Synthesis, structure, and reactivity of fluorous phosphorus/carbon/phosphorus pincer complexes derived from P(CH2)5P backbones

Article abstract of DOI:10.1016/j.ica.2006.07.092

Reactions of the diphosphine H₂P(CH₂)₅PH₂ and fluorous alkenes H₂C{double bond, long}CHR_fn (excess; R_fn = (CF₂)_n-1CF₃; n = a, 6; b, 8; c, 10) at 60 °C in the presence of AIBN give the precursors (R_fnCH₂CH₂)₂P(CH₂)₅P(CH₂CH₂R_fn)₂ (2a-c; 68-74%). These react with Pd(O₂CCF₃)₂ in CF₃C₆F₅ at 80 °C to give the title complexes {A figure is presented} (5a-c, 51-18%). Addition of LiCl to 5b gives {A figure is presented} (6b, 97%); subsequent reaction with MeLi affords the corresponding methyl complex (97%). A solvate of 6b is crystallographically characterized. The structure exhibits CH₂CH₂R_f8 groups with nearly anti C-C-C-C conformations, extending in parallel above and below the palladium square plane to create fluorous lattice domains. Reactions of 2b and other metal complexes are described; in the cases of (PhCN)₂PdCl₂ or (COD)₂PtCl₂ (CF₃C₆H₅, room temperature), bimetallic species in which two MCl₂ moieties are bridged by two diphosphines appear to form. The CF₃C₆F₁₁/toluene partition coefficients of 2a-c and 5a-c establish high fluorophilicities; despite the lower fluorine weight%, those of 5a-c are slightly greater ((97.4-99.7):(2.6-0.3) versus (95.3-99.3):(4.7-0.7)).

Full text of DOI:10.1016/j.ica.2006.07.092

Inorganica Chimica Acta 359 (2006) 4874–4884
www.elsevier.com/locate/ica
Synthesis, structure, and reactivity of fluorous
phosphorus/carbon/phosphorus pincer complexes derived
from P(CH ) P backbones
2
5
Crestina S. Consorti, Frank Hampel, J.A. Gladysz *
Institut f u¨ r Organische Chemie, Friedrich-Alexander Universit a¨ t Erlangen-N u¨ rnberg, Henkestraße 42, 91054 Erlangen, Germany
Received 28 June 2006; accepted 31 July 2006
Available online 10 August 2006
Dedicated to Professor Dr. Wolfgang A. Herrmann in appreciation of his many contributions to inorganic and organometallic chemistry.
Abstract
Reactions of the diphosphine H
0 ꢀC in the presence of AIBN give the precursors (RfnCH
2
P(CH
2
)
5
PH
2
and fluorous alkenes H
CH
2
C@CHRfn (excess; Rfn = (CF
P(CH P(CH CH
2
)
3
nꢀ1CF ; n = a, 6; b, 8; c, 10) at
6
2
2
)
2
2
)
5
2
2
R
fn
)
2
(2a–c; 68–74%). These react with
Pd(O CCF in CF at 80 ꢀC to give the title complexes
2
3
)
2
3 6 5
C F
(5a–c, 51–
1
8%). Addition of LiCl to 5b gives
(6b, 97%); subsequent reaction with
MeLi affords the corresponding methyl complex (97%). A solvate of 6b is crystallographically characterized. The structure exhibits
CH CH f8 groups with nearly anti C–C–C–C conformations, extending in parallel above and below the palladium square plane to cre-
ate fluorous lattice domains. Reactions of 2b and other metal complexes are described; in the cases of (PhCN) PdCl or (COD) PtCl
CF C H , room temperature), bimetallic species in which two MCl moieties are bridged by two diphosphines appear to form. The
2
2
R
2
2
2
2
(
3
6
5
2
CF C F /toluene partition coefficients of 2a–c and 5a–c establish high fluorophilicities; despite the lower fluorine weight%, those of
3
6 11
5
a–c are slightly greater ((97.4–99.7):(2.6–0.3) versus (95.3–99.3):(4.7–0.7)).
2006 Elsevier B.V. All rights reserved.
ꢁ
Keywords: Pincer; Fluorous; Radical addition; Palladium; Platinum; Iridium; Partition coefficient
1
. Introduction
by a variety of liquid/liquid and liquid/solid biphasic tech-
niques [15]. Representative examples are provided in
Scheme 1 (A–D) [13,14]. However, to our knowledge there
have been no attempts to immobilize pincer complexes with
aliphatic backbones.
Pincer ligands and their complexes continue to play
increasingly important roles in metal-catalyzed reactions
1]. Systems based upon aliphatic backbones [2–4] as
[
opposed to the more usual arene-based tethers have pro-
vided several notable recent developments [2g,3e,4d]. A
variety of approaches to recoverable pincer ligands and
complexes have been reported [5–14]. These efforts have
included fluorous derivatives [13,14], which can be recycled
We have described several fluorous arene-based phos-
phorus/carbon/phosphorus or PC(sp )P pincer ligands
2
and metal complexes, as exemplified by D in Scheme 1
[14]. However, the ligands were much more difficult to pre-
pare than their non-fluorous counterparts. New types of
side-reactions were encountered, and significantly lower
yields were obtained. Thus, our attention was drawn to
analogs with aliphatic backbones. A variety of convenient
protocols for synthesizing aliphatic fluorous phosphines
*
Corresponding author. Tel.: +49 9131 8522540; fax: +49 9131
8526865.
E-mail address: gladysz@chemie.uni-erlangen.de (J.A. Gladysz).
0
020-1693/$ - see front matter ꢁ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2006.07.092

C.S. Consorti et al. / Inorganica Chimica Acta 359 (2006) 4874–4884
4875
N(CH3)2
Cl
N(CH3)2
PPh2
Rfn
Rfn
CH3
Si
Rf8
Rf8
Rfn
PPh3
Rfn
Rfn
M
Si
Ru
Cl
PPh2
PH2
P
P
P
CH3
Rf8
Rfn
AIBN
Pd(O CCF )
2
3 2
Pd O CCF
2
3
n = 6, 10; M = Pt, Ni
CF C F
6 5
3
A
B
6
0 C
80 C
PH2
P
n = a, 6
b, 8
Rfn
Rfn
Rfn
Rfn
1
S
Rf6
Rf6
P
c, 10
Rfn
Rfn
Pd Cl
S
2
Rfn
Pd O CCF3
2a, 70%
2b, 74%
2c, 68%
5a, 20%
5b, 51%
5c, 18%
P
Rfn
Rf8
Rf8
Rf8
n = 6, 8
Rf8
Rf8
Rf8
C
D
P
P
P
Scheme 1. Representative fluorous pincer complexes (Rfn = (CF
2 nꢀ1
) -
LiCl
MeLi
CF ).
3
Pd O CCF3
Pd Cl
P
Pd CH3
P
2
methanol/
CF C F ,
THF, rt
3
6 5
P
rt
have been developed in our laboratory [16] and we were
optimistic that these could be applied to pincer systems
without difficulty.
Rf8
Rf8
Rf8
Rf8
Rf8
Rf8
5b
6b, 97%
7b, 97%
Accordingly, we set out to prepare fluorous 1,5-diphos-
phines of the formula (R CH CH ) P(CH ) P(CH -
fn
2
2 2
2 5
2
Scheme 2. Synthesis of fluorous pincer ligands and palladium complexes.
CH R ) , and define their coordination chemistry.
2
fn 2
Analogous non-fluorous ligands have been used as spring-
3
boards to a variety of PC(sp )P pincer complexes [2–4]. We
As summarized in Table 1, the diphosphine 2a was very
report below (1) efficient high yield syntheses of such
ligands, (2) their metalation to give fluorous palladium
PC(sp )P pincer complexes, (3) subsequent substitution
reactions, (4) preliminary data involving adducts of other
metals, (5) the crystallographic characterization an Rf8-
based palladium complex, and (6) key phase properties of
the preceding compounds.
soluble in the fluorous solvent CF
ylcyclohexane)), the hybrid solvent CF
the non-fluorous solvent CF [18]. It was moderately
soluble in THF and CH Cl . The homologs 2b and 2c
exhibited progressively lower solubilities, consistent with
fn length trends observed with other fluorous compounds
[16a]. No dramatic changes in solubilities were noted at
0 ꢀC. The CF C F /toluene partition coefficients were
3
C
6
F
11 (perfluoro(meth-
C H
3 6 5
[18], and
3
C F
3 6 5
2
2
R
6
3
9
6 11
1
2
. Results
determined by F NMR as described in Section 4. As sum-
marized in Table 2, values ranged from 95.3:4.7 (2a) to
99.3:0.7 (2c), indicative of high fluorophilicities.
2
.1. Diphosphine synthesis and characterization
We and others have described many free radical chain
2.2. Diphosphine derivatization
additions of R3 PH species to fluorous terminal alkenes
ꢀx
x
H C@CHR [14,16]. Thus, the known diprimary 1,5-
Reactions of non-fluorous 1,5-diphosphines R
P(CH ) -
2 2 5
2
fn
diphosphine H P(CH ) PH (1) was synthesized from the
PR with L PdCl or L PtCl species often give bimetallic
2
2
2
2
2
2
2 5
2
corresponding 1,5-dibromide by a convenient and easily
scalable Arbuzov/reduction sequence [17]. As shown in
Scheme 2 (top), 1 and excess H C@CHR (n = a, 6; b, 8;
complexes of the type E (Scheme 3) [2a,2b]. These can be
converted at elevated temperatures to monometallic
3
PC(sp )P pincer complexes. Thus, 2b and (PhCN)
PdCl
2
fn
2
2
3
1
c, 10) were reacted neat at 60 ꢀC in the presence of the rad-
ical initiator AIBN. Workups gave the fluorous ditertiary
diphosphines (R CH CH ) P(CH ) P(CH CH R ) (2a–
were combined in CF
3
C
6
F
5
at room temperature. A
P
NMR spectrum of the reaction mixture showed one signal,
suggesting the clean formation of a single complex (3).
Workup gave a seemingly homogeneous material (97%),
but FAB mass spectra did not give informative ion pat-
fn
2
2 2
2 5
2
2
fn 2
c) as air sensitive liquids (2a) or solids (2b,c) in 68–74%
yields on 3–5 g scales.
1
3
The diphosphines 2a–c were characterized by microanal-
terns. The C NMR spectrum showed virtual triplets [19]
for the PCH CH CF signals, suggesting a trans geometry.
An analogous reaction of 2b and (COD) PtCl also
appeared to give a single complex (4; 96%). The
NMR spectrum showed one signal with a JPtP value of
2680 Hz, diagnostic for PtCl complexes with trans
1
13
19
31
yses and NMR spectroscopy ( H, C, F, P), as
summarized in Section 4. The chemical shifts and coupling
constants associated with the P(CH ) P and P(CH -
2
2
2
2
2
3
1
P
2
5
2
CH CF ) segments closely resembled those reported for
2
2
related compounds earlier [2a,16].
2

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C.S. Consorti et al. / Inorganica Chimica Acta 359 (2006) 4874–4884
Table 1
Qualitative solubility profile of palladium pincer ligands and complexes
Room temperature
60 ꢀC
CF
CF
3
C
6
F
11
CF
3
C
H
6 5
CF
3
C
6
F
5
THF
CH
2
Cl
2
3
C
6
H
5
CF
3
C
6
F
5
hexane
THF
2 2
CH Cl
2
2
2
5
5
5
a
b
c
a
b
c
high
high
high
high
moderate
moderate
high
high
high
high
high
high
high
high
high
high
moderate
low
v. low
high
moderate
v. low
moderate
low
v. low
high
v. low
v. low
high
high
high
high
high
high
high
high
high
high
high
moderate
low
v. low
high
moderate
v. low
moderate
low
v. low
high
moderate
v. low
moderate
low
v. low
high
moderate
v. low
moderate
moderate
moderate
Table 2
3 6
CF C F11/toluene partition coefficients of fluorous pincer ligands and
palladium complexes (23 ꢀC) measured by F NMR
Hence, alternative cyclometalation strategies were inves-
tigated. As shown in Scheme 2 (top), the palladium trifluo-
roacetate complex Pd(O CCF ) and 2a–2c were combined
19
2
3 2
Compound
Partition coefficient
in CF C F at 80 ꢀC. In accord with much precedent
3
6 5
2
2
2
5
5
5
a
b
c
a
b
c
95.3:4.7
98.8:1.2
99.3:0.7
97.4:2.6
99.3:0.7
99.7:0.3
[
1a,1b,1c,2e], workups gave the air-stable fluorous palla-
dium pincer complexes 5a–5c in 51–18% yields. These were
1
13
31
19
characterized by NMR spectroscopy ( H, C, P, F)
and mass spectrometry, as described in Section 4. Microa-
nalyses suggested that 5b,c crystallized with a molecule of
CF C H (used in the final silica gel filtration step). Mass
3
6
5
+
spectra showed intense M –CF CO peaks (100%), but
3
2
no parent ions.
Rf8
1
3
The C NMR spectra of 5a–c exhibited diagnostic sig-
nals for the metalated (PdCH) carbon atoms at 56 ppm.
Rf8
1
P
P
The PdCH H NMR resonance was obscured by other
3
1
peaks. The P NMR chemical shifts were ca. 35 ppm
downfield from those of 2a–c, consistent with the forma-
tion of five-membered phosphacycles [21]. In accord with
(
COD)PtCl2
(
PhCN) PdCl2
2
4
3
CF C F
CF C F
(
96%)
3
6
5
3
6
5
(97%)
3
the non-planar bicyclic PC(sp )P pincer cores, two
Rf8
13
PCH CH CF
2
C signals were observed, corresponding
2
2
Rf8
to the ponytails cis and trans to the bridgehead PdCH
hydrogen atom. The F NMR spectra showed three sets
1
9
2
a
of CH CH CF signals (4:2:2, m/m/m), which is a logical
2
2
2
consequence of the diastereotopic relationship of all gemi-
nal fluorine atoms in 5a–c.
proposed
structures
R2P
PR2
As summarized in Table 1, the pincer complexes 5a–c
exhibited solubility trends similar to those of the free
ligands. Interestingly, the CF C F /toluene partition coef-
(
3, 4):
Cl M Cl
R2P
Cl M Cl
PR2
3
6 11
ficients (Table 2) were slightly more biased than those of
the free ligands, indicating enhanced fluorophilicity despite
the diminished weight% of fluorine (e.g., 67.3% for 2b ver-
sus 63.1% for 5b (or 61.3% for 5bÆCF C H )). Similar phe-
nomena have been documented with other metal complexes
of fluorous ligands [22]. As would be expected, the fluoro-
philicity of 5b was greater than that of its aromatic coun-
terpart D in Scheme 1 (99.3:0.7 versus 96.4:3.6) [14].
E
M = Pd, Pt
3
6
5
Scheme 3. Reaction of fluorous pincer ligand 2b with L
2
2
MCl species.
phosphine ligands [20]. Hence, we suggest that 3 and 4 have
structures of the type E. However, other possibilities can-
not be rigorously excluded.
Complexes 3 and 4 were (a) heated as solids and (b)
refluxed in trifluoroacetic acid for extended periods. Under
these conditions, non-fluorous complexes of the type E are
efficiently converted to palladium and platinum pincer
complexes [2a,2b,2d]. However, 3 gave only black palla-
dium metal. With 4, no reaction was apparent (although
some chloride/trifluoroacetate ligand exchange may have
occurred with (b)).
2.3. Further chemistry
Extensions of the preceding reactions were attempted.
First, 5b and excess LiCl were combined in methanol/
CF
(bottom), workup gave the chloride complex 6b as an ana-
lytically pure CF monosolvate in 97% yield. Most
spectroscopic properties were similar to those of 5a–c.
C H at room temperature. As shown in Scheme 2
3 6 5
C H
3 6 5

C.S. Consorti et al. / Inorganica Chimica Acta 359 (2006) 4874–4884
4877
No trace of 6b was detected during the pyrolysis of 3
above).
Certain methyl derivatives of palladium PC(sp )P pincer
Table 3
3 6 5
Crystallographic data for 6bÆCF C H
(
3
Empirical formula
Formula weight
Temperature (K)
52 2
C H30ClF71P Pd
2207.55
173(2)
0.71073
orthorhombic
Pnma
complexes have been reported to be effective catalyst pre-
cursors [2d]. Hence, 6b was treated with MeLi (1.0 equiv.)
in THF at room temperature (Scheme 2, bottom). Workup
gave the crude methyl complex 7b in 97% yield as an air
stable white powder. However, it was quite labile in solu-
tion. After 4 h, a CF C H solution showed substantial
˚
Wavelength (A)
Crystal system
Space group
Unit cell dimensions
˚
a (A)
11.555(2)
34.672(7)
18.721(4)
90
90
90
7500(3)
4
1.955
0.540
4296
3
6
5
˚
3
1
b (A)
decomposition to two new species, as assayed by
P
˚
c (A)
NMR. Hence, 7b was only partially characterized. How-
a (ꢀ)
b (ꢀ)
c (ꢀ)
1
3
ever, the PdCH3 C NMR signal was very close to that
reported for non-fluorous analog (62.6 versus
2.2 ppm) [2d].
Adducts of other catalytically active metals were sought.
a
˚
3
V (A )
6
Z
ꢀ3
q
calc (Mg m
)
2
Iridium PC(sp )P complexes see extensive use in carbon–
hydrogen bond activation reactions [23], and the bis-
ꢀ1
l (mm
F(000)
)
(
cyclooctene) complex [IrCl(COE) ] [24] has often been
Crystal dimensions (mm)
h Range (ꢀ)
Index ranges (h,k,l)
Reflections collected
Independent reflections (Rint
Reflections (I > 2r(I))
Completeness to h = 27.51ꢀ (%)
Maximum and minimum transmission
Refinement method
0.35 · 0.30 · 0.25
1.17–25.00
2
2
used as a precursor [4b,14,23]. Thus, 2a and [IrCl-
(
material that was pure by P NMR and exhibited an
ꢀ13,13; ꢀ41,41; ꢀ22,22
COE) ] were reacted in THF at 80 ꢀC. Workup gave a
2
2
11964
31
)
6649 (0.0416)
4195
98.6
0.8768 and 0.8334
full-matrix least-squares on F
1
upfield IrH H NMR signal (d ꢀ28.18) that was
furthermore coupled to phosphorus (t, J = 15.0 Hz).
HP
This was tentatively assigned to the target molecule
2
Data/restraints/parameters
Goodness-of-fit on F
6649/5/598
1.426
(
8b).
2
1
13
Final R indices [I > 2r(I)]
R
1
= 0.1211
wR = 0.3440
= 0.1686
wR = 0.3788
1.659, ꢀ0.881
However, H and C spectra of the reaction mixture
showed that other species were present, and 8b could only
be isolated in 10% yield. Attempts to effect cyclometala-
tions with RhCl Æ3H O analogous to protocols for non-
2
R indices (all data)
R
1
2
˚
ꢀ3
]
3
2
Largest difference in peak, hole [eA
fluorous systems [3a] were unsuccessful.
2
.4. Crystallography
methyl analog [2d]; 165.9(7)ꢀ, PPh /chloride analog [2f]).
2
One ponytail on each phosphorus atom extends above
the palladium square plane, and the other below. Both
run parallel to the ponytails on the trans phosphorus
atom, which are nearly in van-der-Waals contact (Fig. 1,
bottom).
In what remains somewhat of a rare event with flu-
orous molecules, single crystals of 6bÆCF C H were
3
6
5
obtained. They were of marginal quality, but X-ray
data could be collected as described in Table 3 and Sec-
tion 4. Refinement gave the structures shown in Figs. 1
and 2.
It is now well-established that the lowest energy (anti)
conformations of n-perfluoroalkanes and perfluoroalkyl
groups exhibit C–C–C–C torsion angles somewhat less
than those of n-alkanes (ca. 166ꢀ versus 180ꢀ) [25,26].
Accordingly, the C–C–C–C torsion angles within the Rf8
segments of 6bÆCF C H average 162.8ꢀ (high 167.8(12)ꢀ,
As illustrated in Fig. 2, the carbon atoms adjacent to the
PdCH moiety were disordered in an up/up versus down/
down sense about a crystallographic mirror plane. The
plane runs vertically thought the structures in Fig. 1, con-
tains all palladium-bound atoms, and requires a simulta-
neous disorder of the bridgehead hydrogen atom (not
located). Analogous phenomena have been observed with
3
6
5
low 157(2)ꢀ). This imparts a slight twist, which propagates
in the same direction to give helical (CF ) moieties, as evi-
2
n
dent in Fig. 1 and exploited in two recent papers in other
fluorous molecules [26].
3
other crystalline PC(sp )P pincer complexes [2f]. Several
fluorine atoms in two of the ponytails were also disordered,
as signaled by large thermal ellipsoids (bottom chains, top
structure).
As illustrated in Fig. 3, the crystal lattice is divided into
fluorous and non-fluorous domains, with the ponytails of
neighboring molecules nearly in van-der-Waals contact.
Other square planar metal complexes with fluorous alkyl-
phosphines crystallize similarly [14,27]. The van-der-Waals
Key metrical parameters of 6bÆCF C H are summa-
3
6
5
rized in Table 4. Most bond lengths and angles are routine.
The palladium atom exhibits a distorted square planar
geometry, but with a P–Pd–P angle (168.1(1)ꢀ) larger than
in similar non-fluorous complexes (166.2(1)ꢀ, P(t-Bu)2/
˚
radius of fluorine is 1.40 A [28], and the shortest intermo-
˚
lecular fluorine–fluorine distances (2.789–2.914 A) are
included in Table 4.

4878
C.S. Consorti et al. / Inorganica Chimica Acta 359 (2006) 4874–4884
3 6 5
Fig. 1. Molecular structure of palladium pincer complex 6bÆCF C H , with the solvent omitted.
3 6 5
Fig. 2. Limiting structures for the disordered bicyclic core of 6bÆCF C H .
3
. Discussion
biphase conditions. However, increasing numbers of fluor-
ous catalysts and reagents are being recovered by fluorous/
organic solid/liquid phase separations [29]. Towards this
end, the much lower solubilities of 2c and 5c (Table 1)
should prove advantageous.
Many palladium PCP pincer complexes are effective cat-
alyst precursors for Heck alkenylations of aryl halides
[1d,30,31]. However, it is increasingly appreciated that
many of these merely serve as precursors for pincer-free
palladium(0) nanoparticles or low-coordinate molecular
species, which constitute the active catalysts [31]. Much
The fluorous ditertiary 1,5-diphosphines 2a–c are easily
synthesized on 3–5 g scales as shown in Scheme 1. Under
appropriate conditions, they can be converted to pincer
complexes that feature aliphatic backbones. This is most
readily accomplished with Pd(O CCF ) at elevated tem-
perature. As illustrated by the partition coefficients in
Table 2, the diphosphines and resulting palladium adducts
2
3 2
5
a–c exhibit appreciable fluorophilicities that will lead to
high recoveries under fluorous/organic liquid/liquid

C.S. Consorti et al. / Inorganica Chimica Acta 359 (2006) 4874–4884
4879
Table 4
Selected bond lengths (A), bond angles (ꢀ), and intermolecular contacts
and precursors of the types in Scheme 3 are ineffective. The
development of functionalized fluorous 1,5-diphosphines
that would undergo more ready cyclometalation would
be especially helpful. Although some leads have been
reported for non-fluorous systems [3c], one particularly
appealing approach would involve the replacement of the
central methylene group of 2 by a CHRfn moiety. This
might promote metalation while at the same time enhanc-
˚
˚
3 6 5
A) for 6bÆCF C H
(
˚
Bond lengths (A)
Pd(1)–C(1)
Pd(1)–P(1)
Pd(1)–P(2)
Pd(1)–Cl(1)
P(1)–C(11)
P(1)–C(3)
2.112(12)
2.268(4)
2.290(3)
2.394(4)
1.798(10)
1.821(5)
C(1)–C(4)
C(1)–C(2)
C(2)–C(3)
P(2)–C(5)
P(2)–C(21)
C(4)–C(5)
1.48(2)
1.497(13)
1.397(10)
1.828(13)
1.835(17)
1.57(2)
ing
fluorophilicity.
Alternatively,
transmetalations
Bond Angles (ꢀ)
C(1)–Pd(1)–P(1)
C(1)–Pd(1)–P(2)
P(1)–Pd(1)–P(2)
C(1)–Pd(1)–Cl(1)
P(1)–Pd(1)–Cl(1)
P(2)–Pd(1)–Cl(1)
C(11)–P(1)–C(3)
C(3)–P(1)–Pd(1)
[1a,1b,1c] involving 5b (available in the highest yield,
83.8(3)
84.3(3)
C(4)–C(1)–C(2)
C(4)–C(1)–Pd(1)
C(2)–C(1)–Pd(1)
C(3)–C(2)–C(1)
C(5)–P(2)–Pd(1)
C(2)–C(3)–P(1)
C(1)–C(4)–C(5)
C(4)–C(5)–P(2)
119.0(11)
51%) could be investigated.
112.7(9)
111.4(7)
120.0(5)
104.0(5)
108.4(2)
113.0(14)
106.8(10)
Finally, this study has also expanded the modest range
168.08(13)
177.5(3)
93.66(14)
98.25(13)
108.1(6)
104.09(19)
of crystallographically characterized fluorous metal com-
plexes. Further examples will be reported in due course
[36]. Additional efforts involving fluorous ligand develop-
ment for catalytic reactions remain in progress [36b], and
will be described in future publications.
˚
Intermolecular contacts (A)
F17A–F26A
F19A–F28A
F14A–F29A
2.789
2.914
2.876
F26B–F16A
F26B–F18A
2.793
2.804
4
. Experimental
4.1. General data
Reactions were conducted under N atmospheres unless
2
data now support analogous pathways for Heck reactions
catalyzed by palladium SCS pincer complexes [9c,9d],
and other types of palladacycles [32–34]. Hence, during
the course of this study we became much less enthusiastic
about testing 5a–c as recoverable catalysts or catalyst pre-
cursors for any type of aryl halide coupling reaction, which
was originally a major impetus for this work.
Nonetheless, there are many other types of reactions
catalyzed by pincer complexes that might be targeted in
future efforts [1d,2d,3e,8b,35]. In this context, several issues
are deserving of attention. First, the yields of 5a–c are
modest, that of the related iridium complex 8b is lower still,
noted. Chemicals were treated as follows: THF, ether, and
toluene, distilled from Na/benzophenone; CF
CF , and CF (3 · Fluorochem or ABCR), dis-
tilled from CaH [d ]DMSO (Deutero GmbH),
C@CHRf6, H C@CHRf8, H C@CHRf10 (3 · ABCR),
(PhCN) PdCl , Pd(O CCF , RhCl Æ3H O (3 · Strem,
C F ,
3 6 11
C
6
F
C H
3 6 5
3
5
;
2
6
H
2
2
2
)
2
2
2
2
3
3
2
99–97%), AIBN (Merck, >98%), and MeLi (Acros, 1.0 M
in hexane), used as received.
NMR spectra were obtained on a Bruker 400 MHz spec-
1
trometer and referenced as follows: H, external residual
1
3
[d
(d = 39.5 ppm); F, internal C
]DMSO (d = 2.49 ppm);
C, external [d
]DMSO
6
5
1
9
31
F
6 6
(d = ꢀ162.0 ppm); P,
3 6 5
Fig. 3. Packing diagram for 6bÆCF C H .

4880
C.S. Consorti et al. / Inorganica Chimica Acta 359 (2006) 4874–4884
1
3
external H PO (d = 0.00 ppm). The highly coupled
C
4.4. (Rf10CH CH ) P(CH ) P(CH CH R ) (2c)
2 2 2 2 5 2 2 f10 2
3
4
signals of the fluorinated carbons are not listed. Mass spec-
1
tra were recorded on a Micromass Zabspec instrument.
H P(CH ) PH (0.442 g, 3.25 mmol), AIBN (0.100 g,
2 2 5 2
DSC and TGA data were recorded with a Mettler-Toledo
DSC821 instrument (heating rate, 10 ꢀC/min) and treated
by standard methods [37]. Microanalyses were conducted
with a Carlo Erba EA1110 instrument.
1.00 mmol) and H C@CHR
combined in a procedure analogous to that for 2b. An iden-
tical workup gave 2c as a light brown solid (5.11 g,
(10.8 g, 19.6 mmol) were
f10
2
2.21 mmol, 68%), m.p. 73 ꢀC (T , DSC). Anal. Calc. for
e
C H F P : C, 27.43; H, 1.13. Found: C, 27.43; H, 1.09%.
5
6
26 84 2
1
NMR (d, CF C F , [d ]DMSO capillary): H 1.70–1.50
3
6
5
6
4
.2. (R CH CH ) P(CH ) P(CH CH R ) (2a)
f6 2 2 2 2 5 2 2 f6 2
(
(
m, 4CH CF ), 1.14–1.04 (m, 4PCH CH CF ), 1.01–0.91
2 2 2 2 2
m, 5CH2); C{ H} 31.2 (t, J = 10.8 Hz, PCH CH -
1
3
1
CP
2
2
A Schlenk flask was charged with H P(CH ) PH
2
2
2 5
CH ), 26.2 (dt, J = 19.3 Hz, JCF = 21.7 Hz, CH CF ),
2
CP
2
2
(
0.700 g, 5.14 mmol) [17], AIBN (0.100 g, 1.00 mmol),
25.0 and 23.6 (2 d, JCP = 13.6 and 13.9 Hz, PCH CH CH ),
2 2 2
and H C@CHR (12.4 g, 36.0 mmol) in a glove box. The
2
f6
19
3
1
14.9 (d, JCP = 16.0 Hz, PCH
2
CH
2
CF
2
); F ꢀ84.5 (t, JFF
=
mixture was stirred at 65 ꢀC (oil bath). After 4 h, a
P
1
0.4 Hz, 12F, 4CF ), ꢀ118.3 (m, 8F), ꢀ124.4 (m, 40F),
3
NMR spectrum of an aliquot showed the starting material
to be consumed. Excess alkene was removed by oil pump
vacuum. The oil was washed with CH Cl to remove the
3
1
1
ꢀ
125.4 (m, 8F), ꢀ126.1 (m, 8F), ꢀ129.1 (m, 8F); P{ H}
ꢀ
26.6 (s).
2
2
remaining AIBN and dried by oil pump vacuum to give
4.5. trans,trans-Cl Pd[(R CH CH ) P(CH ) -
P(CH CH R ) ] PdCl (3)
2 f8 2 2 2 2 5
2
a as a slightly yellow viscous liquid (5.42 g, 3.59 mmol,
0%). Anal. Calc. for C H F P : C, 29.26; H, 1.72.
2
2
f8 2 2
2
7
3
7
26 52 2
Found: C, 29.39; H, 1.71%.
NMR (d, CF C F , [d ]DMSO capillary): H 1.62–1.44
1
A Schlenk flask was charged with 2b (0.175 g,
3
6
5
6
0
.0910 mmol), (PhCN) PdCl (0.035 g, 0.091 mmol), and
2
2
(
(
m, 4CH CF ), 1.08–1.00 (m, 4PCH CH CF ), 0.95–0.88
2
2
2
2
2
1
3
1
CF C H (2 mL). The mixture was stirred for 4 h. The sol-
3 6 5
m, 5CH2);
C{ H} 31.3 (t, J = 11.9 Hz, PCH2-
CP
vent was removed by rotary evaporation. The light yellow
solid was extracted twice with hot THF. The solvent was
removed by rotary evaporation to give 3ÆCF C H as a light
CH CH ), 26.2 (dt, JCP = 19.0 Hz, JCF = 23.6 Hz,
2
2
CH CF ), 25.1 and 23.7 (2 d, J = 13.4 and 13.8 Hz,
2
2
CP
3
6
5
PCH CH CH ), 15.0 (d, J = 16.0 Hz, PCH CH CF );
2
2
2
CP
2
2
2
1
9
yellow solid (0.185 g, 0.882 mmol, 97%), m.p. 92 ꢀC (T
,
e
F ꢀ84.6 (t, J = 10.4 Hz, 12F, CF ), ꢀ118.5 (m, 8F),
FF
3
DSC, dec). Anal. Calc. for C H Cl F P PdÆCF C H :
4
5
26
2
68
2
3
6
5
ꢀ
124.8 (m, 8F), ꢀ125.8 (m, 8F), ꢀ126.3 (m, 8F), ꢀ129.3
31 1
C, 27.83; H, 1.39. Found: C, 27.83; H, 1.72%.
(
m, 8F); P{ H} ꢀ26.8 (s).
2
1
NMR (d, CF C F , [d ]DMSO capillary) : H 2.07–1.27
3
6
5
6
1
3
1
(
br m); C{ H} 30.7 (t, J = 7.5 Hz, PCH CH CH ),
CP 2 2 2
4
.3. (R CH CH ) P(CH ) P(CH CH R ) (2b)
f8
24.9 (t, JCF = 23.2 Hz, CH CF ), 22.1 and 21.2 (s and
2 2
2
2 2
2 5
2
2
f8 2
virtual t [19], JCP = 13.3 Hz, PCH CH CH ), 12.1 (virtual
2
2
2
1
9
H P(CH ) PH (0.305 g, 2.24 mmol), AIBN (0.100 g,
t, JCP = 12.9 Hz, PCH CH CF ); F ꢀ84.6 (t, J
=
FF
2
2 5
2
2
2
2
1
.00 mmol) and H C@CHR (7.01 g, 15.4 mmol) were
10.3 Hz, 12F, 4CF ), ꢀ118.3 (m, 8F), ꢀ124.6 (m, 24F),
2
f8
3
combined in a procedure analogous to that for 2a. Excess
alkene was removed by oil pump vacuum. The yellow solid
was extracted with CF C H . The extract was concentrated
ꢀ125.5 (m, 8F), ꢀ125.8 (m, 8F), ꢀ129.2 (m, 8F);
3
1
1
P{ H} 12.3 (s).
3
6
5
and cooled to 0 ꢀC. The white solid was collected by filtra-
tion and dried by oil pump vacuum to give 2b (3.16 g,
4.6. trans,trans-Cl Pt[(R CH CH ) P(CH ) -
2 f8 2 2 2 2 5
P(CH CH R ) ] PtCl (4)
2
2
f8 2 2
2
1
.65 mmol, 74%), m.p. 42 ꢀC (T , DSC). Anal. Calc. for
e
C H F P : C, 28.14; H, 1.36. Found: C, 28.24; H, 1.09%.
A Schlenk flask was charged with 2b (0.251 g,
4
5
26 68 2
1
NMR (d, CF C F , [d ]DMSO capillary): H 1.68–1.50
0.131 mmol), (COD) PtCl (0.059 g, 0.13 mmol) [38] and
3
6
5
6
2
2
(
(
m, 4CH CF ), 1.13–1.06 (m, 4PCH CH CF ), 1.03–0.93
CF C F (2 mL). The mixture was stirred for 4 h. The sol-
3 6 5
2
2
2
2
2
1
3
1
m,
5CH2);
C{ H}
31.2
(t,
JCP = 11.2 Hz,
vent was removed by oil pump vacuum to give 4 as a light
yellow solid (0.216 g, 0.122 mmol, 96%). NMR (d,
PCH CH CH ), 26.1 (dt, J = 19.8 Hz, JCF = 23.2 Hz,
CH CF ), 25.0 and 23.6 (2 d, J = 13.6 and 13.9 Hz,
2
2
2
CP
3
1
1
1
2
2
CP
CF C F , [d ]DMSO capillary): P{ H} 8.6 (s, JPPt =
3 6 5 6
2680 Hz).
3
PCH CH CH ), 15.0 (d, J = 17.4 Hz, PCH CH CF );
2
2
2
CP
2
2
2
1
9
F ꢀ84.5 (t, J = 10.4 Hz, 12F, 4CF ), ꢀ118.3 (m, 8F),
FF
3
ꢀ
ꢀ
124.6 (m, 24F), ꢀ125.5 (m, 8F), ꢀ126.2 (m, 8F),
31 1
129.1 (m, 8F); P{ H} ꢀ26.7 (s).
2
1
The H signals of the solvate are obscured by protic impurities in the
1
3
3 6 5
CF C F solvent, and the CH C signals of the solvate are obscured by
the CF signals of the solvent.
This coupling represents a satellite (d;
reflected in the peak multiplicity given.
1
3
195
The m/z values represent the most intense peak of the isotope envelope.
The diphosphines 2a–c exhibited only ions derived from the bis(oxides).
Pt = 33.8%), and is not

C.S. Consorti et al. / Inorganica Chimica Acta 359 (2006) 4874–4884
4881
4
(
.7.
5a)
ꢀ118.5 (m, 4F of 4PCH CH CF ), ꢀ124.6 (m, 24F),
2
2
2
ꢀ125.5 (m, 8F), ꢀ125.9 (m, 8F), ꢀ129.2 (m, 8F);
1 1 1
3
P{ H} 48.4 (s). MS (positive FAB, m/z) : 2026 ([5b–
+
+
A
Schlenk tube was charged with 2a (0.802 g,
CF CO ] , 100%), 1578 ([5b–CF CO –CH CH R ] ,
3 2 3 2 2 2 f8
+
0
.527 mmol), Pd(O CCF ) (0.174 g, 0.523 mmol), and
10%), 1099 ([5b–CF CO –P(CH CH R ) +H] , 60%).
3 2 2 2 f8 2
2
3 2
CF C F (5 mL) in a glove box. The mixture was stirred
3
6 5
at 80 ꢀC for 2 d, during which time aliquots were assayed
4
(
.9.
5c)
3
1
by P NMR. The solvent was removed by oil pump vac-
uum and the brown residue extracted with 1:1 v/v
CH Cl /hexane (3 · 5 mL). The solvents were removed
2
2
Diphosphine 2c (0.800 g, 0.345 mmol), Pd(O CCF )
2
3 2
from the extract by oil pump vacuum. The dark residue
was filtered through silica using CF C H . The solvent
was removed from the filtrate by oil pump vacuum to give
(
0.114 g, 0.345 mmol), and CF C F (5 mL) were com-
3 6 5
3
6
5
bined in a procedure analogous to that for 5a. After 6 d
at 80 ꢀC, the solvent was removed by oil pump vacuum.
The brown residue was filtered through silica using 1:1 v/v
CF C H /CF C F . The solvent was removed from the fil-
5
aÆCF C H as light yellow crystalline solid (0.180 g,
3 6 5
4
0
.105 mmol, 20%), m.p. 87 ꢀC (T , DSC).
e
2
1
3
6
5
3 6 5
NMR (d, CF C F , [d ]DMSO capillary) : H 1.95–1.13
3
6
5
6
trate by oil pump vacuum to give 5cÆCF C H as a light
1
3
1
5
3
6
5
(
br m); C{ H} 54.5 (s, PdCH), 35.9 (virtual t [19],
yellow crystalline solid (0.159 g, 0.0621 mmol, 18%), m.p.
JCP = 6.7 Hz, PCH CH CH), 25.8 (overlapping signals,
2
2
1
29 ꢀC (capillary, dec), solid phase transition 105 ꢀC (Te,
PCH CH CH and CH CF ), 15.8 (virtual t, J = 11.9 Hz,
2
2
2
2
CP
endotherm, DSC), m.p. 135 ꢀC (T , endotherm, DSC).
e
2
C of 4PCH CH CF ), 15.1 (virtual t, J = 11.8 Hz, 2C
2 2 2 CP
The TGA trace shows 3.7% mass loss at ca. 105 ꢀC (calcu-
1
9
of 4PCH CH CF ); F ꢀ78.7 (s, 3F, CO CF ), ꢀ84.6 (t,
2
2
2
2
3
lated for CF C H loss, 5.3%), with additional mass loss
3
6
5
JFF = 10.1 Hz, 12F, 4CF ), ꢀ117.6 (m, 2F of 4PCH -
3
2
beginning gradually above 135 ꢀC. Anal. Calc. for
C H F O P PdÆCF C H : C, 27.73; H, 1.13. Found:
CH CF ), ꢀ117.9 (m, 2F of 4PCH CH CF ), ꢀ118.6 (m,
2
2
2
2
2
5
5
25 87
2
2
3
6
5
4
F of 4PCH CH CF ), ꢀ124.7 (m, 8F), ꢀ125.6 (m, 8F),
2
2
2
C, 27.83; H, 1.25%.
NMR (d, CF C F , [d ]DMSO capillary) : H 1.97–0.93
3
1
1
ꢀ
125.9 (m, 8F), ꢀ129.3 (m, 8F); P{ H} 48.6 (s). MS
2
1
1 +
positive FAB, m/z) : 1625 ([5a–CF CO ] , 100%), 1278
3
6
5
6
(
(
3
2
19
(
1
4
br m); F ꢀ78.7 (s, 3F, CO CF ), ꢀ84.5 (t, J = 10.2 Hz,
+
2
3
FF
[5a–CF CO –CH CH R ] , 10%), 899 ([5a–CF CO –
3
2
2
2
f6
3
2
2F, 4CF ), ꢀ117.4 (m, 1F of 4PCH CH CF ), ꢀ117.8 (m,
+
3
2
2
2
P(CH CH R ) +H] , 40%).
2
2
f6 2
F of PCH CH CF ), ꢀ118.1 (m, 1F of 4PCH CH CF ),
2
2
2
2
2
2
ꢀ
118.5 (m, 2F of 4PCH CH CF ), ꢀ124.4 (m, 40F),
2
2
2
4
(
.8.
5b)
ꢀ
125.4 (m, 8F), ꢀ125.9 (m, 6F), ꢀ126.4 (m, 2F), ꢀ129.1
3
1
1
1
(
m, 8F); P{ H} 48.7 (s). MS (positive FAB, m/z) : 2425
+
(
[5c–CF CO ] , 100%).
3
2
Diphosphine 2b (0.800 g, 0.416 mmol), Pd(O CCF3)2
2
(
0.138 g, 0.416 mmol) and CF C F (5 mL) were combined
3 6 5
in a procedure analogous to that for 5a. The brown residue
extracted with hot THF (3 · 10 mL). The solvents were
removed from the extract by oil pump vacuum. The dark
residue was filtered through silica using CF C H . The sol-
4.10.
(6b)
A Schlenk flask was charged with 5b (0.102 g,
3
6
5
vent was removed from the filtrate by oil pump vacuum to
0.0477 mmol), CF C H (5 mL), and a solution of LiCl
3
6
5
give 5bÆCF C H as a light yellow crystalline solid (0.455 g,
(0.0432 g, 0.935 mmol) in methanol (2 mL). The mixture
was stirred for 4 h. The solvent was removed by oil pump
vacuum. Then CF C H was added, and the mixture fil-
3
6
5
0
.212 mmol, 51%), m.p. 123 ꢀC (T , DSC). Anal. Calc. for
e
C H F O P PdÆCF C H : C, 28.38; H, 1.32. Found: C,
4
7
25 71
2
2
3
6
5
3
6
5
2
8.38; H, 1.27%.
NMR (d, CF C F , [d ]DMSO capillary) : H 1.91–0.99
tered through a short plug of silica. The solvent was
removed from the filtrate by oil pump vacuum to give
6bÆCF C H as a white crystalline solid (0.0953 g,
2
1
3
6
2
5
6
1
3
1
1
(
br m);
C{ H} 54.5 (s, PdCH), 36.0 (virtual t ,
3
6
5
JCP = 6.9 Hz, PCH CH CH), 25.9 (overlapping signals,
0.0462 mmol, 97%), m.p. 105 ꢀC (T , DSC). Anal. Calc.
2
2
e
PCH CH CH and CH CF ), 15.8 (virtual t, J = 11.4 Hz,
for C H ClF P PdÆCF C H : C, 28.29; H, 1.37. Found:
2
2
2
2
CP
45 25
68
2
3
6
5
2
C of 4PCH CH CF ), 15.1 (virtual t, J = 11.7 Hz, 2C
C, 28.38; H, 1.27%.
NMR (d, CF C F , [d ]DMSO capillary) : H 2.44–1.12
2
2
2
CP
1
9
2 1
of 4PCH CH CF ); F ꢀ78.7 (s, 3F, CO CF ), ꢀ84.5 (t,
2
2
2
2
3
3
6
5
6
1
3
1
5
JFF = 10.4 Hz, 12F, 4CF ), ꢀ117.5 (m, 2F of
(br m); C{ H} 58.8 (s, PdCH), 35.6 (virtual t [19],
JCP = 7.7 Hz, PCH CH CH), 27.0 (virtual [19],
JCP = 11.5 Hz, PCH CH CH), 25.8 (m, CH CF ), 14.5
3
4
PCH CH CF ), ꢀ117.9 (m, 2F of 4PCH CH CF ),
t
2
2
2
2
2
2
2
2
2
2
2
2
1
9
(
4
m, PCH CH CF ); F ꢀ84.5 (t, J = 10.3 Hz, 12F,
2
2
2
FF
4
The solvate is inferred from the related compounds (5b, 5c, 6b) that
CF ), ꢀ117.6 (m, 2F of 4PCH CH CF ), ꢀ117.9 (m, 2F
3
2
2
2
crystallize similarly. However, while the carbon analysis agreed with a
monosolvate, the hydrogen analysis was too high.
of 4PCH CH CF ), ꢀ118.5 (m, 4F of 4PCH CH CF ),
2
2
2
2
2
2
5
ꢀ124.5 (m, 24F), ꢀ125.5 (m, 8F), ꢀ125.9 (m, 8F),
31 1
These signals were assigned by analogy of those of similar complexes in
Ref. [2f].
ꢀ129.2 (m, 8F); P{ H} 47.7 (s). MS (positive FAB,

4882
C.S. Consorti et al. / Inorganica Chimica Acta 359 (2006) 4874–4884
1
+
+
m/z) : 2025 ([6–Cl] , 100%), 1578 ([6–Cl–CH CH R ] ,
5
(0.127 g after a 2.000/0.500 scale factor) closely agrees
with that utilized.
2
2
f8
+
%), 1099 ([6–Cl–P(CH CH R ) +H] , 67%).
2 2 f8 2
4.11.
4.14. Crystallography
(7b)
A nearly saturated CF C H solution of 6b was
3
6
5
A Schlenk flask was charged with 6b (0.173 g,
allowed to slowly concentrate at room temperature. After
0
.0839 mmol), ether (5 mL), and MeLi (0.84 mL, 1.0 M
2 weeks, a transparent colorless prism of 6bÆCF C H
5
3
6
in hexane, 0.084 mmol). The mixture was stirred for 4 h.
Degassed water was added (0.10 mL). The solvents were
removed by oil pump vacuum. Then CF C H was added,
and the mixture was filtered using a cannula. The solvent
was removed from the filtrate to give 7b as a white crystal-
line solid (0.166 g, 0.0813 mmol, 97%).
was taken to a Nonius KappaCCD diffractometer for
data collection as outlined in Table 3. Cell parameters
were obtained from 10 frames using a 10ꢀ scan and
refined with 4195 reflections. Lorentz, polarization and
empirical (Scalepack) absorption corrections [39] were
applied. The space group was determined from systematic
absences and subsequent least-squares refinement. The
structure was solved by direct methods. The parameters
3
6
5
1
NMR (d, CF C H , [d ]DMSO capillary): H 2.13–0.4
3
6
5
6
1
3
1
6
19
(
br m);
C{ H} 62.6 (s, PdCH ) ;
F ꢀ84.5 (t,
3
JFF = 10.3 Hz, 12F, 4CF3), ꢀ117.1 (br m, 4F of
were refined with all data by full-matrix-least-squares on
2
4
PCH CH CF ), ꢀ118.6 (br m, 4F of 4PCH CH CF ),
F
using SHELXL-97 [40]. Non-hydrogen atoms were
2
2
2
2
2
2
ꢀ
ꢀ
124.2 (br m, 24F), ꢀ125.5 (m, 8F), ꢀ126.0 (m, 8F),
refined with anisotropic thermal parameters. The hydro-
gen atoms were fixed in idealized positions using a riding
model. The pincer chelate atoms C2 and C4 were disor-
dered (50:50) about a crystallographic mirror plane.
Several fluorine atoms of the ponytail extending from
C21 to C30 were disordered, and could not be resolved.
3
1
1
129.2 (m, 8F); P{ H} 49.1 (s).
4
(
.12.
8b)
A Schlenk flask was charged with 2b (0.798 g,
The CF group of the solvate was disordered, but could
3
0
0
.41 mmol), THF (2 mL), and [IrCl(COE)2]2 (0.140 g,
.20 mmol) [24]. The mixture was stirred for 2 d under
be modeled by a set of four conformations, each with
75% occupancy. Scattering factors were taken from the
literature [41].
argon at 80 ꢀC. The THF phase was removed and the
resulting oil extracted twice with hot THF (much oil
remained). The THF phases were combined, and solvent
was removed by oil pump vacuum to give 8b as a slightly
yellow oil (0.081 g, 0.042 mmol, 10%).
5. Supporting information
Crystallographic data for 6bÆCF C H have been
3
6
5
1
NMR (d, CF C F , [d ]DMSO capillary): H 2.22–1.19
deposited with the Cambridge Crystallographic Data Cen-
tre, CCDC reference number 611620. Copies may be
obtained free of charge from The Director, CCDC, 12,
Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223
336033; e-mail: deposit@ccdc.cam.ac.uk or http://
www.ccdc.cam.ac.uk).
3
6
5
6
3
1
1
(
br m), ꢀ28.18 (t, IrH, J = 15.0 Hz); P{ H} 27.2 (s).
HP
1 +
MS (positive FAB, m/z) : 2111 ([9–HCl] , 100%).
4
.13. Partition coefficients
The following is representative. A 10 mL vial was
charged with 2b (0.120 g, 0.0995 mmol), CF C F
3
6
11
Acknowledgments
(
2.000 mL), and toluene (2.000 mL), fitted with a mininert
valve, and gently heated until 2b dissolved. The vial was
vigorously shaken (2 min) to ensure good phase mixing,
and kept in a darkened location at room temperature
We thank the Deutsche Forschungsgemeinschaft (DFG,
GL 300/3-3), the Humboldt Foundation (fellowship to
CSC), and Johnson Matthey PMC (precious metal loans)
for support.
(
24 h, 23 ꢀC). An aliquot (0.500 mL) was removed from
each layer and added to a stock solution of C F6 in
6
CF C H (0.200 mL, 0.176 M). A [d ]DMSO capillary
was added, and F NMR spectra were recorded. The
3
6
5
6
1
9
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