting dirhodadioxetane complex (see picture) and kinetic measurements support a dimetallic mechanism for this process that occurs with 100% atom economy. (Figure Presented)

Full text of DOI:10.1002/anie.200463073

Angewandte
Chemie
À
O O Activation
Dimetallic Dioxygen Activation Leading to a
Doubly Oxygen-Bridged Dirhodium Complex**
Cristina Tejel,* Miguel A. Ciriano, Eduardo Sola,
M. Pilar del Rꢀo, Gustavo Rꢀos-Moreno,
Fernando J. Lahoz, and Luis A. Oro
Catalytic oxygenation constitutes an important method of
converting readily available alkenes into chemicals with high
added value. These oxygenations should preferably use the
cheap and environmentally benign dioxygen as oxidant, and
incorporate both oxygen atoms into the substrate molecules,
thus optimizing atom economy.[1] However, with the excep-
tion of the Wacker process, such practical use of oxygen seems
nowadays restricted to a few heterogeneous catalysts,[2]
[*] Dr. C. Tejel, Prof. M. A. Ciriano, Dr. E. Sola, M. P. del Rꢀo,
Dr. G. Rꢀos-Moreno, Prof. F. J. Lahoz, Prof. L. A. Oro
Departamento de Quꢀmica Inorgꢁnica
Instituto de Ciencia de Materiales de Aragꢂn
C.S.I.C.-Universidad de Zaragoza
50009 Zaragoza (Spain)
Fax: (+34)976-761-187
E-mail: ctejel@unizar.es
Prof. L. A. Oro
Instituto Universitario de Catꢁlisis Homogꢃnea
Universidad de Zaragoza
50009 Zaragoza (Spain)
[**] The generous financial support from MCyT(DGI)/FEDER (Projects
BQU2002-00074 and BQU2003-05412) is gratefully acknowledged.
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DOI: 10.1002/anie.200463073
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although important progress towards this goal has been
Exposure of 1 to dioxygen in toluene at 293 K and
atmospheric pressure gave the dinuclear dirhodadioxetane
complex [{Rh(PhN3Ph)(OC8H12)}2] (2, Scheme 1) in 90%
yield. Volumetric gas-burette measurements with O2 indi-
cated a consumption of 0.5 molecules of gas per atom of
rhodium (0.51 Æ 0.03 equiv), thus showing that all the reacting
dioxygen was incorporated into 2. The molecular structure of
complex 2 (Figure 1)[12] confirms that, despite the presence of
reported in the chemistry of soluble metal complexes.[3]
A recent review by Gal and co-workers[4] analyzes in
detail the reactivity of rhodium and iridium complexes
relevant to alkene oxygenation. Often, the use of peroxides
as oxidants leads to facile monooxygenation reactions,
À
through C O bond-forming steps, to afford reactive 2-metal-
laoxetane intermediates.[5–7] In contrast, the more scarce C O
À
bond-forming reactions using dioxygen are assumed to
involve the initial formation of 3-metalla-1,2-dioxolanes,[8]
from which the evolution to oxygenated products seems to
follow unselective routes and most often requires the
presence of sacrificial reductants.[4] An exception to this
inconvenient behavior has been reported for the 1,5-cyclo-
octadiene dianionic complex [Ir(P3O9)(C8H12)]2À, in which the
formation of a 2-metallaoxetane intermediate from 0.5 molar
equivalents of dioxygen has been suggested to be the
[9]
À
consequence of a dimetallic O O bond cleavage. Herein
we provide further evidence for the feasibility of this atom-
economic dimetallic oxygenation route, by describing the
facile formation of a dinuclear 2-metallaoxetane compound
from dioxygen and an equilibrium mixture of the mono- and
dinuclear rhodium complexes [Rh(PhN3Ph)(C8H12)] (1M) and
[{Rh(m-PhN3Ph)(C8H12)}2] (1D).
The bis(phenyl)triazenide rhodium(i) compound [{Rh-
(PhN3Ph)(C8H12)}n] (1), first reported by Knoth,[10] was easily
prepared by treating [{Rh(m-OMe)(C8H12)}2] with bis-
(phenyl)triazene in toluene. By comparison with rhodium
triazenide compounds previously characterized by X-ray
diffraction studies,[11] it was likely that the red solid obtained
from the reaction was a dinuclear compound with bridging
triazenide ligands. However, the NMR spectra of the
compound dissolved in [D6]benzene is indicative of an
equilibrium mixture of the mono- and dinuclear complexes
shown in Scheme 1. The dissociation equilibrium constant Keq
was estimated by NMR spectroscopic analysis to be
0.092 molLÀ1 at 293 K.
Figure 1. Solid-state structure of the dinuclear complex 2. Selected
bond distances [ꢄ] and angles [8]: Rh(1)-N(1) 2.040(3), Rh(1)-N(3)
2.347(3), Rh(1)-O(1) 2.076(3), Rh(1)-O(1’) 2.064(3), Rh(1)-C(2)
2.037(4), Rh(1)-C(5) 2.223(4), Rh(1)-C(6) 2.206(4); N(1)-Rh(1)-O(1)
167.42(11), N(3)-Rh(1)-C(2) 167.62(13), O(1’)-Rh(1)-C(5) 162.51(12).
potentially bridging triazenide ligands, the dinuclear structure
is held by bridging oxygen atoms—a feature by itself
suggestive of a dimetallic activation of dioxygen. Moreover,
among the few 2-metallaoxetane moieties resulting from
insertion of oxygen atoms into metal–alkene bonds,[5,6,9]
compound 2 constitutes the first example of a bridging one.
Complex 2 was found to be kinetically unstable in
solution, slowly evolving to [{Rh(PhN3Ph)(HO-C8H11)}n] (3n,
Scheme 1). The transformation was found to be complete in
about three days at room temperature in dichloromethane. As
confirmed by the solid-state structure shown in Figures 2 and
3,[13] the transformation involves the isomerization of the (h2-
Scheme 1. Equilibration between the mono- and dinuclear complexes,
and the products of the reaction of 1 with dioxygen.
Figure 2. Polymeric chains formed in the crystal structure of complex
3n by the two independent dimeric units.
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Figure 3. Solid-state structure of one of the two independent dimeric
moieties of 3n. Selected bond distances [ꢄ] and angles [8] (mean
values for the four equivalent parameters)[11]: Rh-N(1) 2.121(4), Rh-
N(3) 2.139(4), Rh-O(1) 2.359(3), Rh-C(18) 2.051(5), Rh-C(13) 2.163(5),
Rh-C(14) 2.080(5), Rh-C(15) 2.163(5); N(1)-Rh-C(13) 168.8(2), N(3)-
Rh-C(15) 170.4(2), O(1)-Rh-C(18) 175.8(2).
Figure 4. Top: Examples of O2 uptake experiments in solutions of 1 in
toluene ([Rh]0 =6.18ꢅ10-3 molLÀ1) at 293 K; : P=1.00 bar;
*
k-O,C-OC8H12) ligand of 2 into a hydroxyallyl (h3-k-C-
(HO)C8H11) isomeric ligand (Scheme 1). Such an isomer-
ization has been proposed to involve a metal-mediated
&
: P=0.65 bar. Bottom: Dependence of the initial reaction rates upon
the initial concentration of 1 (left) and dependence of the pseudo-first-
order rate constants kobs upon the O2 partial pressure (right).
À
activation of an allylic C H bond followed by the transfer
Table 1: Kinetic data for the reaction of 1 with dioxygen.
of the activated hydrogen atom to the alkoxy oxygen
atom.[5,6,9]
[Rh]0 [ꢅ10À3 m]
P(O2) [bar]
v0 [mmol O2 sÀ1
]
kobs [ꢅ10À3 sÀ1
]
The solid-state structure of 3n consists of a polymeric chain
8.48
8.08
6.18
4.24
1.94
8.08
8.08
8.08
0.97
0.97
0.97
0.97
0.97
1.07
0.62
0.32
1.56ꢅ10À4
1.45ꢅ10À4
1.14ꢅ10À4
8.84ꢅ10À5
3.76ꢅ10À5
3.76ꢅ10À5
3.76ꢅ10À5
3.76ꢅ10À5
1.34
1.27
1.29
1.28
1.27
1.43
0.83
0.37
À
of mononuclear complexes (Figure 2) connected by Rh O
À
bonds (mean Rh O(1) bond lengths 2.359(3) ꢀ). Such bonds
are long and presumably fragile, since they take place at a
rhodium coordination position strongly labilized by the large
trans effect of a s-sp3 carbon atom. Therefore, it seems
unlikely that such a polymeric structure could remain in
solution.
Accordingly, the NMR spectra of solutions of 3n are
indicative of two equivalent phenyl groups, a feature hardly
compatible with the polymeric structure, but likely for a
potentially fluxional 16-electron RhIII fragment.
to be the kinetically relevant species in this oxygenation. The
dependence of the pseudo-first-order rate constants kobs upon
dioxygen pressure confirms that the oxygenation rate is also
first order in dioxygen.
The dioxygen activation reaction leading to complex 2 has
been investigated kinetically by O2-uptake experiments on
solutions of 1 in toluene at 293 K. The initial concentrations of
1 in these solutions, expressed as concentrations of rhodium
atoms [Rh]0, were about 5 ꢁ 10À3 molLÀ1. At these concen-
trations and below, the equilibrium between 1D and 1M is
greatly shifted toward the mononuclear compound, so that
the concentration of 1M approaches a linear dependence upon
that of rhodium, namely [1M] ꢀ [Rh]. In turn, that of 1D is
better described by the expression of the equilibrium
constant, namely [1D] ꢀ [Rh]2/Keq, thus depending upon the
square of the rhodium concentration. Figure 4 and Table 1
shows examples for the reaction profiles obtained under
constant pressure of dioxygen, which correspond well to those
expected for a first-order dependence upon complex concen-
tration. The logarithmic representation of the initial reaction
rates (v0) versus [Rh]0 indicates a linear dependence, there-
fore confirming the mononuclear complex 1M, rather than 1D,
These kinetic data discount any mechanism initiated by
reaction of dioxygen with the dinuclear complex 1D, and
evidence a reaction of dioxygen with the mononuclear
complex 1M as the most likely rate-determining step in the
process (Scheme 2). This conclusion is compatible with the
mechanism previously proposed by Klemperer and co-work-
ers for the aforementioned singular example of dioxygen
activation.[9] Adaptation of this proposal to our reaction in
Scheme 2 would result in a mononuclear complex coordinat-
ing dioxygen, which undergoes the attack by an intact
mononuclear complex (1M) to complete a dimetallic dioxygen
cleavage. In our system, such a dimetallic activation step
seems to be fast; likely as a consequence of the unsaturated
character of the triazenide–rhodium complex 1M. The coor-
3À
dination requirements of the Klempererꢂs tridentate P3O9
ancillary ligand were proposed to favor the splitting of the
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mental analysis (%) calcd for C40H44N6O2Rh2: C 56.75,
H 5.24, N 9.93; found: C 57.01, H 5.03, N 9.79; 1H NMR
(CDCl3, 258C) (assigned from 1H,1H-COSY spectrum)
d = 7.47 (m, 8H, Hortho-C6H5), 7.36 (t, J(H,H) = 7.5 Hz,
4H) and 7.32 (t, J(H,H) = 8.2 Hz, 4H; Hmeta-C6H5), 7.11
(t, J(H,H) = 7.3 Hz, 2H) and 7.04 (t, J(H,H) = 7.2 Hz,
2H; Hpara-C6H5), 6.25 (t, J(H,H) = 7.4 Hz, 2H) and 5.00
=
(m, 2H; CH), 5.25 (t, J(H,H) = 6.9 Hz, 2H; HC-O-
Rh), 4.78 (m, 2H; HC-Rh), 2.62 (m, 2H), 2.38 (m, 2H),
1.91 (m, 8H), 1.50 (m, 2H) and 0.80 (m, 2H; CH2);
Scheme 2. Proposed mechanism for the reaction of dioxygen with 1.
13C{1H} NMR (CDCl3, 258C) d = 149.6 and 148.4 (Cipso
-
C6H5), 129.1 and 128.6 (Cmeta-C6H5), 123.7 and 123.3
(Cpara-C6H5), 119.2 and 117.7 (Cortho-C6H5), 100.5 (d,
dinuclear species resulting after dioxygen activation, a feature
not required in our triazenide oxygenation product, which
remains dinuclear (Scheme 2).
=
J(C,Rh) = 8 Hz) and 95.7 (d, J(C,Rh) = 7 Hz; CH), 94.6 (d, J-
(C,Rh) = 2 Hz; HC-O-Rh), 33.6 (d, J(C,Rh) = 17 Hz; HC-Rh), 33.9,
27.8, 24.8 and 20.6 (CH2); MS: m/z (%): 847 (12) [M+], 423 (100) [(M/
2)+].
Although the above mechanism could be within the reach
of other unsaturated mononuclear complexes or fragments,
our preliminary investigation of rhodium compounds isoelec-
tronic and very closely related to 1 indicates that this dioxygen
activation is far from general. Actually, the complex [{Rh(m-
PhNCHNPh)(C8H12)}2],[13] which remains dinuclear at all
concentration ranges, did not undergo reaction with dioxygen
under the conditions described for 1, while the mononuclear
species [Rh(PhNC(Ph)NPh)(C8H12)],[14] which does not form
detectable dimers in solution, did not activate dioxygen
either. These observations might suggest a correlation
between the ability of unsaturated mononuclear fragments
to reversibly form dinuclear species in solution and its activity
in these dioxygen cleavage reactions. Whether or not this
correlation exists is currently being investigated within our
search for oxygenation catalysts, which can benefit from such
facile, selective, and atom-economic dioxygen dimetallic
activation.
3: An orange solution of 2 (100 mg, 0.12 mmol) in CH2Cl2
(10 mL) became green over 72 h in an argon atmosphere. Concen-
tration of the solution to about 2 mL and addition of hexane (10 mL)
afforded the product as a green solid, which was separated by
filtration and dried under vacuum. Yield: 70 mg (70%). Elemental
analysis (%) calcd for C20H22N3O1Rh1: C 56.75, H 5.24, N 9.93; found:
C 56.85, H 5.23, N 9.75; 1H NMR (CDCl3, 258C): (assigned from
1H,1H-COSY spectrum) d = 7.56 (d, J(H,H) = 7.8 Hz, 4H; Hortho
-
C6H5), 7.34 (t, J(H,H) = 7.8 Hz, 4H; Hmeta-C6H5), 7.06 (t, J(H,H) =
7.2 Hz, 2H; Hpara-C6H5), 5.15 (m, 2H; H4 and H6), 4.01 (t, J(H,H) =
8.7 Hz, 1H; H5), 3.52 (m, 1H; H1), 2.68 (m, 1H; H8), 2.36 (d, J(H,H) =
9.0 Hz, 1H; OH), 2.03 (m, 3H; H2a, H3a, H7a), 1.32 (m, 1H; H7b), 1.27
(m, 1H; H3b), 0.67 (m, 1H; H2b); MS: m/z (%): 423 (100) [M+].
Kinetic measurements: Dioxygen uptake experiments were
performed in an apparatus consisting of a (7.99 mL) stainless-steel
gas reservoir triply connected to a high-pressure dioxygen source, a
pressure transmitter, and an electronic pressure meter/controller
(EL-Press, Bronkhorst HI-TEC). The outlet of the pressure con-
troller was connected to a 100-mL reaction flask, also connected to a
Schlenk manifold to allow for manipulation of the reaction and
degassing. In a typical reaction, a solution of 1 at the desired
concentration in toluene was transferred to the reaction flask,
degassed in vacuo over 30 s, and then exposed to dioxygen at the
desired total pressure. The pressure was programmed at the computer
connected to the pressure controller. The reaction flask was shaken
vigorously during reaction. Consumption of dioxygen was registered
as a pressure decrease in the closed reservoir, by means of the
pressure transmitter, at intervals of 15 s. The pressure decrease was
converted into the moles of dioxygen consumed by using the
precalibrated volume of the reservoir and considering an ideal gas
behavior. Initial rates were obtained through a least-square fitting of
the initial 10% of the reactions. Pseudo-first-order rate constants kobs
were calculated by fitting the experimental reaction profiles to
exponentials. The toluene vapor pressure at the temperature of the
Experimental Section
1: The addition of PhNNNHPh (165.7 mg, 0.84 mmol) to a yellow
solution of [{Rh(m-OMe)(cod)}2] (203.4 mg, 0.42 mmol; cod = cyclo-
octa-1,5-diene) in toluene (10 mL) produced a red solution from
which a red solid precipitated in a few minutes. Hexane (5 mL) was
added after 30 min to complete the precipitation of the solid. The
solid was filtered under argon, washed with hexane (2 ꢁ 4mL), and
vacuum-dried. Yield: 290.8 mg (85%). Elemental analysis (%) calcd
for C20H22N3Rh: C 58.97, H 5.44, N 10.32; found: C 59.19, H 5.34, N
10.31; 1H NMR ([D6]benzene, 258C) for 1M: d = 7.33 (brd, J(H,H) =
7.7 Hz, 4H), 7.14 (t, J(H,H) = 6.9 Hz, 4H) and 6.93 (tt, J(H,H) = 7.4,
1.1 Hz, 2H; C6H5), 4.32 (brs, 4H, CH), 2.05 (m, 4H, CH2exo), 1.36 (q,
=
J(H,H) = 7.9 Hz, 4H, CH2endo); for 1D: d = 7.77 (brs, 8H), 7.23 (t,
J(H,H) = 8.3 Hz, 8H) and 7.03 (tt, J(H,H) = 7.4, 1.1 Hz, 4H; C6H5),
=
4.64 (brs, 4H) and 4.11 (brs, 4H; CH), 2.76 (m, 4H) and 2.18 (m,
4H; CH2exo), 1.70 (q, J(H,H) = 7.7 Hz, 4H) and 1.47 (q, J(H,H) =
7.9 Hz, 4H; CH2endo); 13C{1H} NMR ([D6]benzene, 258C) for 1M: d =
149.5 (Cipso-C6H5), 129.2 (Cmeta-C6H5), 124.1 (Cpara-C6H5), 117.2 (Cortho
-
=
C6H5), 80.3 (d, J(C,Rh) = 12 Hz, CH), 30.6 (CH); for 1D: d = 152.9
(Cipso-C6H5), 128.4 (Cmeta-C6H5), 124.9 (Cpara-C6H5), 124.1 (Cortho
-
=
C6H5), 87.6 (br) and 76.8 (br; CH), 31.1 and 30.8 (CH); MS: m/z
(%): 814 (20) [M+] (1D), 407 (100) [M+] (1M).
2: A suspension of [{Rh(PhNNNPh)(C8H12)}n] (150.0 mg) in
toluene (8 mL) was stirred in an oxygen atmosphere for 2 h. The
initial dark red suspension evolved to an orange solution, which was
concentrated to about 3 mL. Hexane (15 mL) was added to complete
the precipitation of the solid, which was filtered off, washed with
hexane (2 ꢁ 5 mL), and vacuum-dried. Yield: 156 mg (90%). Ele-
system was considered in calculating dioxygen partial pressures.[16]
.
Received: December 27, 2004
Revised: March 2, 2005
Published online: April 21, 2005
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À
observed reflections) and wR2 = 0.1737. Data/restrains/parame-
Keywords: metallacycles · N ligands · O O activation ·
oxidation · rhodium
.
ters 12544/42/901; GOF = 0.998. All residual peaks above
1 eꢀÀ3 were found in close proximity to the rhodium metal
and have no chemical sense.
[14] P. Piraino, G. Tresoldi, F. Faraone, J. Organomet. Chem. 1982,
224, 305.
[15] F. J. Lahoz, A. Tiripicchio, M. Tiripicchio-Camellini, L. A. Oro,
M. T. Pinillos, J. Chem. Soc. Dalton Trans. 1985, 1487.
[16] TRC Thermodynamic Tables, Vol. VIII, p. Kb-3290.
[1] D. H. R. Barton, The Activation of Dioxygen and Homogeneous
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[2] W. N. M. Van Leeuwen, Homogeneous Catalysis, Kluwer Aca-
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[3] a) S. S. Stahl, Angew. Chem. 2004, 116, 3480; Angew. Chem. Int.
Ed. 2004, 43, 3400; b) “Catalysis by Metal Complexes”: Advan-
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Dordrecht 2003; c) A. L. Gavrilova, C. J. Qin, R. D. Sommer,
A. L. Rheingold, B. Bosnich, J. Am. Chem. Soc. 2002, 124, 1714.
[4] B. De Bruin, P. H. M. Budzelaar, A. W. Gal, Angew. Chem. 2004,
116, 4236; Angew. Chem. Int. Ed. 2004, 43, 4142.
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D. Feichtinger, D. A. Plattner, Chem. Eur. J. 2001, 7, 416; b) B.
De Bruin, M. J. Boerakker, J. A. W. Verhagen, R. De Gelder,
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Concolino, Chem. Commun. 2000, 1681.
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[12] Crystal data for 2·3C7H8: C40H44N6O2Rh2·3C7H8, Mr = 1123.04,
prismatic crystal (0.16 ꢁ 0.05 ꢁ 0.05 mm), triclinic, space group
¯
P1, a = 9.7616(11), b = 11.5598(13), c = 12.4273(14) ꢀ, a =
86.458(2), b = 68.865(2), g = 87.552(2)8, V= 1305.2(3) ꢀÀ3, Z =
1, 1calcd = 1.429 gcmÀ3, F(000) = 582.0, T= 100(2) K, MoKa radi-
ation (l = 0.71073 ꢀ, m = 0.682 mmÀ1). Data collected with a
Bruker SMART APEX CCD diffractometer. Of 15557 mea-
sured reflections (2q: 3.5–558, w scans 0.38), 5903 were unique
(Rint = 0.0406); a multiscan absorption correction was applied
(SADABS program) with min./max. transmission factors of
0.932/0.955. Structure solved by Patterson and difference-Four-
ier maps; refined using SHELXTL. A disordered toluene
molecule was found in the asymmetric unit. Final agreement
factors were R1 = 0.0506 (5226 obs. reflections, F2 > 4s(F2)) and
wR2 = 0.1086; data/restrains/parameters 5903/0/454; GOF =
1.112. CCDC-258836 (2) and CCDC-258837 (3) contain the
supplementary crystallographic data for this paper. These data
can be obtained free of charge from the Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[13] Crystal data for 3: C20H22N3ORh, Mr = 423.31, monoclinic, space
group P21/n, a = 10.7068(11), b = 16.5017(18), c = 40.470(4) ꢀ,
b = 95.299(2)8, V= 7119.7(13) ꢀÀ3, Z = 16, 1calcd = 1.580 gcmÀ3
,
F(000) = 3456, T= 100(2) K, MoKa radiation (l = 0.71073 ꢀ, m =
0.972 mmÀ1). Data collected as described for 2 with an irregular
prism (0.084 ꢁ 0.054 ꢁ 0.054 mm). Of 38220 measured reflections
(2q: 2–508), 12544 were unique (Rint = 0.1048); a multiscan
absorption correction was performed (SADABS program) with
min./max. transmission factors of 0.923/0.942. Structure solution
and refinement as described for 2. Two independent, but
chemically equivalent, dimeric complexes were found in the
asymmetric unit. Final agreement factors were R1 = 0.068 (6315
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