Reactivity of ortho-palladated phenol derivatives with unsaturated molecules: Insertion of nitriles into a late-transition-metal-carbon bond

Article abstract of DOI:10.1002/anie.200501202

(Chemical Equation Presented) Helpful neighbors: [Pd{2-(OH)C ₆H₄}I-(tmeda)] reacts at room temperature with excess RCN (R = Me, C₆F₅, CH₂=CH) and T|OTf (1 equiv) to give [Pd{1-O-2-[C(R)= NH]C₆H₄-κ²-O,N} (tmeda)]OTf (see scheme). The proximal OH group plays a crucial role in this first example of the insertion of a nitrile into a late-transition-metal-carbon bond. Tf=trifluoromethanesulfonyl, tmeda = N,N,N′,N′- tetramethylethylenediamine.

Full text of DOI:10.1002/anie.200501202

Angewandte
Chemie
catalytic metal-mediated conversions of organonitriles into
important organic compounds are currently being devel-
oped.[1,3] In contrast to other unsaturated molecules, such as
alkynes, alkenes, CO, or RNC, nitriles insert less easily into
metal–carbon bonds. Most of the known examples involve
nitriles RCN and early-transition or actinide metal organo-
À
À
complexes [M] R’ to give azaalkenylidene complexes [M]
[4,5]
=
N CRR’ upon insertion.
In a few cases, the azaalkenyli-
À =
dene ligand in [M] N C(R)CH2R’ rearranges by a 1,3-H shift
[5]
À
=
to the corresponding enamide [M] NHC(R) CHR’. Some
special cases involve low-valent transition-metal organocom-
À
plexes [M] CH2C(O)R’ that react at high temperature with a
nitrile RCN and PPh3 to give a k2-C,O-cyclometalated imino
complex [M] NHC(R)CHC(O)R’.[6] Another unusual case is
À
the reaction between the extremely reactive Fe2Mes4 (Mes =
2,4,6-Me3C6H2) and PhCN to give the dimer [{(PhCN)-
[7]
=
(Mes)Fe}2(m-N CPhMes)2]. Herein, we report a new type
of nitrile insertion that also represents the first example of the
À
insertion of a nitrile into a C M bond (in which M is a late-
transition element).
[Pd{2-(OH)C6H4}I(tmeda)] (tmeda = N,N,N’,N’-tetrame-
thylethylenediamine) reacts at room temperature with
excess RCN and 1 equivalent of TlOTf (OTf = CF3SO3) to
2
=
give [Pd{1-O-2-[C(R) NH]C6H4-k -O,N}(tmeda)]OTf [R =
=
Me (1), C6F5 (2), CH2 CH (3)] (Scheme 1). As many known
Insertion Reactions
DOI: 10.1002/anie.200501202
Reactivity of ortho-Palladated Phenol Derivatives
with Unsaturated Molecules: Insertion of Nitriles
into a Late-Transition-Metal–Carbon Bond**
Scheme 1. Reaction of [Pd{2-(OH)C6H4}I(tmeda)], excess nitrile, and
TlOTf (1 equiv).
JosØ Vicente,* JosØ Antonio Abad,
María-JosØ López-Sµez, and Peter G. Jones
stable alkyl– and aryl–palladium complexes contain a cis-
coordinated nitrile ligand,[8] we can assume that the ortho-
hydroxy group plays a crucial role in the process and that after
substitution of the iodo ligand by RCN (A in Scheme 2), the
following step B is the protonation of the nitrogen atom of the
nitrile. Unexpectedly, however, the usual nucleophilic attack
at the nitrile carbon atom by the oxygen function[1,2] to give
the addition product C does not occur. In our opinion, the
resonance form B’ contributes significantly to the electronic
structure of the protonated intermediate because of the
electron-withdrawing character of the positively charged
metal center and the electron-releasing nature of the neg-
atively charged oxygen substituent. Both favor the location of
a partial negative charge on the ipso carbon atom of the aryl
ligand. Therefore, our results can be explained through the
nucleophilic attack at the nitrile carbon by the ipso carbon
atom, probably via the four-membered metallacycle D.
Consequently, this insertion process differs from those
reported previously with other unsaturated molecules in the
role played by the ortho-hydroxy group, first in the proto-
Nitriles have a very rich coordination chemistry because they
are activated by some metals towards nucleophilic or electro-
philic attack.[1,2] Based on this reactivity, stoichiometric and
[*] Prof. Dr. J. Vicente, Dr. J. A. Abad, M.-J. López-Sµez
Grupo de Química Organometµlica
Departamento de Química Inorgµnica
Facultad de Química, Universidad de Murcia
Aptdo. 4021, 30071 Murcia (Spain)
Fax: (+34)968-364-143
E-mail: jvs1@um.es
Prof. Dr. P. G. Jones
Institut für Anorganische und Analytische Chemie
Technische Universität Braunschweig
Postfach 3329, 38023 Braunschweig (Germany)
[**] This work was supported by the Ministerio de Educación y Ciencia
(MEC, Spain) and the FEDER (EU) by contract CTQ2004–05396.
M.-J.L.S. is grateful to the MEC for a grant.
Supporting information for this article is available on the WWW
under http://www.angewandte.org or fromthe author.
Angew. Chem. Int. Ed. 2005, 44, 6001 –6004
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6001

Communications
Scheme 2. Proposed mechanism for the reaction of
[Pd{2-(OH)C6H4}I(tmeda)] with nitriles.
Figure 1. Thermal ellipsoid plot (50% probability) of 1. Selected bond
lengths [Š] and angles [8]: Pd–O1 1.9655(14), Pd–N1 1.9800(16), Pd–
N2 2.0685(16), Pd–N3 2.0710(16), N1–C7 1.297(3), O1–C1 1.313(2);
O1-Pd-N1 91.58(6), O1-Pd-N2 87.55(6), N1-Pd-N3 95.55(7), N2-Pd-N3
85.62(6), C7-N1-Pd 128.74(14), C1-O1-Pd 126.31(12), N1-C7-C2
123.24(17), N1-C7-C8 117.75(18), C2-C7-C8 118.95(17).
nation of the nitrile ligand and then in the generation of a
partial negative charge on the ipso carbon atom of the aryl
ligand.
Recently, the reaction of acrylonitrile with [PdMe-
(NMe2Ph)L2]+, [{PdMe(L2)}2(m-Cl)]+ (L2 = various bidentate
N-donor ligands),[9] and [Pd(O,N)Me(NCMe)] (O,N =
Grubbs salicylaldiminato and related diazene ligands)[10]
were reported to give a-cyanopropyl derivatives, that is, the
insertion products of the olefinic part of the nitrile into the
À
Pd Me bond. In all cases, the first step was, as we propose in
our case, the N-coordination of the nitrile but the difference
from our result (complex 3) proves to be the crucial role
played by the hydroxy group in our reactions. We have
À
reported that CO and olefins insert into the C Pd bond of
[Pd{2-(OH)C6H4}I(tmeda)] without intervention of the hy-
droxy group.[11]
The insertion of a nitrile group into an aryl–Pd bond has
been postulated as a step in the mechanism of the synthesis of
aryl ketones by the Pd-catalyzed reaction of arenes with
nitriles at 75–1008C.[12] The proposed subsequent step is the
protonation of the resulting imido complex to give an imine.
Our results suggest that these two steps could occur in the
reverse order.
Figure 2. Thermal ellipsoid plot (30% probability) of 2. Selected bond
lengths [Š] and angles [8]: Pd–N1 1.9769(13), Pd–O1 1.9804(12), Pd–
N2 2.0636(15), Pd–N3 2.0698(14), O1–C1 1.308(2), N1–C7 1.288(2);
N1-Pd-O1 90.91(5), N1-Pd-N2 94.21(6), O1-Pd-N3 89.00(5), N2-Pd-N3
85.88(6), C1-O1-Pd 125.59(10), C7-N1-Pd 127.26(11), N1-C7-C2
125.08(15), N1-C7-C11 115.63(14), C2-C7-C11 119.29(14).
Complexes similar to 1–3 were prepared by the reaction of
1) [Ru(L2)2(CO3)] (L2 = bpy (2,2’-bipyridyl), phen (1,10-phe-
[13]
=
nanthroline)) with p-{CH2N C(Me)(2-OHC6H4)}2C6H4,
2) [Ru(PPh3)3Cl2] with oximes of salicylaldehyde, 2-hydroxy-
acetophenone, or 2-hydroxynaphthylaldehyde,[14] and
3) aqueous ammonia, 2-hydroxo-4-methoxyacetophenone,
and copper(ii) salts.[15] Therefore, in the known complexes
the main skeleton of the ligand is preformed in the organic
reagent. Complexes 1–3 contain ligands of the same family as
that present in Grubbs nickel catalysts.[16]
The crystal structures of the three complexes were solved
by X-ray diffraction studies (Figures 1–3).[17] They show a
distorted square-planar geometry at the palladium center,
with normal bond lengths and angles. The chelate ring
involving N1 and O1 is essentially planar in 1 but becomes
less planar for 2 and 3 (mean deviations 0.03, 0.08, 0.11 Š).
À
Cation/anion N H···O(O2)SCF3 hydrogen bonds are
observed.
In conclusion, we have reported the first examples of the
insertion of nitriles into a late-transition-metal–carbon bond.
The process involves the insertion of an alkyl (Me), aryl
(C6F5), or vinyl nitrile into an aryl–palladium bond. The
insertion is assisted by the protonation of the nitrile nitrogen
atom by the ortho-hydroxy group present in the aryl ligand
and thus represents a new type of insertion reaction.
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Angewandte
Chemie
1H NMR (400 MHz, CDCl3): d = 8.38 (s, 1H; NH), 7.46 (dd, 1H,
3JHH = 8.2 Hz, 4JHH = 1.6 Hz; C6H4), 7.29 (ddd, 1H, 3JHH = 6.8 Hz,
3JHH = 8.5 Hz, 4JHH = 1.7 Hz; C6H4), 6.96–6.89 (m, 2H; C6H4, CH2
=
CH), 6.64 (ddd, 1H, 3JHH = 7.0 Hz, 3JHH = 8.1 Hz, 4JHH = 1.1 Hz,
=
=
C6H4), 5.83(m, 2H; CH CH, CH2 CH), 2.91 (s, 6H; Me), 2.89 (s,
2
4H; CH2 (tmeda)), 2.75 ppm (s, 6H; Me); 13C{1H} NMR (400 MHz,
=
CDCl3): d = 171.05 (C), 164.64 (C), 134.77 (CH (C6H4)), 133.32 (CH2
=
CH), 132.34 (CH (C6H4)), 126.73( CH2 CH), 121.10 (CH (C6H4)),
115.85 (CH (C6H4)), 120.58 (C), 115.85 (CH (C6H4)), 63.30 (CH2
(tmeda)), 60.46 (CH2 (tmeda)), 50.91 (Me), 49.36 ppm (Me);
elemental analysis: calcd for C16H24N3O4F3SPd: C 37.11, H 4.67, N
8.11, S 6.19; found: C 36.86, H 4.78, N 8.11, S 6.03; single crystals were
grown by slow diffusion of Et2O into a solution of 3 in CH2Cl2.
Received: April 5, 2005
Published online: August 22, 2005
Figure 3. Thermal ellipsoid plot (30% probability) of 3. The anion has
been omitted. Selected bond lengths [Š] and angles [8]: Pd–O1
1.966(2), Pd–N1 1.983(2), Pd–N3 2.054(2), Pd–N2 2.060(2), O1–C1
1.319(3), N1–C7 1.287(4), C8–C9 1.310(4); O1-Pd-N1 90.11(11), N1-
Pd-N3 95.10(11), O1-Pd-N2 88.65(9), N3-Pd-N2 86.12(10), C1-O1-Pd
123.44(18), C7-N1-Pd 128.7(2), N1-C7-C2 121.4(3), N1-C7-C8 116.8(3),
C2-C7-C8 121.8(3).
Keywords: insertion · N ligands · neighboring-group effects ·
nitriles · palladium
.
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Experimental Section
General procedure: The nitrile (1.15 mmol) and TlOTf (81 mg,
0.23mmol) was added to a solution of [Pd{2-(OH)C 6H4}I(tmeda)][11]
(100 mg, 0.23mmol) in CH 2Cl2 (15 mL). The resulting mixture was
stirred for 4 h at room temperature, the suspension was filtered over
celite, the yellow solution was concentrated (3mL), and Et 2O
(10 mL) was added, which resulted in the precipitation of a solid.
The precipitate was filtered, washed with Et2O (3” 5 mL), and dried
to give the corresponding complex as a yellow solid.
1: Yield: 90 mg, 78%; m.p. 1648C; LM = 143 WÀ1 cm2 molÀ1. IR:
n˜ = 3275 n(NH), 1605 cmÀ1 n(C N); H NMR (300 MHz, CDCl3): d =
1
=
8.71 (s, 1H; NH), 7.47 (dd, 1H, JHH = 8.3Hz, 4JHH = 1.5 Hz; C6H4),
3
7.27 (ddd, 1H, 3JHH = 6.9 Hz, 3JHH = 8.4 Hz, 4JHH = 1.6 Hz; C6H4), 6.91
(dd, 1H, 3JHH = 8.4 Hz, 4JHH = 1 Hz; C6H4), 6.64 (ddd, 1H, JHH
=
3
6.9 Hz, 3JHH = 8.1 Hz, 4JHH = 1.6 Hz; C6H4), 2.92 (s, 6H; Me
(tmeda)), 2.85 (s, 4H; CH2), 2.74 (s, 6H; Me (tmeda)), 2.68 ppm (s,
3H; Me (MeCN)); 13C{1H} NMR (100 MHz, CDCl3): d = 172.11 (C),
163.24 (C), 134.30 (CH), 130.93 (CH), 121.04 (CH), 120.92 (C), 115.93
(CH), 63.30 (CH2), 60.39 (CH2), 50.92 (Me (tmeda)), 48.99 (Me
(tmeda)), 24.53ppm (Me (MeCN)); elemental analysis: calcd for
C15H24N3O4SF3Pd: C 35.62, H 4.78, N 8.31, S 6.34; found: C 35.31, H
4.67, N 8.21, S 6.09; single crystals were grown by slow diffusion of n-
hexane into a solution of 1 in CH2Cl2.
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2: Yield: 125 mg, 83%; m.p. 218 8C (decomp.); LM
=
125 WÀ1 cm2 molÀ1
;
IR: n˜ = 3193 n(NH), 1601 cmÀ1 n(C N);
=
1H NMR (400 MHz, [D6]acetone): d = 9.75 (s, 1H; NH), 7.39 (ddd,
3
3
4
1H, JHH = 6.9 Hz, JHH = 8.6 Hz, JHH = 1.7 Hz; C6H4), 7.11 (dd, 1H,
3JHH = 8.3Hz, 4JHH = 1 Hz; C6H4), 7.04 (dd, 1H, 3JHH = 8.6 Hz, 4JHH
=
=
1 Hz; C6H4), 6.58 (ddd, 1H, 3JHH = 7 Hz, 3JHH = 8.30 Hz, JHH
4
1.1 Hz; C6H4), 3.14 (s, 4H; CH2), 2.96 (s, 6H; Me), 2.91 ppm (s, 6H;
Me); 13C{1H} NMR (100 MHz, [D6]acetone): d = 166.65 (C), 161.16
(C), 136.80 (CH), 133.27 (CH), 122.64 (CH), 120.70 (C), 117.15 (CH),
64.15 (CH2), 61.45 (CH2), 51.31 (Me), 49.67 ppm (Me); elemental
analysis: calcd for C20H21N3O4SF8Pd: C 36.52, H 3.22, N 6.39, S 4.87;
found: C 36.41, H 3.20, N 6.43, S 4.80; single crystals were grown by
slow diffusion of n-hexane into a solution of 2 in acetone.
3: Yield: 100 mg, 84%; m.p. 1698C (decomp.); LM
=
100 WÀ1 cm2 molÀ1
;
IR: n˜ = 3293 n(NH), 1603cm À1 n(C N);
=
Angew. Chem. Int. Ed. 2005, 44, 6001 –6004
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Communications
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[17] CCDC-267823( 1), -267824 (2), and -267825 (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.
Data were recorded at À1408C on a Bruker SMART 1000 CCD
diffractometer in w and f scan modes to 2qmax 608 with
monochromated MoKa radiation (l = 0.71073Š). Absorption
corrections were based on multiple scans. Structures were
refined on F2 by using the program SHELXL-97 (G. M.
Sheldrick, University of Göttingen). Hydrogen atoms were
refined using rigid methyl groups or a riding model, except for
NH hydrogen atoms, which were refined freely. The triflate
group of 3 is disordered over two positions in the ratio 4:1.
Crystal data for 1: C15H24F3N3O4PdS, monoclinic, a = 8.4900(6),
b = 12.0785(8), c = 19.4179(14) Š, b = 95.648(4)8, U = 1981.6 Š3,
space group P21/n, Z = 4, m(MoKa) = 1.10 mmÀ1, 36424 reflec-
tions measured, 5789 unique (Rint = 0.026); refinement pro-
ceeded to wR(F2) 0.073(all data), R(F) 0.027 for 253parame-
ters; max. D1 1.3eŠ À3. Crystal data for 2: C20H21F8N3O4PdS,
orthorhombic, a = 8.9198(6), b = 11.4033(8), c = 23.1269(14) Š,
U = 2352.4 Š3, space group P212121, Z = 4, m(MoKa) = 0.98 mmÀ1
,
49530 reflections measured, 6890 unique (Rint = 0.027); refine-
ment proceeded to wR(F2) 0.047 (all data), R(F) 0.019, Flack
À3
parameter À0.009(11) for 342 parameters; max. D1 0.7 eŠ
.
Crystal data for 3: C16H24F3N3O4PdS, orthorhombic, a =
8.0816(11), b = 13.332(2), c = 19.339(3) Š, U = 2083.6 Š3, space
group P212121, Z = 4, m(MoKa) = 1.04 mmÀ1, 44074 reflections
measured, 6095 unique (Rint = 0.047); refinement proceeded to
wR(F2) 0.063(all data), R(F) 0.029, Flack parameter À0.01(2)
for 334 parameters and 307 restraints; max. D1 1.0 eŠÀ3. The
Supporting Information for this article contains a listing of all
refined and calculated atomic coordinates, anisotropic thermal
parameters, and bond lengths and angles for complexes 1–3.
6004 www.angewandte.org
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 6001 –6004