MS-TOFstudyoftheformationofthiolato-bridgedrhodiumoligomers

Article abstract of DOI:10.1002/ejic.200901201

The complex [Cp*Rh(μ-SPh)₃RhCp*]Cl was used as a starting material to synthesize various oligomeric materials of the general formula [Cp *Rh(μ-SPh)_x(μ-Cl)_3-x(Rh(μ-SPh) ₃}_n,RhCp*] (x = 1 to 3; n = 1 to 4), which are formally formed by insertion of nRh(SPh)₃ units into one μ-Rh-SPh. bond. The insertion of Ir(SPh)₃ was also observed to generate the heterotrimetallic species. All complexes were observed by using HRMS-TOF and [Cp*Rh(μ-SPh)₃Rh(μ-SPh)₃RhCp*]Cl, [3⁺]Cl, was characterized, by using X-ray crystallography.

Full text of DOI:10.1002/ejic.200901201

FULL PAPER
DOI: 10.1002/ejic.200901201
MS-TOF Study of the Formation of Thiolato-Bridged Rhodium Oligomers
Josée Boudreau,[a] Jérôme Grenier-Desbiens,[a] and Frédéric-Georges Fontaine*[a]
Keywords: Rhodium / S ligands / Mass spectrometry / Oligomerization / Cluster compounds
The complex [Cp*Rh(µ-SPh)3RhCp*]Cl was used as a start-
ing material to synthesize various oligomeric materials of the
insertion of Ir(SPh)3 was also observed to generate the
heterotrimetallic species. All complexes were observed by
using HRMS-TOF and [Cp*Rh(µ-SPh)3Rh(µ-SPh)3RhCp*]Cl,
[3+]Cl, was characterized by using X-ray crystallography.
general
formula
[Cp*Rh(µ-SPh)x(µ-Cl)3–x{Rh(µ-SPh)3}n-
RhCp*] (x = 1 to 3; n = 1 to 4), which are formally formed
by insertion of nRh(SPh)3 units into one µ-Rh–SPh bond. The
achieved.[13] To gain more insight on the possibility of such
transformations, time-of-flight (TOF) high-resolution mass
spectrometry (HRMS) studies were undertaken.[14]
Introduction
Polynuclear thiolato complexes of transition metals have
been widely studied for their structural, chemical, and elec-
tronic properties,[1] and as models for active centers in bi-
omolecules.[2] Many µ-thiolato-bridged metal oligomers of
the general formula [M(µ-SR)x]n have been reported, where
x = 1–4, with a wide variety of metals, oxidation states, and
ancillaries.[3] More specifically, the dimeric species
Results and Discussion
The complex [Cp*Rh(µ-SPh)3RhCp*]Cl ([1+]Cl) was
used as a substrate and was synthesized by adding thio-
phenol to a refluxing solution of [Cp*RhCl2]2 in technical-
grade ethanol, as described by Chérioux and co-workers for
the synthesis of [Cp*Rh(µ-p-SC6H4OH)3RhCp*]Cl
(Scheme 1).[9] The HRMS spectrum of a solution of [1+]Cl
in CH2Cl2 shows the single ion [Cp*Rh(µ-SPh)3RhCp*]+
[CpRh(µ-p-SC6H4Me)3RhCp]+ (Cp
=
η5-C5H5)[4] and
[Cp*Rh(µ-SR)3RhCp*]+ (Cp* = η5-C5Me5) have been re-
ported for RhIII where R = Ph, iBu, allyl,[5] Me,[6] H,[7] or
fluorinated aromatics.[8] Further functionalization of the
bridging thiolato group for specific purposes was also ac-
complished by esterification with R = p-C6H4OH[9] or Su-
zuki coupling with R = p-C6H4Br.[10]
1
(1+) (m/z = 803.08), as expected. The H NMR spectrum
in [D]chloroform exhibits multiplets in the aromatic region
corresponding to the ortho hydrogen atoms of the thiophen-
olato ligands at δ = 7.82–7.77 and to the meta and para
hydrogen atoms at δ = 7.40–7.33, as well as a singlet at δ =
1.34 accounting for the 30 protons of the two Cp* ligands.
Although the rhodium centers in each of these complexes
are 18-electron saturated species, the thiolato ligands can
shift from a bridging to a terminal position, giving access
to free coordination sites that can become available for in-
coming ligand coordination. For example, the binding of a
substrate can occur in the complex CpMo(µ-SMe)3(µ-Cl)-
MoCp by opening of a chlorido bridge by controlled redox
chemistry.[11] Of course, other factors, such as pH, can mod-
ify the coordination mode of the thiolato ligand.[12] It was
therefore expected that under the correct experimental con-
ditions, the addition of n equivalents of [Rh(SPh)3][3a] to
triply bridged thiolato binuclear Cp*RhIII complexes would
yield new thiolato bridges that would form oligomeric clus-
ters with added n[Rh(SPh)3]. Such stepwise control could
eventually lead to the formation of hybrid metal–organic
polymers if good control of the insertion process was
1
This is in perfect accordance with the H NMR spectro-
scopic data for complex 1+, which has previously been char-
acterized as the triflate salt [1+]OTf.[5]
Scheme 1. Synthesis of dinuclear complex [Cp*Rh(µ-SPh)3RhCp*]-
Cl ([1+]Cl).
The ethanol solution proves perfectly adequate to obtain
[1+]Cl cleanly, as only 1+ was observed (m/z = 803.08,
100%) by HRMS after heating [1+]Cl for 48 h at reflux with
RhCl3·xH2O (x = 2 or 3) and PhSH (3 equiv.). However,
heating a solution [1+]Cl at reflux in toluene, where the salt
is not totally soluble, and then dissolving the residues in
[a] Département de Chimie, Université Laval,
1045 Avenue de la Médecine, Québec, Québec, Canada,
G1V 0A6
Fax: +1-418-656-7916
E-mail: frederic.fontaine@chm.ulaval.ca
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.200901201.
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MS-TOF Study of the Formation of Thiolato-Bridged Rhodium Oligomers
dichloromethane, affords by HRMS species [Cp*Rh(Cl)(µ- ditions, only 1+ was observed when an aliquot of the solu-
SPh)2RhCp*]+ (2-Cl1+; m/z = 729.04, 30%) in addition to tion was diluted in CH2Cl2 and analyzed by HRMS (m/z =
1+ (m/z = 803.08, 70%; Scheme 2). The low dielectric con- 803.08). Therefore, as stated previously, toluene was chosen
stant of toluene compared to that of ethanol suggests that as the solvent of choice for reactions with [1+]Cl. Addition
the neutral complex [Cp*Rh(Cl)(µ-SPh)2Rh(SPh)Cp*] of tBuSH (3 equiv.) to [1+]Cl in toluene resulted in a very
1+Cl is favored in toluene and could show as the [M –SPh] slow exchange of thiol. Only trace amounts of [Cp*Rh(µ-
peak in the mass spectrum. Similar neutral binuclear S-tBu)(µ-SPh)2RhCp*]+ (m/z = 783.11) (2-tBuS1+) were ob-
rhodium(III) Cp* complexes are know in which the rho- tained after 48 h in refluxing toluene.
dium centers are bridged by two thiolato ligands and each
Under the same reaction conditions, however, an ex-
contains one nonbridging chlorido ligand either in a syn[6b] change between thiophenolato and p-bromothiophenolato
or anti conformation.[7] In addition, the cationic binuclear ligands occurs to give a mixture of [1+]Cl (30%), [Cp*Rh(µ-
analogue [CpRh(µ-p-SC6H4Me)2(µ-Cl)RhCp]+ has been re- S-p-BrC6H4)(µ-SPh)2RhCp*]+ (m/z = 880.99, 20%; 2-p-
ported with the weakly coordinated SbCl6 counteranion.[4a] BrC6H4-S1+),
[Cp*Rh(µ-S-p-BrC6H4)2(µ-SPh)RhCp*]+
It should be noted, however, that if the species observed (m/z = 960.90, 27%; 2-p-BrC6H4-S2+), and [Cp*Rh(µ-S-p-
(m/z = 729.04) corresponds to a cationic complex, it has to Br-C6H4)3RhCp*]+ (m/z = 1038.81, 15%; 2-p-BrC6H4-S3
;
+
contain a phenylthiolato counteranion. Whereas it is much Scheme 3). The protonation of the phenylthiolato ligand by
less likely to observe a phenylthiolato counteranion rather more acidic p-BrC6H4SH and the coordination of the con-
than chlorido or SbCl6, the formation of a cationic ana- jugate base of the latter mercaptan is therefore favored, as
logue of [1+]Cl having a bridging chloride ligand and a expected.[12e]
thiophenolato anion [Cp*Rh(µ-Cl)(µ-SPh)2RhCp*]SPh
[2-Cl1+]SPh cannot be discarded, as a few transition-metal
complexes are known to have such phenylthiolato counter-
ions.[15]
Scheme 2. Formation of neutral complex 1+Cl or cationic complex
+
2-Cl1
.
A similar solvent effect was observed by Maitlis and co-
workers, where the position of the equilibrium between the
ionic [Cp*Rh(µ-SArf)3RhCp*][Cp*Rh(SArf)3] (Arf = C6F5)
and neutral Cp*Rh(SArf)2 complexes depended on the po-
larity of the solvent.[8] The implication of these observations
is that in nonpolar solvents, one of the thiolato bridge op-
ens, thus leaving one coordination site available for further
bonding interactions with the chloride counteranion or
other nucleophiles in its environment. Therefore, it should
be possible to observe chain growing of an inorganic pre-
cursor through the controlled addition of [Rh(SR)3]n units.
Scheme 3. Ligand exchange of [1+]Cl with p-BrC6H4SH to form
[Cp*Rh(µ-SPh)3–x(µ-S-p-BrC6H4)xRhCp*]Cl {x = 1, [2-p-BrC6H4-
S1+]Cl; x = 2, [2-p-BrC6H4-S2+]Cl; and x = 3, [2-p-BrC6H4-S3+]Cl}.
Formation of Oligomers
After the addition of one equivalent of rhodium(III)
chloride and three equivalents of thiophenol to a solution
of [Cp*Rh(µ-SPh)3RhCp*]Cl, [1+]Cl, in toluene, the reac-
tion mixture was heated under reflux for 48 h. It should be
noted that in most of these reactions, an aliquot of the tolu-
ene solution was taken and diluted in methylene chloride
Ligand Exchange
Polar solvents, such as ethanol, water, and DMF, seem for HRMS analysis. Unless stated otherwise, the products
to inhibit any ligand exchange or addition reactions. In- exhibit poor solubility, and a solid residue is present in the
[3a]
deed, after mercaptans or [Rh(SPh)3]n
are added to a reaction flask, which can account for more than 70% of
solution of [1+]Cl and heated for 48 h under refluxing con- the overall yield of material. However, when dissolving the
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J. Boudreau, J. Grenier-Desbiens, F.-G. Fontaine
FULL PAPER
residual solid in dichloromethane, the product distribution Table 1. Distribution of oligomers formed by addition of
[RhClx(SPh)3–x] units to [1+]Cl.
observed by HRMS does not differ significantly from the
[b]
Entry[a]
1+
[%]
Rh2
[%]
3+
[%]
Rh3
[%]
4+
Rh4 Other[c]
one in the original aliquot of the toluene solution. (See the
Supporting Information for HRMS data supporting this
statement) NMR spectroscopy proves to be unreliable to
get chemical information on this system for two reasons.
First, the low solubility of the solids in usual NMR solvents
in most of the experiments makes the acquisition of good
data and the isolation of each species difficult. Also, the
solutions obtained contain complex mixtures of many spe-
cies that all have very similar signatures to the starting ma-
terials. This results in very broad resonances in the 1H
NMR spectra and very weak or absent resonances in the
13C{1H} NMR spectra, even with over 8000 acquisitions
(1H and 13C{1H} NMR spectra for a typical oligomeriza-
tion reaction along with the corresponding HRMS spec-
trum are given in the Supporting Information). The only
[%]
[%]
[%]
1
2
3
4
5
6
7
8
9
10
35
13
3
76
78
44
0
0
74
10
77
37
3
82
96
70
19
65
74
10
1
3
15
3
0
2
6
1
6
0
14
35
76
6
0
Ͻ1
1
0
0
0
1
0
3
4
8
18
2
5
20
3
10
2
2
0
17
50
20
6
2
24
4
4
6
11
7
11
16
34
50
0
[a] See the Supporting Information for complete distribution of
products and detailed reaction conditions. [b] Rhx: Content of spe-
cies containing x rhodium atoms, including the parent X+ species.
[c] Other species include Rh5 and Rh6 as well as unidentified com-
pounds with m/z values ranging from 600 to 2000 amu.
1
species that could be identified by H NMR spectroscopy
is [3+]Cl, which has a single resonance for the Cp* region
at a chemical shift of δ = 1.27 ppm.
The HRMS spectrum in CH2Cl2 of the previously men- were under 5 ppm. (See the Supporting Information for
tioned reaction reveals many new species, among which the HPLC chromatogram and HRMS data) Trace amounts of
anticipated compound [Cp*Rh(µ-SPh)3Rh(µ-SPh)3Rh- compounds were also observed, whose m/z ratios corre-
Cp*]Cl, [3+]Cl, as the cationic ion [Cp*Rh(µ-SPh)3Rh(µ- spond to the penta- and hexanuclear thiolato-bridged rho-
SPh)3RhCp*]+ (3+, m/z = 1233.02) in a 1% yield only dium analogues of 3+ each containing two Cp* ligands,
(Table 1, Entry 1). The species containing one or two and, respectively, one or two chlorido ligands, [5-Cl1,2+],
chlorido ligands, [3-Cl1+] (m/z = 1158.98) and [3-Cl2+] (m/z and two or three chlorido ligands, [6-Cl2,3+], (Table 1, En-
= 1084.93), were also observed in 12 and 1% yield, respec- try 7). Possible structures of these complexes are depicted
tively, as well as the tetrameric complex with one chlorido in Scheme 5, although the exact structures, particularly the
ligand, [Cp*Rh(µ-SPh)2ClRh(µ-SPh)3Rh(µ-SPh)3RhCp*]+, position of the chloride ligands, cannot be deducted from
[4-Cl1+] (m/z = 1588.92), in 4% yield (Scheme 4). Addition the HRMS data. It can be speculated that the acid pro-
of one more equivalent of RhCl3 and three equivalents of tonates the thiophenolato ligand, therefore helping to open
thiophenol to this reaction mixture shifts the equilibrium a coordination site for chloride coordination to form the
towards tri-, tetra-, and pentanuclear rhodium species after neutral analogue, which should have better solubility in tol-
heating for another 24 h under refluxing conditions uene. Dilution of this reaction mixture in excess ethanol
(Table 1, Entry 2). This shows the possibility of controlling (10ϫ the volume) once again resulted in the displacement
the distribution of the oligomers by stepwise addition of the of the product distribution towards the dimeric species
reagents. The yields for the tri- and tetranuclear compounds (Table 1, Entry 8), putting forward the dynamic process at
after heating at reflux for 48 h are higher if RhCl3 and hand. When the reaction was carried out in a biphasic sys-
PhSH are stirred in methanol under reflux for 2 h and dried tem (toluene/water, 1:1) with NBu4Br as a phase-transfer
[3a]
to give an orange powder of oligomeric [Rh(SPh)3]x be- agent, a distribution where the thiolate ligands are favored
fore adding to the solution of [1+]Cl (Table 1, Entry 3). In over the chloride ligands was observed (Table 1, Entry 9).
this last reaction mixture, addition of thiophenol (3 equiv.) Finally, high yields in trinuclear compounds (50%) can be
does not result in the replacement of the chlorido ligands obtained by heating [1+]Cl, RhCl3, and thiophenol in xy-
by thiolato as expected. Instead it shifts the product distri- lene under reflux; however, a large amount of decomposi-
bution towards the binuclear species (Table 1, Entry 4).
Just like the coordinating solvents inhibit the chain grow- to 2000 is obtained (34%) (Table 1, Entry 10).
ing process, an excess amount of thiol or coordinating According to the proposed reaction scheme, it could be
tion to unidentifiable compounds of mass ranging from 600
bases, such as NEt3, also prevent the insertion of RhX3 (X possible to form heterometallic complexes by using the
= Cl or SR) species (Table 1, Entry 5; NEt3) even after heat- same strategy. Indeed, the addition of one equivalent of
ing at reflux for 12 d (Table 1, Entry 6). The addition of IrCl3 and three equivalents of PhSH to a solution of [1+]Cl
three equivalents of HCl (2% in Et2O), on the other hand, in toluene with HCl resulted in the insertion of the IrIII
favors insertion and greatly helps to increase the solubility fragment to give [Cp*Rh(µ-SPh)3Ir(µ-SPh)3RhCp*]+ [3Ir+]
of the resulting mixture. Indeed, a clean red solution is ob- (m/z = 1323.08, Ͻ1%) as well as the chloride-containing
tained after 48 h in refluxing toluene. The HRMS spectrum compound [3Ir-Cl1+] (m/z = 1249.03, 12%), albeit in low
of this solution reveals di-, tri-, and tetrarhodium species, yields (Scheme 6). It should be noted, however, that the ad-
[2-Cl2+], [3-Cl0,1,2,3+], and [4-Cl0,1,2,3+], most of which were dition of iron(III) chloride did not yield any insertion prod-
separated by HPLC and identified by HRMS; all errors uct.
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MS-TOF Study of the Formation of Thiolato-Bridged Rhodium Oligomers
Scheme 4. Formation of oligomers by stepwise insertion of Rh(SPh)3–xClx units into dinuclear cation 1+. The chlorido-containing species
are depicted as cationic species bearing bridging chlorido ligands; however, as previously discussed they may also exist in their neutral
form containing an additional chlorido or phenylthiolato ligand, in which case the species observed by HRMS would be [M – Cl] or
[M –SPh], respectively.
Structure of [3+]Cl
trimetallic structure has all Rh atoms aligned (the Rh–Rh–
Rh angle is 180°), where the two terminal metal centers
have piano-stool conformation and with the central atom
adopting a pseudo-octahedral geometry. The Rh–S dis-
tances on the terminal rhodium atoms vary from 2.377(3)
to 2.420(3) Å, whereas the central rhodium atoms have Rh–
S distances that vary from 2.350(3) to 2.385(3) Å. The
phenyl rings of bridging thiophenolato ligands are rotated
It was possible to isolate single crystals of complex [3+]-
Cl, which were analyzed by X-ray crystallography.[16] The
ORTEP diagram is shown in Figure 1. The complex crys-
tallizes in the P21/c space group with Z = 4, but with two
independent molecules. For each of the molecules, the cen-
tral rhodium atoms are located on inversion centers. The
Eur. J. Inorg. Chem. 2010, 2158–2164
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J. Boudreau, J. Grenier-Desbiens, F.-G. Fontaine
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Scheme 5. Putative structures of the penta- and hexanuclear complexes [5-Cl1,2+] and [6-Cl2,3+]. The exact position of the chlorido ligands
on the chain is unknown as is its bridging or terminal position, as these complexes were identified on the basis of HRMS results.
Two types of disorder were observed in this crystal struc-
ture, accounting for the relatively high R factor (5.96%).
First, on one of the complexes, the Cp* ring has rotational
disorder. Additionally, it was possible to observe in the
Fourier map the presence of large Q peaks in proximity to
the rhodium centers that were attributed to the sulfur
atoms. The refinement of the occupation for the two inde-
pendent molecules gave ratios of 85:15 and 90:10 between
the sulfur atoms of the thiophenolato ligands that were
originally assigned and the residual Q peaks. Although no
new phenyl ring was assigned to the minor sulfur compo-
nents, the orientation of the phenyl ring suggests that in
Scheme 6. Formation of [Cp*Rh(µ-SPh)3Ir(µ-SPh)3RhCp*]+ [3Ir+]
some of the molecules, the thiophenolato ligands adopt a
and [Cp*Rh(µ-SPh)2ClIr(µ-SPh)3RhCp*]+ [3Ir-Cl1+] by insertion
counterclockwise orientation relative to the major compo-
of an Ir fragment into [1+]Cl.
nent (Figure 2). Therefore, no good model for the phenyl
rings of the minor components was found to withstand the
by an average angle of 29.4° from the plane formed by the
three sulfur atoms in fac position of the terminal Rh atoms.
Interestingly, there is no significant π stacking between the
thiophenolato ligands within a molecule.
structure refinements.
Figure 1. ORTEP view of [3+]Cl showing the numbering scheme
adopted. Anisotropic atomic displacement ellipsoids for the non-
hydrogen atoms are shown at the 50% probability level. Hydrogen
atoms were removed for clarity. The symmetry transformation used
to generate equivalent atoms is –x, –y, –z.
Figure 2. ORTEP view of one of the Rh(SPh)3 fragments of [3+]Cl
in the fac conformation. The Q peaks that were labeled as sulfur
atoms show possible disorder where the thiophenolate ligands are
in a counterclockwise orientation compared to the original model.
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MS-TOF Study of the Formation of Thiolato-Bridged Rhodium Oligomers
tions; results of HPLC separation of the complexes and their char-
Conclusions
acterization with relative errors; crystallographic details for [3+]Cl.
The complex [Cp*Rh(µ-SPh)3RhCp*]Cl shows a propen-
sity to open up a coordination site in nonpolar solvents and
under acidic conditions to favor the insertion of nRh(SPh3)3
units to form [Cp*[Rh(µ-SPh)3]nRhCp*]Cl and its chlorido
derivatives. The oligomeric material formed, which consists
of species having up to six rhodium atoms, were observed
by using HRMS-TOF. Although the isolation and the puri-
Acknowledgments
We are grateful to the Natural Sciences and Engineering Research
Council of Canada (NSERC), the Canada Foundation for Innova-
tion (CFI), Le Fonds québécois de la recherche sur la nature et les
technologies (FQRNT-Québec), and Université Laval for financial
fication of these complex mixtures prove to be quite diffi- support. J. B. is grateful to NSERC for a scholarship. We thank
Johnson Matthey for the gift of RhCl3·xH2O.
cult on the scale that the reactions were carried out on,
it is nevertheless possible to use HPLC to observe them
individually. The crystal structure of [3+]Cl confirms a lin-
ear trimeric species. Although similar coordination environ-
ments could be obtained with species having more than
three metal atoms, no structural proof could be obtained
that a similar arrangement is present in higher rhodium-
containing clusters. Current studies are aimed at the isola-
tion of larger species to confirm their solid-state structures
and at increasing the selectivity in the distribution of the
products.
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Experimental Section
The complex [Cp*Rh(µ-SPh)3RhCp*]Cl, [1+]Cl, was prepared ac-
cording to a literature procedure for [Cp*Rh(µ-p-SC6H4OH)3-
RhCp*]Cl.[9] The HRMS analyses were performed with an Agilent
6210 Time-of-flight LC–MS with an electrospray ion source. Sam-
ples for HRMS analysis were prepared by taking a 10-µL aliquot
of the desired solution and diluting it in dichloromethane (1 mL),
or by dissolving a few milligrams of solid material in dichlorometh-
ane (1 mL), after which the solutions were filtered (0.2 µm) for di-
rect injection. 1H NMR spectra were recorded with a Varian Inova
NMR AS400 spectrometer at 400.0 MHz.
For the ligand exchange reactions, the thiol (3 equiv.) was added
to [1+]Cl (10 mg, 0.012 mmol) in a round-bottomed flask in the
appropriate solvent (10 mL), after which the solution was heated
to reflux, and the samples were taken for HRMS analysis at 24-h
intervals.
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0.036 mmol) were added to [1+]Cl (10 mg, 0.012 mmol) in toluene
(10 mL) in a round-bottomed flask, and the mixture was heated at
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for HRMS analysis. The percentage given represents the HRMS
intensity of one fragment compared to the summation of the inten-
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was removed under reduced pressure and extracted with CH2Cl2.
An aliquot was taken to confirm that the species observed in the
toluene solution was the same as that in the bulk sample (Support-
ing Information). 1H and 13C{1H} NMR spectra were recorded for
some of the samples, but yielded very little information other than
the identification of [1+], which has been previously characterized
as the triflate salt,[5] and [3+]Cl, which has a 1H NMR chemical
shift for the Cp* ring of 1.27 ppm. Typical NMR spectra are shown
in the Supporting Information.
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Supporting Information (see footnote on the first page of this arti-
cle): Reaction conditions, product distributions and corresponding
mass spectra for the ligand exchange and oligomer formation reac-
Eur. J. Inorg. Chem. 2010, 2158–2164
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
2163

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Received: December 11, 2009
Published Online: April 8, 2010
2164
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 2158–2164