Phosphine/Sulfoxide-Supported Carbon(0) Complex

Article abstract of DOI:10.1002/chem.201705557

A new carbon(0) complex 2 with two different L ligands, a phosphine and a sulfoxide, was synthesized and fully characterized. This new type of carbone exhibits excellent coordination ability, in contrast to the related phosphine/sulfide-supported carbon(0

Full text of DOI:10.1002/chem.201705557

A Journal of
Accepted Article
Title: Phosphine/Sulfoxide-Supported Carbon(0) Complex
Authors: Mariana Lozano González, Laura Bousquet, Sophie
Hameury, Cecilio Alvarez Toledano, Nathalie Saffon-
Merceron, Vicenç Branchadell, Eddy Maerten, and Antoine
Baceiredo
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COMMUNICATION
Phosphine/Sulfoxide-Supported Carbon(0) Complex
[
a,b]
[a]
[a]
[b]
Mariana Lozano González,
Laura Bousquet, Sophie Hameury, Cecilio Alvarez Toledano,
[
c]
[d]
,[a]
,[a]
Nathalie Saffon-Merceron, Vicenç Branchadell, Eddy Maerten* and Antoine Baceiredo*
Abstract: A new carbon(0) complex 2 with two different L ligands, a
phosphine and a sulfoxide, was synthesized and fully characterized.
This new type of carbone exhibits excellent coordination ability, in
contrast to the related phosphine/sulfide-supported carbon(0)
complexes. Several organometallic complexes were isolated and, of
special interest, the av(CO) value of Rh(I)-dicarbonyl complex
indicates that 2 has a donor capability superior to classical NHCs.
second lone pair at the central carbon atom to stabilize electron-
deficient organometallic complexes thus obtaining high activities
[
15]
for hydrogenation reactions. Alcarazo used the four electron-
donor ability of carbodiphosphoranes II (L = PR ) to stabilize the
3
+
[16]
highly reactive dihydroborenium ion (BH
2
).
Finally, Ong
evidenced an unexpected -accepting ability of carbodicarbenes
V
resulting in an ambiphilic-type reactivity, allowing the
[
17]
activation of small molecules.
As a part of our program to design, synthesize and develop new
carbon(0) complexes, we report here the synthesis and the
[
1]
The discovery of the first stable carbenes almost 30 years ago
has initiated intensive research leading to deeper
understanding of physical and chemical properties of these
a
characterization of
a
new phosphine/sulfoxide-supported
carbon(0) complex 2 and its ability to act as an efficient ligand
for the preparation of transition metal complexes.
[
2]
divalent species. As a consequence, stable carbenes rapidly
became essential as synthetic tools, organocatalysts, and
[
3]
[4]
[5]
efficient ligands for transition-metal homogeneous catalysis. As
represented by N-heterocyclic carbenes (NHCs) I, the catalytic
activity of the corresponding NHC-metal-complexes relies mainly
on the electronic properties of I as strong electron-donating
auxiliary ligands. The related divalent carbon(0) II species (also
named carbones), bearing two lone pairs on the central carbon
[
6]
atom, discovered by Ramirez in the 60s, were considered as
such only very recently. Indeed, Frenking et al. have suggested
that, based on their electronic structure and chemical behavior,
these molecules are best described as a carbon atom in the
[
7]
oxidation state zero stabilized by two L-ligands. This vision has
shed new light on this family of compounds encouraging the
development of new carbon(0) complexes by combining various
Figure 1. Carbenes and carbon(0) complexes (for a better readability, formal
charges were omitted in III, IV, V and 2.
[
8]
types of L-ligands.
It is well established that carbon(0)
complexes such as cyclic carbodiphosphoranes (CDP) III, cyclic
bent allenes IV and carbodicarbenes V present a powerful
electron-donating ability, which is far stronger than that of
The phosphine/sulfoxide carbon(0) complex
prepared in two steps from the corresponding
chlorophosphonium and methyldiphenylsulfoxonium salts in
2
was
[
9]
classical NHCs I. Therefore, carbon(0) species have been
presence of 2 equivalents of a non-nucleophilic strong base
[
10]
used as ligands for the preparation of metal complexes
showing interesting catalytic activities.
[18]
(
1
LDA) (Scheme 1). In a second step, the deprotonation of salt
[
11-14]
Although the
was performed in THF solution at RT, either with potassium
robustness of the corresponding organometallics complexes still
deserves improvement, their catalytic efficiency often surpass
that observed with the related NHC-metal catalysts. Of particular
interest, Stephen recently took advantage of the presence of the
hydride (KH) or potassium hexamethyldisilazane (KHMDS)
leading to the selective formation of 2, which was isolated in
69 % overall yield.
[
a]
Dr. M. Lozano González, L. Bousquet, Dr. S. Hameury, Dr. E.
Maerten, Dr. A. Baceiredo
Université de Toulouse, UPS, and CNRS, LHFA UMR 5069
118 route de Narbonne, 31062 Toulouse (France)
E-mail: baceired@chimie.ups-tlse.fr; maerten@chimie.ups-tlse.fr
Dr. M. Lozano González, Prof. C. Alvarez Toledano,
Instituto de Química-UNAM, Circuito Exterior, Ciudad Universitaria,
Coyoacán C.P. 04510 Ciudad de México (México)
Dr. N. Saffon-Merceron
[
[
[
b]
c]
d]
Scheme 1. Synthesis of ylide 1 and phosphine/sulfoxide carbon(0) complex 2.
Université de Toulouse, UPS, and CNRS, ICT FR2599
118 route de Narbonne, 31062 Toulouse
Prof. V. Branchadell
Departament de Quimica, Universitat Autonoma de Barcelona
31
In the P NMR spectrum, 2 displays a signal shifted to
higher field (29.0 ppm) compared to 1 (45.0 ppm). The central
08193 Bellaterra (Spain)
1
carbon of 2 exhibits a doublet signal at  = 31.2 ppm ( JPC = 84.8
Supporting information for this article is given via a link at the end of
the document.
Hz) with a large coupling constant in agreement with a direct P-
C connectivity. The structures of both 1 and 2 were confirmed by
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COMMUNICATION
[
19]
X-Ray diffraction analysis (Figures 2 and 3). The P1-C1 bond
To gain more insight into the electronic structures of 1 and
2, DFT calculation were performed at the M06-2X/6-31G(d) level
of theory. The optimized geometries are consistent with the
experimental X-Ray data (See Sup. Info for complete
comparison). The variation of Wiberg bond indices ongoing from
1 to 2 (for P1-C1: +0.266, C1-S1: +0.241 and S1-O1: -0.089)
correlates with the measurement obtained from the X-Ray data
(for P1-C1: -0.0627 Å, C1-S1: -0.0610 Å and S1-O1:
length [1.6563(13) Å] in 2 is significantly shorter than in 1
1.7190(15) Å] and the value remains slightly longer than those
reported for CDPs (1.584 - 1.648 Å). The S1-C1 bond length
also undergoes significant shortening upon deprotonation [from
.6539(15) Å in 1 to 1.5929(14) Å in 2], this value is the shortest
[
[
20]
1
S-C bond length reported to date in the sulfur-stabilized carbone
[
8c,h,21]
series (1.602 – 1.713 Å).
bond lengths get slightly longer (ΔS-Xmax = + 0.02 Å). These
data clearly indicate the delocalization of p -lone pair at the
carbon center toward sulfoxide ligand. Similarly to the case of
The S1-O1, S1-C16, and S1-C22
[
22]
+0.0145 Å).
The central carbon atom in 2 bears a large

negative charge (-1.388) similarly to iminosulfane/phosphine-
[
8h]
carbone (-1.38). The two highest occupied molecular orbitals
(HOMO-1 nC, HOMO nC) correspond to the two lone pairs at
the central carbon in 2 (Figure 4). The HOMO-1, the in-plane -
lone pair, is partially deformed towards the sulfur atom of
[
7a]
carbodiphosphoranes,
the P-C-S angle remains almost
unchanged between the precursor 1 and carbone 2 [120.98(9)°
vs 120.74(8)° respectively], and this value is in the range of
those
observed
for
iminosulfane/phosphine-
or
sulfoxide ligand, suggesting a negative hyperconjugaison nC /
[
8a,h]
bis(iminosulfane)-carbones.
*(S-C or S-O)
.
Figure 4. Calculated frontier orbitals of 2 at the M06-2X/6-31G(d) level of
theory.
Figure 2. Molecular structure of 1. Thermal ellipsoids represent 30
probability. H atoms (except on C1) and counterion (TfO ) were omitted for
clarity. Selected bond lengths [Å] and angles [°]: S1-C1 1.6539(15), P1-C1
%
-
The nucleophilic character of
2 was experimentally
confirmed by an immediate reaction with methyl iodide, giving
raise to the corresponding C-methylated salt 3. The P NMR
spectrum indicates a selective reaction with a unique signal at 
1
.7190(15), S1-C16 1.7764(15), S1-C22 1.7771(16), P1-C10 1.7888(16),
3
1
S1-O1 1.4531(12), S1-C1-P1 120.98(9).
=
51.9 ppm. The methylation was confirmed by the presence of
two characteristic doublets at  = 1.72 ppm (JPH = 12.5 Hz) and
1
13
at  = 16.4 (d, JCP = 9.3 Hz) in the H and C NMR spectra
respectively. Compound 3 was isolated in crystalline form and its
structure was confirmed by X-Ray diffraction analysis (See
Supporting Information). The molecular structure of 3 shows a
significantly elongated S1-C1 bond [1.6717(16) Å] relative to that
of 2 [1.5929(14) Å], which is in good agreement with the loss of
one of the two lone pairs at the central carbon atom upon C-
methylation.
Figure 3. Molecular structure of 2. Thermal ellipsoids represent 30
%
probability. H atoms were omitted for clarity. Selected bond lengths [Å] and
angles [°]: S1-C1 1.5929(14), P1-C1 1.6563(13), S1-C16 1.7995(14), S1-
C22 1.7956(14), P1-C10 1.8083(13), S1-O1 1.4676(10), S1-C1-
P1 120.74(8).
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COMMUNICATION
Scheme 2. Methylation and complexation of 2.
phosphine/sulfoxide-carbone 2 was reacted with 0.5 equiv. of
[
RhCl(COD)]
2
, leading to the clean formation of rhodium(I)
complex 5 as indicated by a doublet at = 42.6 ppm (d, JPRh
=
3
1
13
The potential usefulness of phosphine/sulfoxide-carbone 2
2.7 Hz) in the P spectrum. In the C NMR spectrum, the
as ligand for transition metals was demonstrated by selective
central carbon atom appears at  = 16.3 ppm as a doublet of
doublet (JCP = 56.7 Hz, JCRh = 37.5 Hz). Complex 5 is stable in
solution at low temperature, but decomposes slowly at RT. The
corresponding Rh(I) dicarbonyl complex 6 was prepared by
bubbling carbon monoxide gas through a THF solution of 5 at -
2
reaction with two equivalents of [AuCl(SMe )] affording cleanly
the neutral gem-aurated complex 4, in good yield (68 %).
[
8b,23]
Similarly to carbodisphosphoranes and carbodicarbenes,
the formation of complex 4 demonstrates the ability of 2 to act as
3
1
a four-electron donor ligand. In the P NMR spectrum 4 displays
7
8 °C (Scheme 3). The formation of 6 was indicated by a color
3
1
a singlet signal at  = 41.2 ppm, while the central carbon atom
change from yellow to brown-red. The P spectrum indicates a
1
3
1
3
appears as a doublet at  = 35.8 ppm (JCP = 47.5 Hz) in
C
new doublet at  = 43.3 ppm (JPRh = 2.3 Hz) and in the C NMR
spectrum, the signal corresponding to the central carbon atom is
relatively deshielded at  = 20.8 ppm (JCP = 66.6 Hz, JCRh = 33.0
Hz) compared to 5.
complexes 5 and 6 were confirmed by X-ray diffraction analysis
Figures 6 and 7). In both complexes, P1-C1 [1.7070(14) Å (5)
and 1.709(2) Å (6)] and S1-C1 [1.6400(14) Å (5) and 1.654(2) Å
6)] bond lengths are very similar to those observed in 1 and 3,
NMR spectrum. Complex 4 has been isolated as colorless
crystals from a concentrated dichloromethane solution, and its
structure was unambiguously confirmed by X-Ray diffraction
analysis (Figure 5).
[
26]
The molecular structures of both
(
(
meaning that only one lone pair of the central carbon atom
interacts with the Rh center.
Scheme 3. Formation of Rh(I) complexes 5 and 6.
Figure 5. Molecular structure of 4. Thermal ellipsoids represent 30
%
probability. H and disordered atoms and solvent molecule (dichloromethane)
were omitted for clarity. Selected bond lengths [Å] and angles [°]: S1-C1
1
1
3
.737(4), P1-C1 1.781(4), C1-Au1 2.071(4), C1-Au2 2.056(4), P1-C10
.805(4), S1-C16 1.819(7), S1-C22 1.786(4), O1-S1 1.447(3), Au1-Au2
.018(1), Au1-Cl1 2.287(1), Au2-Cl2 2.289(1), S1-C1-P1 110.2(2), P1-
C1-Au1 109.92(19), Au1-C1-Au2 93.99(15), C1-Au1-Au2 42.81(11),
Au1-Au2-C1 43.20(11), C1-Au1-Cl1 176.22(11), C1-Au2-Cl2 172.52(11)
.
The C-Au bond lengths [2.056(4) and 2.071(4) Å] are
shorter than those observed in the related
carbodisphosphorane- and carbodicarbene-diaurated complexes
2.074, 2.078 Å and 2.080, 2.103 Å respectively). The aurophilic
(
interaction is classical with Au1-Au2 distance of 3.018(1) Å,
which is in the range of other gem-diaurated carbones (2.952 -
Figure 6. Molecular structure of 5. Thermal ellipsoids represent 30
probability. H atoms were omitted for clarity. Selected bond lengths [Å] and
angles [°]: S1-C1 1.6400(14), P1-C1 1.7070(14), C1-Rh1 2.1757(13), P1-C10
%
[
8b, 8h, 18c, 20]
3.143 Å).
Finally, the P1-C1 [1.781(4) Å] and the S1-
C1 [1.737(4) Å] bonds lengths are significantly longer than in 1,
typical for single bonds (P-C : 1.79 - 1.82 Å and S-C : 1.73 –
1.8144(14), S1-C16 1.7996(15), S1-C22 1.7928(15), O1-S1 1.4650(11), Rh1-
[
24]
Cl1 2.4503(4), S1-C1-P1 114.36(8), P1-C1-Rh1 125.80(7), Rh1-C1-
S1 118.60(7).
1
.75 Å) confirming that the two lone pairs are involved in the
formation of complex 4.
One established method for measuring the electron-donor
ability of ligands is based on the carbonyl stretching frequencies
[
25]
of
cis-[RhCl(CO)
2
L]
complexes.
Therefore,
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COMMUNICATION
are currently underway to extend the diversity of organometallic
complexes and in order to test their catalytic activities.
Acknowledgements
This work was supported by the CNRS and the Université de
Toulouse, UPS. We would also like to thank CONACyT México
207613-FOIINS-France project and Conacyt-México for the
Ph.D. grant extended to M.L-G. Financial support from the
Spanish Ministry of Economy and Competitiveness (grant
CTQ2016-77978-R) is acknowledged.
Keywords: carbon(0) complexes • phosphine • sulfoxide • ligand
•
-donor
Figure 7. Molecular structure of 6. Thermal ellipsoids represent 30
probability. H and disordered atoms and solvent (C D ) were omitted for clarity.
6 6
Selected bond lengths [Å] and angles [°]: S1-C1 1.654(2), P1-C1 1.709(2), C1-
Rh1 2.165(2), P1-C10 1.806(2), S1-C16 1.794(2), S1-C22 1.788(2), O1-S1
%
[
[
1]
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9
8
4.46(6), Cl1-Rh1-C29 85.06(8), C29-Rh1-C28 90.60(11), C28-Rh1-C1
9.95(9).
The IR spectrum of 6 shows the characteristic CO-stretching
frequencies with an average value of 2016 cm , which is in the
range of those observed for cyclic or acyclic bent allenes (2018
and 2014 cm
phosphine/sulfoxide carbone 2 appears to be stronger electron-
-1
[
3]
a) Carbene Chemistry: From Fleeting Intermediates to Powerful
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-1
[5b,
9b,
9c,
27]
respectively).
Therefore,
-1
donating ligand than classical NHCs (2060 – 2036 cm ) but
weaker compared to cyclic carbodiphosphoranes (2001 cm )
-1
[
9a, 28]
[4]
(
Figure 8).
2
988; d) A. Grossmann, D. Enders, Angew. Chem. Int. Ed. 2012, 51,
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[
5]
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1
Neutral  -Carbon Ligands, Vol. 30, XI ed. (Eds.: R. Chauvin, Y.
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Figure 8. Comparison of
RhCl(CO) L] complexes.
av(CO) stretching frequencies of cis-
[
2
[6]
7]
F. Ramirez, N. B. Desai, B. Hansen, N. McKelvie, J. Am. Chem. Soc.
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[
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In summary, we have successfully synthesized and
characterized an original phosphine/sulfoxide-carbone 2 easily
obtained from the corresponding cationic salt. As expected, the
introduction of the sulfoxide ligand dramatically enhances the
stability of this new carbon(0) complex. In comparison with
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previous phosphine/sulfide-carbone model,
2
exhibits an
excellent coordination ability and thus allowed the stabilization
and characterization of several organometallic complexes [Au(I),
Rh(I)]. The carbone character of 2 was demonstrated by the
isolation of neutral gem-aurated complex 4, establishing the
ability of ligand 2 to act as a four-electron donor. Moreover, the
electron-donating character of 2 is much stronger than that of
NHCs and we can expect that the corresponding transition-metal
complexes could exhibit interesting catalytic activities. Efforts
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Chemistry - A European Journal
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COMMUNICATION
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theory. Wiberg bond order increases for bonds that get shorter upon
deprotonation and vice versa. See supporting information.
and yldiides see selected reviews and references therein: a) "Transition
1
Metal Complexes of Neutral η -Carbon Ligands", In Top. Organomet.
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Chemistry - A European Journal
10.1002/chem.201705557
COMMUNICATION
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COMMUNICATION
A stable phosphine/sulfoxide carbone
was isolated and fully characterized
by NMR spectroscopy and by X-Ray
crystallography. This species exhibits
excellent coordination ability and the
M. Lozano González, L. Bousquet, S.
Hameury, N. Saffon-Merceron, C.
Alvarez Toledano, V. Branchadell, E.
Maerten* and A. Baceiredo*
O1
S1
C22
corresponding
complex indicates
nucleophilic character, in clear
Rh(I)-dicarbonyl
P1
Page No. – Page No.
a
strong
C16
C10
C1
Phosphine/Sulfoxide-Supported
Carbon(0) Complex
agreement
with
theoretical
calculations.
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