Synthesis and coordination chemistry of perfluoroalkyl-derivatised triarylphosphites

Article abstract of DOI:10.1016/S0040-4020(02)00208-9

A series of ortho-, meta- and para-perfluoroalkyl-substituted triaryl phosphites have been prepared and their coordination chemistry investigated. Spectroscopic and structural data for the metal complexes indicate that, even with the additional oxygen spacer unit, complete electronic insulation of the phosphorus(III) centres is not achieved.

Full text of DOI:10.1016/S0040-4020(02)00208-9

TETRAHEDRON
Pergamon
Tetrahedron 58 (2002) 3827±3834
Synthesis and coordination chemistry of
per¯uoroalkyl-derivatised triarylphosphites
p
Dave J. Adams, David Gudmunsen, John Fawcett, Eric G. Hope and Alison M. Stuart
Department of Chemistry, University of Leicester, Leicester, LE1 7RH, UK
Received 3 November 2001; revised 3 January 2002; accepted 16 January 2002
AbstractÐA series of ortho-, meta- and para-per¯uoroalkyl-substituted triaryl phosphites have been prepared and their coordination
chemistry investigated. Spectroscopic and structural data for the metal complexes indicate that, even with the additional oxygen spacer
unit, complete electronic insulation of the phosphorus(III) centres is not achieved. q 2002 Elsevier Science Ltd. All rights reserved.
One of the major foci in the development of catalysis under
uorous biphase conditions has been the electronic
outline the application of some of these ligands for the
rhodium-catalysed hydroformylation of long chain alkenes
under FBS conditions. We note that the synthesis of
P(OC H ±4-C F ) has been brie¯y described previously
¯
insulation of the ligand donor/metal centre from the power-
ful electron withdrawing in¯uence of the per¯uoroalkyl
substituents. In Horv a th and R a bai's seminal paper this
6
5
4
6 13 3
1
b y us and Mathivet et al. have also prepared similar
ligands.
1
6
was attempted using C H units but, subsequently,
2
4
2
theoretical calculations and experimental studies on
3
4
per¯uoroalkyl-phosphines and amines have shown that
complete electronic insulation is not achieved even with a
1. Ligand synthesis
5
±11
12±17
pentyl, C H , spacer group. We
5
and others
have
10
focussed our attentions on aryl electronic insulating units.
The direct attachment of one, two or three per¯uoroalkyl
groups in the ortho-, meta- or para-positions of triaryl-
phosphine ligands causes stepwise reductions in the
s-donor strength of these ligands indicating that the aryl
groups are also not perfect electronic insulators. Indeed,
although C H OCH and C H C H spacer units in
The triaryl phosphite ligands (4±6) were prepared
(Scheme 1), in 36±42% overall yields, following our
5
previous synthetic rationale involving the copper-mediated
coupling reaction of per¯uoroalkyl iodides with iodo-
phenols followed by reaction of the derivatised phenol
products (1±3) with PCl in the presence of triethylamine.
3
Although two of the phenols (1 and 3) were obtained
analytically pure following vacuum distillation, the product
from the coupling of C F I with 3-iodophenol was always
6
4
2
6
4
2
4
1
0
14,15
P(C H ±4-OCH C F )
2
and P(C H ±4-C H C F )
6 4 2 4 6 13 3
6
4
7
15 3
further reduce the electron withdrawing effect of the
uorous ponytails, they do not eliminate the electronic
6
13
¯
contaminated with large quantities of DMSO, as shown by
H NMR spectroscopy. Previously, it has been shown that
1
18
effects completely. In an attempt to establish whether it is
possible, or even desirable, to completely insulate the donor
phosphorus atoms without recourse to extremely sophisti-
cated spacer units, here we describe the synthesis and
coordination chemistry of a range of per¯uoroalkyl-
1,3-bis(2-hydroxyhexa¯uoro-2-propyl)-5-(per¯uoro-n-alkyl)-
benzenes can form extremely stable 1:1 molecular
complexes with DMSO which can be sublimed under
reduced pressure without dissociation. Consequently,
3-trideca¯uorohexylphenol (2) was obtained free from
3
5
derivatised triaryl phosphite ligands. In a sister paper we
Scheme 1. Synthesis of per¯uoroalkyl-substituted triarylphosphites
Keywords: ¯uorous biphase; triaryl phosphite; platinum group metals; X-ray analysis.
Corresponding author. Tel.: 144-116-252-2108; fax: 144-116-252-3789; e-mail: egh1@le.ac.uk
p
0040±4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(02)00208-9

3828
D. J. Adams et al. / Tetrahedron 58 (2002) 3827±3834
Scheme 2. Coordination chemistry of per¯uoroalkyl-substituted triarylphosphites.
DMSO by heating at 808C with a 5% sodium hydroxide
solution followed by precipitation with hydrochloric acid.
The per¯uoroalkyl-derivatised phenols were characterised
by standard procedures, the only unusual observation is
suggests that the presence of the oxygen atom between the
aryl ring and the phosphorus atom reduces, but does not
completely eliminate, the electronic in¯uence of the
¯uorous ponytails. Complexes 7a, 8a, 9a and 12a, which
contain the ortho-per¯uoroalkyl derivatised phosphite
ligand, each show the largest differences in their DP and
1
the H NMR resonance for the hydroxy proton in 2-trideca-
¯
uorohexylphenol which appears as a triplet due to through-
space coupling with the a-CF group; Jˆ8.3 Hz.
1
JMP values when compared to those for the underivatised
2
triarylphosphite complexes, and this probably arises from a
combination of the increased electronic in¯uence of the
ortho-substituent and the large steric bulk of this ligand.
These effects are mirrored in the carbonyl stretching
frequency of trans-[RhCl(CO){P(OC H ±2-C F ) } ] (13)
All the phosphites were obtained as air-stable clear viscous
oils. The electron withdrawing in¯uence of the per¯uoro-
alkyl chains is manifest in an increased susceptibility to
hydrolysis.
6
4
6 13 3 2
2
1
which is ca. 30 cm
higher than those for trans-
RhCl(CO)L ] {LˆP(OPh) Ð2016 cm ; P(OC H ±2-
) Ð2012 cm } indicating a signi®cant reduction in
3 3
2
1 20
[
2
3
6
4
2
1 21
2
. Coordination chemistry and spectroscopic studies
CH
electron density at the metal centre for the per¯uoroalkyl-
ated metal complex.
We have previously used the spectroscopic and structural
properties of transition metal complexes as a clear guide to
the electronic and steric impact of per¯uoroalkyl sub-
However, it is very unlikely that the electronic in¯uence of
the per¯uoroalkyl substituents can account for the most
unusual reactions of these ¯uorous-derivatised phosphite
ligands. In contrast to the reactions of phosphine, phos-
phinite, phosphonite and most phosphite ligands, including
P(OC H ±2-C F ) (4), with [Rh(m-Cl)(CO) ] , which
6 4 6 13 3 2 2
result in the elimination of one equivalent of carbon
monoxide and cleavage of the halide bridge to afford the
6
±8,11
stituents on the donor properties of ligands.
The
derivatised phosphites (4±6) react with platinum metal
starting materials in, for the most part, exactly the same
way as triphenylphosphite or per¯uoroalkyl derivatised
triaryl phosphines (Scheme 2); i.e. substitution of weakly
coordinated ligands and cleavage of halide bridged dimers.
The only exception to this rule arises in the reactions of two
of the phosphites with [Rh(m-Cl)(CO) ] (see below). As
ubiquitous trans-[RhCl(CO)L
the meta- and para-per¯uoroalkyl derivatised phosphites (5
and 6) with [Rh(m-Cl)(CO) afford only [Rh(m-Cl)L ]
2 2
] complexes, the reactions of
2
2
2
expected, the large steric in¯uence of the per¯uoroalkyl
groups in the ortho-positions in tris(2-trideca¯uorohexyl-
phenyl)phosphite (4) is evidenced in the formation of
]
2
2
2
2,23
(12). Normally, this reaction
the incoming ligand with the metal centre followed by
involves interaction of
the, usually, less-thermodynamically favourable trans-
[
for trans-[PtCl {(P(OC H ±2-CH ) } ] (Table 1) which
1
PtCl (ligand) ] (8a), for which J is comparable to that
elimination of one equivalent of CO to give [Rh(m-
Cl)(CO)L] followed by cleavage of the halide bridges
2
2
2
PtP
1
9
2
6
4
3 3 2
contains the bulky tris-ortho-tolyl phosphite ligand, and
the failure to prepare the analogue of Wilkinson's complex
with the second equivalent of ligand to give the mono-
nuclear product. However, although tri-substituted
[
RhCl(ligand)3].
complexes [RhL
have been observed in solution,
precedent for the isolation of the tetra-substituted [Rh(m-
Cl)L (12) as the exclusive product of this reaction. We
can only surmise that the per¯uoroalkyl substituents suf®-
ciently alter the physical properties of the halide-bridged
intermediates, which have been shown by X-ray crystallo-
2
(m-Cl)
2
Rh(CO)L] (LˆPPh
3
, P(OMe)
we can ®nd no
3
)
2
4,25
The complexes have been characterised by a combination of
elemental analysis, IR spectroscopy, mass spectrometry and
multinuclear NMR spectroscopies. A comparison of the
NMR data with those for related triarylphosphite metal
complexes (Table 1), illustrates a small, but consistent,
]
2 2
1
decrease in DP; JMP varies non-systematically. This
graphy to usually have folded (1238) RhCl Rh bridges in the
2

D. J. Adams et al. / Tetrahedron 58 (2002) 3827±3834
3829
31
1
Table 1. P{ H} NMR data for metal±phosphite complexes
a
DP (ppm)
1
Complex
dP
free ligand)
ppm)
dP
(complex)
(ppm)
JM±P (Hz)
(
(
b
trans-[PdCl
trans-[PdCl
trans-[PdCl
trans-[PdCl
2
2
2
2
{P(OC
{P(OC
{P(OC
{P(OC
6
6
6
6
H
H
H
H
4
4
4
4
±2-CH
3
)
3
}
2
]
}
}
}
]
129.8
124.9
126.1
125.0
129.8
124.9
127.8
126.1
125.0
127.8
124.9
126.1
125.0
125.0
127.8
125.0
127.8
124.9
126.1
125.0
127.8
124.9
127.8
126.1
125.0
86.8
85.5
82.3
83.6
74.9
77.2
59.1
60.9
43.0
39.4
43.8
41.4
54.9
47.7
68.7
65.2
59.6
23.6
15.1
19.0
18.5
57.3
65.1
58.7
12.9
16.7
12.5
11.8
12.6
9.7
8.9, 15.9
7.1, 12.5
3.8, 11.4
±
±
±
±
±2-C
±3-C
±4-C
6
6
6
F
F
F
13
13
13
)
3
)
3
)
3
2
] (7a)
] (7b)
] (7c)
2
2
b
trans-[PtCl
trans-[PtCl
2
{P(OC
{P(OC
6
H
H
4
4
±2-CH
±2-C
3
)
3
}
2
4405
4589
5800
5777
5660
240
251
244
245
±
6261
6300
311
318
309
313
217
223
2
6
6
F
13
)
3
}
2
] (8a)
b
cis-[PtCl
cis-[PtCl
cis-[PtCl
2
2
2
{P(OC
{P(OC
{P(OC
6
6
6
H
H
H
5
4
4
)
3
}
2
]
±3-C
±4-C
6
F
F
13
)
)
3
}
2
] (8b)
] (8c)
6
c
13
3
}
2
65.4
p
[
[
[
[
[
Cp RhCl
2
2
2
2
{P(OC
6
H
6
H
6
H
6
H
5
4
4
4
)
3
}]
104.2
109.8
107.1
106.5
67.7
p
Cp RhCl
{P(OC
{P(OC
{P(OC
±2-C
±3-C
±4-C
6
F
6
F
6
F
13
13
13
)
)
)
3
3
3
}] (9a)
}] (9b)
}] (9c)
p
Cp RhCl
p
Cp RhCl
p
Cp IrCl
2
{P(OC
6
H
4
±4-C
6
F
13
)
}]
3
}] (10)
c
d
cis-[PtCl
cis-[PtCl
2
(PEt
(PEt
3
){P(OC
){P(OC
6
H
5
)
3
62.7
66.3
d
2
3
6
H
4
±4-C
6
F
13
)
3
}] (11)
[
[
[
[
[
[
[
[
[
Rh(m-Cl){P(OC
6
6
6
6
H
H
H
H
5
4
4
)
3
2
} ]
2
114.9
108.2
113.6
113.2
115.2
115.2
118.9, 111.9
119.0, 113.6
121.2, 113.6
Rh(m-Cl){P(OC
Rh(m-Cl){P(OC
Rh(m-Cl){P(OC
RhCl(CO){P(OC
RhCl(CO){P(OC
RhCl{P(OC
RhCl{P(OC
RhCl{P(OC
±2-C
±3-C
±4-C
6
6
6
F
F
F
13
13
13
)
)
)
3
3
3
}
}
}
2
]
2
]
2
]
2
2
2
(12a)
(12b)
(12c)
4
e
6
H
5
)
3
}
2
]
6
H
4
f
]
±2-C
F
6 13
)
3
}
2
] (13)
6
H
6
H
6
H
5
4
4
)
3
}
3
285, 224
276, 227
286, 225
±3-C
±4-C
6
F
F
13
)
)
3
}
3
] (14a)
] (14b)
6
13
}
3 3
a
b
c
d
e
f
DPˆdP(free ligand)2dP(complex).
Data taken from Ref. 17.
Data taken from Ref. 32.
Phosphite ligand.
Data taken from Ref. 33.
Data taken from Ref. 34.
2
6
p
of [Cp RhCl {P(OC H ±4-C F ) }] (9c) were obtained by
slow evaporation from acetone solution. Selected bond
lengths and angles are shown in Table 2 and the molecular
structure is shown in Fig. 1.
solid state, to promote CO substitution over halide-bridge
cleavage.
2
6
4
6 13 3
3
. Structural characterisation
In previous structural determinations of metal complexes
incorporating ligands with per¯uoroalkyl substituents, we
Crystals, suitable for single crystal X-ray structural analysis,
p
Table 2. Selected bond distances (A), angles (8), torsion angles (8) and non-bonded F´´´F distances (A) for [Cp RhCl
Ê
Ê
2 6
{P(OC H
4
6
±4-C F
13
)
3
}] (9c)
Rh(1)±C(4)
Rh(1)±C(5)
Rh(1)±C(1)
Rh(1)±C(3)
Rh(1)±C(2)
P(1)±O(1)
P(1)±O(2)
P(1)±O(3)
P(1)±Rh(1)±Cl(1)
P(1)±Rh(1)±Cl(2)
Cl(1)±Rh(1)±Cl(2)
O(2)±P(1)±O(1)
O(2)±P(1)±O(3)
O(1)±P(1)±O(3)
C(43)±C(44)±C(45)±C(46)
C(41)±C(42)±C(43)±C(44)
C(31)±C(32)±C(33)±C(34)
C(29)±C(30)±C(31)±C(32)
C(19)±C(20)±C(21)±C(22)
C(17)±C(18)±C(19)±C(20)
F(33B)´´´F(46A)
F(21B)´´´F(21B)
F(20B)´´´F(42B)
F(34A)´´´F(32A)
F(17B)´´´F(31A)
2.167(12)
2.194(11)
2.197(11)
2.231(12)
2.236(12)
1.581(10)
1.571(10)
1.600(10)
89.96(11)
87.78(11)
89.70(11)
96.9(7)
Rh(1)±P(1)
Rh(1)±Cl(1)
Rh(1)±Cl(2)
2.237(3)
2.386(3)
2.405(3)
O(1)±C(11)
O(2)±C(23)
O(3)±C(35)
O(2)±P(1)±Rh(1)
O(1)±P(1)±Rh(1)
O(3)±P(1)±Rh(1)
C(11)±O(1)±P(1)
C(23)±O(2)±P(1)
C(35)±O(3)±P(1)
C(42)±C(43)±C(44)±C(45)
C(38)±C(41)±C(42)±C(43)
C(30)±C(31)±C(32)±C(33)
C(26)±C(29)±C(30)±C(31)
C(18)±C(19)±C(20)±C(21)
C(14)±C(17)±C(18)±C(19)
F(21A)´´´F(21B)
F(42A)´´´F(46B)
F(17A)´´´F(19A)
F(30B)´´´F(41A)
F(17B)´´´F(29A)
1.399(16)
1.360(15)
1.421(17)
121.6(4)
115.5(4)
120.4(4)
121.7(10)
136.9(10)
129.8(9)
2166.68
2169.02
2167.72
2162.43
165.32
171.55
2.964
2.954
2.864
2.796
2.652
95.6(7)
102.5(6)
2175.25
2165.14
2175.25
250.16
166.18
166.38
2.947
2.875
2.691
2.944
2.903

3830
D. J. Adams et al. / Tetrahedron 58 (2002) 3827±3834
p
2 6 4 6 13 3
Figure 1. Molecular Structure of [Cp RhCl {P(OC H ±4-C F ) }] (9c). Displacement ellipsoids are shown at the 30% probability level. The H atoms are
omitted for clarity.
2
1
have concluded that the ¯uorous ponytails have a negligible
effect upon the geometry of the metal ®rst coordination
sphere but dominate the packing of these molecules in the
DigilabFTS40 Fourier-transform spectrometer at 4 cm
resolution for the complexes as Nujol mulls held between
KBr discs. Elemental analyses were performed by
Butterworth Laboratories Ltd. Mass spectra were recorded
on a Kratos Concept 1H mass spectrometer.
6
,8,11
solid state.
crystal structure of [Cp RhCl {P(OC H ±4-C F ) }] (9c)
Similar conclusions can be drawn from the
p
2
6
4
6 13 3
that displays the expected three-legged piano-stool
geometry about the rhodium centre in which the bond
lengths to rhodium and angles at rhodium and phos-
phorus are very similar to those for the related
2
9
The complexes cis-[MCl (MeCN) ] (MˆPd, Pt) and
2
2
3
3 2
0
[PtCl (PEt )] were prepared as described previously and
the complexes, [RhCl(C H ) ] , [RhCl(CO) ] [Cp MCl ]
2 2
2
p
2
4 2 2
2 2,
p
27
[
distance, 1.583(6) A, is slightly smaller than the average
Cp IrCl {P(OC H -2,6-F }]. The average P±O bond
(MˆRh, Ir) (Aldrich) were used as supplied. Dichloro-
methane and per¯uoro-1,3-dimethylcyclohexane (PP3)
were each dried by re¯uxing over calcium hydride under
nitrogen, distilled under nitrogen and stored in closed
ampoules over molecular sieves. PP3 was also freezed/
pumped/thawed three times to remove all dissolved gases.
Hexane was dried by re¯uxing over potassium metal under
nitrogen, distilled and was stored similarly. Diethyl ether
was dried by re¯uxing over sodium metal under nitrogen,
distilled and stored similarly.
2
6
3
2
Ê
Ê
for coordinated triphenylphosphite ligands, 1.600(11) A,
28
which could arise from the electronic in¯uence of the
per¯uoroalkyl substituents. The three per¯uoroalkyl tails
radiate away from the metal centre, two in a regular linear
fashion and the third with a single C±C±C±C torsion angle
around 508, and the extended view of the structure reveals
¯
uorous domains in which the per¯uoroalkyl chains line up
affording a number of relatively short, non-bonded, inter-
molecular ¯uorine´´´ ¯uorine contacts.
2-Trideca¯uorohexylphenol (1) and 3-trideca¯uorohexyl-
phenol (2) were prepared following our previously
5
4. Experimental
described procedure for the preparation of 4-trideca¯uoro-
hexylphenol (3) in 69 and 89% yields, respectively. Tris(2-
trideca¯uorohexylphenyl)phosphite (4) and tris(3-tri¯uoro-
hexylphenyl)phosphite (5), were similarly prepared
following the procedure for the preparation of tris(4-tri-
deca¯uorohexylphenyl)phosphite (6) in 52 and 45% yields,
respectively.
4
.1. General
1
9
31
5
Proton, F and P NMR spectroscopies were carried out on
a Bruker ARX 250 spectrometer at 250.13, 235.34 and
1
4
01.26 MHz or on a Bruker DRX 400 spectrometer at
00.13, 376.50 and 161.98 MHz. All chemical shifts are
quoted in ppm using the high-frequency positive conven-
tion; H NMR spectra were referenced to external SiMe ,
4.1.1. 2-Trideca¯uorohexylphenol (1). Bp 96±978C
(20 mmHg). H NMR (CDCl ) d 7.31 (m, 2H), 6.89 (m,
1
1
4
3
1
9
31
F NMR spectra to external CFCl and P NMR spectra to
19
1
2H), 6.32 (t, 1H, JHFˆ8.3 Hz, OH). F{ H} NMR
3
4
external 85% H PO . The IR spectra were recorded on a
3
(CDCl
3
) d 281.30 (tm, 3F, JFFˆ10.1 Hz, CF
), 2108.66
3
4

D. J. Adams et al. / Tetrahedron 58 (2002) 3827±3834
3831
4
(
tm, 2F, J ˆ14.8 Hz, a-CF ), 2122.09 (m, 2F, CF ),
4.2. General procedure for the preparation of [MCl L ]
2 2
(MˆPd, Pt)
FF
2
2
2123.24 (m, 4F, CF ), 2126.65 (m, 2F, CF ). MS (EI)
m/z 412 (M ), 393 (M2F ); HRMS (EI) calcd for
2
2
1
1
C H F O 412.01328, found 412.01328.
1
A slurry of [MCl (MeCN) ] (MˆPd, Pt) (0.29 mmol) and
2
5
13
2
2
the ligand (0.80 mmol) in dichloromethane was heated
under re¯ux under nitrogen for 2 h to give a clear colourless
solution. After cooling, the solution was concentrated in
vacuo and petroleum ether added to precipitate the product
as a yellow (Pd) or white (Pt) solid, which was ®ltered,
washed with petroleum ether and dried in vacuo.
4.1.2. 3-Trideca¯uorohexylphenol (2). Following
Kulgelrohr distillation, 2 was puri®ed by heating at 808C
with a 5% sodium hydroxide solution, followed by precipi-
tation with dilute hydrochloric acid. White solid. Bp 60±
1
28C (0.01 mmHg). H NMR (CDCl ) d 7.30 (t, 1H,
6
3
3
3
JHHˆ7.9 Hz, 5-H), 7.09 (d, 1H, J ˆ7.6 Hz, 6-H), 6.96
HH
1
9
1
m, 2H), 5.21 (s, 1H, OH). F{ H} NMR (CDCl ) d 281.34
(
4.2.1. trans-[PdCl {P(OC H ±2-C F ) } ] (7a). Obtained
2
3
6
4
6 13 3 2
4
1
6
19
in 43% yield. H NMR (d -acetone) d 7.50 (m, 4H). F{ H}
1
(
tm, 3F, J ˆ11.3 Hz, CF3), 2111.03 (tm, 2F,
FF
4
6
4
J ˆ14.2 Hz, a-CF ), 2122.05 (m, 2F, CF ), 2122.46
NMR (d -acetone) d 282.31 (tm, 3F, J ˆ11.0 Hz, CF ),
2 2
FF
2
2
FF
3
(m, 2F, CF ), 2123.34 (m, 2F, CF ), 2126.67 (m, 2F,
CF ). MS (EI) m/z 412 (M ), 393 (M2F ); HRMS (EI)
2108.91 (m, 2F, a-CF ), 2121.90 (m, 2F, CF ), 2122.67
2
2
1
1
2
(m, 2F, CF ), 2123.91 (m, 2F, CF ), 2127.41 (m, 2F,
2 2
31 1 6
calcd for C H F O 412.01328, found 412.01328.
1
CF2). P{ H} NMR (d -acetone) d 85.5 (s). MS (FAB)
2
5 13
1
m/z 2634 (M22Cl ). Anal. calcd for C H Cl F O P Pd:
7
2
24
2
78
6 2
4
.1.3. 4-Trideca¯uorohexylphenol (3). Bp 558C
7.31 (d, 2H,
C, 31.94; H, 0.89; P, 2.29; found: C, 31.95; H, 0.91; P,
2.14%.
1
(
0.01 mmHg).
H
NMR (CDCl3)
d
3
3
JHHˆ7.1 Hz, 3,5-H's), 6.92 (d, 2H, JHHˆ7.1 Hz, 2,6-
1
H's), 5.23 (s, 1H, OH). F{ H} NMR (CDCl ) d 281.26
9
1
3
4.2.2. trans-[PdCl {P(OC H ±3-C F ) } ] (7b). Obtained
6 13 3 2
2
6
4
3
4
1
(
tt, 3F, J ˆ2.5 Hz, J ˆ10.1 Hz, CF ), 2110.15 (tm, 2F,
in 62% yield. H NMR (CDCl ) d 7.42 (m, 3H), 7.11 (s, 1H,
3
1 4
FF
FF
3
4
1
9
J ˆ14.6 Hz, a-CF ), 2121.92 (m, 2F, CF ), 2122.42 (m,
2-H). F{ H} NMR (CDCl ) d 281.54 (tm, 3F, J ˆ
FF
2
2
3
FF
4
2F, CF ), 2123.24 (m, 2F, CF ), 2126.55 (m, 2F, CF ).
MS(EI) m/z 412 (M ), 393 (M2F ); HRMS (EI) calcd
11.3 Hz, CF ), 2111.72 (tm, 2F, J ˆ14.2 Hz, a-CF ),
2122.25 (m, 2F, CF ), 2122.39 (m, 2F, CF ), 2123.62
2 2
2
2
2
3 FF 2
1
1
3
1
1
for C H F O 412.01328, found 412.01327.
13
(m, 2F, CF ), 2126.89 (m, 2F, CF ). P{ H} NMR
2 2
1
2
5
1
CDCl ) d 82.3 (s). MS (FAB) m/z 2671 (M2Cl ). Anal.
(
3
4
1
.1.4. Tris(2-trideca¯uorohexylphenyl)phosphite (4). Bp
808C (0.01 mmHg). H NMR (d -toluene) d 7.50 (d, 1H,
calcd for C H Cl F O P Pd: C, 31.94; H, 0.89; P, 2.29;
72 24 2 78 6 2
found: C, 31.73; H, 0.98; P, 2.20%.
1
8
3
3
JHHˆ8.1 Hz, 6-H), 7.41 (d, 1H, J ˆ8.1 Hz, 3-H), 7.10 (t,
HH
3
3
1
H, J ˆ8.1 Hz, 5-H), 6.79 (t, 1H, J ˆ8.1 Hz, 4-H).
4.2.3. trans-[PdCl {P(OC H ±4-C F ) } ] (7c). Obtained
4
HH
HH
2
6
6 13 3 2
1
9
1
8
4
1
3
F{ H} NMR (d -toluene) d 281.55 (tm, 3F, J ˆ
FF
in 62% yield. H NMR (CDCl ) d 8.10 (d, 2H, J ˆ8.7 Hz,
3
HH
1
4
3
19
1
0.1 Hz, CF ), 2107.97 (tm, 2F, J ˆ14.9 Hz, a-CF ),
2,6-H's), 7.82 (d, 2H, J ˆ8.7 Hz, 3,5-H's). F{ H} NMR
3
FF
2
HH
3
4
2
121.29 (m, 2F, CF ), 2122.08 (m, 2F, CF ), 2123.14
2
(CDCl ) d 280.86 (tt, 3F, J ˆ2.2, J ˆ11.3 Hz, CF ),
2
3
FF
FF
3
3
m, 2F, CF ), 2126.64 (m, 2F, CF ). P{ H} (d -toluene)
1
1
8
4
(
d 124.9 (s). MS (EI) m/z 1264 (M ), 995 (M2C F ), 853
2109.75 (tm, 2F, J ˆ14.6 Hz, a-CF ), 2121.17 (m, 2F,
CF ), 2121.63 (m, 2F, CF ), 2122.57 (m, 2F, CF ),
2 2 2
2
2
FF 2
1
1
11
5
1
13
31
1
(
M2OC H C F ). Anal. calcd for C H F O P: C,
3
2125.98 (m, 2F, CF2). P{ H} NMR (CDCl ) d 83.6 (s).
3
1
IR (Nujol) n(Pd±Cl) 332, 308 cm . MS (FAB) m/z 2671
6
4
6
36 12 39
2
3
4.17; H, 0.95; P, 2.45; found: C, 34.05; H, 1.02; P, 2.46%.
1
M2Cl ),
1
(M22Cl ).
(
2634
Anal.
calcd
C H Cl F O P Pd: C, 31.94; H, 0.89; Cl, 2.62; found:
for
4
1
2
8
.1.5. Tris(3-trideca¯uorohexylphenyl)phosphite (5). Bp
7
2
24
2
78
6 2
1
858C (0.01 mmHg). H NMR (d -toluene) d 7.31 (s, 1H,
8
C, 30.68; H, 0.77; Cl, 2.24%.
3
3
-H), 7.14 (d, 1H, J ˆ7.6 Hz, 6-H), 6.99 (d, 1H, J
ˆ
HH
HH
3
19
1
.0 Hz, 4-H), 6.75 (t, 1H, J ˆ8.0 Hz, 5-H). F{ H} NMR
4.2.4. trans-[PtCl {P(OC H ±2-C F ) } ] (8a). Obtained
2
HH
6
4
6 13 3 2
8
3
4
1
in 25% yield. H NMR (d -acetone) d 7.76 (d, 1H,
6
(
d -toluene) d 281.86 (tt, 3F, J ˆ2.5 Hz, J ˆ9.3 Hz,
FF
FF
4
3
3
CF ), 2111.38 (t, 2F, J ˆ15.9 Hz, a-CF ), 2121.99 (m,
JHHˆ8.5 Hz, 6-H), 7.69 (d, 1H, J ˆ8.5 Hz, 3-H), 7.58
3
FF
2
HH
3
3
2
F, CF ), 2122.27 (m, 2F, CF ), 2123.40 (m, 2F, CF ),
2
(t, 1H, J ˆ7.3 Hz, 5-H), 7.48 (t, 1H, J ˆ7.6, 4-H).
2
2
HH
HH
3
1
1
126.85 (m, 2F, CF2). P{ H} (d -toluene) d 126.1 (s).
8
19
1
6
4
2
MS (EI) m/z 1264 (M ), 995 (M2C5F11 ), 853
F{ H} NMR (d -acetone) d 282.29 (tm, 3F, J ˆ
FF
1
1
4
8.5 Hz, CF ), 2108.87 (tm, 2F, J ˆ14.2 Hz, a-CF ),
3
FF
2
1
13
(
M2OC H C F ). Anal. calcd for C H F O P: C,
6
2121.84 (m, 2F, CF ), 2122.65 (m, 2F, CF ), 2123.90
2
4
6
36 12 39
3
2
3
1
1
6
3
2
4.17; H, 0.95; P, 2.45; found: C, 34.20; H, 1.04; P,
.25%.
(m, 2F, CF ), 2127.39 (m, 2F, CF ). P{ H} NMR (d -
2 2
1
acetone) d 77.2 (s, J ˆ4589 Hz). MS (FAB) m/z 2759
PtP
1
M2Cl ),
1
(M22Cl ).
(
2724
Anal.
calcd
for
4
.1.6. Tris(4-trideca¯uorohexylphenyl)phosphite (6). Bp
208C (0.01 mmHg). H NMR (d -toluene) d 7.24 (d, 2H,
C H Cl F O P Pt: C, 30.92; H, 0.86; P, 2.22; found: C,
72 24 2 78 6 2
30.84; H, 0.85; P, 2.14%.
1
8
2
3
3
J
ˆ8.6 Hz, 3,5-H's), 6.88 (d, 2H, J ˆ8.6 Hz, 2,6-H's).
HH
HH
1
9
1
8
3
F{ H} NMR (d -toluene) d 281.45 (tt, 3F, J ˆ2.5 Hz,
FF
4.2.5. cis-[PtCl {P(OC H ±3-C F ) } ] (8b). Obtained in
6 13 3 2
2
6
6
4
4
4
1
J ˆ10.1 Hz, CF ), 2110.50 (t, 2F, J ˆ14.6 Hz, a-CF ),
60% yield. H NMR (d -acetone) d 7.45 (m, 3H), 7.08 (s,
19 1 6
1H, 2-H). F{ H} NMR (d -acetone) d 281.85 (m, 3F,
FF
3
FF
2
2
2
1
121.68 (m, 2F, CF ), 2122.05 (m, 2F, CF ), 2123.09 (m,
2
2
3
F, CF ), 2126.51 (m, 2F, CF ). P{ H} (d -toluene) d
1
1
8
4
2
2
CF ), 2111.79 (tm, 2F, J ˆ14.2 Hz, a-CF ), 2122.41
3
FF
2
1
25.1 (s). MS (EI) m/z 1264 (M ), 995 (M2C F ), 853
1
5
11
(m, 2F, CF ), 2122.65 (m, 2F, CF ), 2123.68 (m, 2F,
2
2
1
13
31
1
6
(
M2OC H C F ). Anal. calcd for C H F O P: C,
36 12 39
CF ), 2127.01 (m, 2F, CF ). P{ H} NMR (d -acetone) d
2 2
1
60.9 (s, J ˆ5777 Hz). MS (FAB) m/z 2759 (M2Cl ),
6
4
6
3
1
3
4.17; H, 0.95; found: C, 34.04; H, 1.00%.
PtP

3832
D. J. Adams et al. / Tetrahedron 58 (2002) 3827±3834
1
724 (M22Cl ). Anal. calcd for C H Cl F O P Pt: C,
3
2
3,5-H's), 7.38 (d, 6H, J ˆ8.7 Hz, 2,6-H's), 1.49 (d, 15H,
7
2
24
2
78
6
2
HH
1
9
1
3
0.92; H, 0.86; P, 2.22; found: C, 30.96; H, 0.84; P, 2.30%.
J ˆ3.8 Hz, CH ). F{ H} NMR (CDCl ) d 281.30 (tt, 3F,
PH
3
3
3
4
J ˆ2.3 Hz, J ˆ10.0 Hz, CF ), 2110.93 (tm, 2F,
FF
FF
3
4
4
5
.2.6. cis-[PtCl {P(OC H ±4-C F ) } ] (8c). Obtained in
13 3 2
J ˆ14.4 Hz, a-CF ), 2121.88 (m, 2F, CF ), 2122.33
2
6
4
6
FF
2
2
1
9% yield. H NMR (d -acetone) d 7.80 (d, 2H,
6
(m, 2F, CF ), 2123.29 (m, 2F, CF ), 2126.62 (m, 2F,
2 2
3
3
31
1
CF2). P{ H} NMR (CDCl ) d 67.7 (s). Anal. calcd for
JHHˆ8.8 Hz, 2,6-H's), 7.64 (d, 2H, JHHˆ8.8 Hz, 3,5-
3
1
9
1
4
H's). F{ H} NMR (D O) d 282.17 (t, 3F, J ˆ10.0 Hz,
C H Cl F O PIr: C, 33.21; H, 1.62; Cl, 4.27; found: C,
46 27
33.20; H, 1.45; Cl, 3.45%.
2
4
FF
2
39
3
CF ), 2111.20 (tm, 2F, J ˆ13.9 Hz, a-CF ), 2122.36 (m,
3
FF
2
4
F, CF ), 2123.78 (m, 2F, CF ), 2127.24 (m, 2F, CF ).
2 2 2
1 1
3
1
P{ H} NMR (D O) d 65.4 (s, JPtPˆ5660 Hz). IR
4.3.5. cis-[PtCl (PEt ){P(OC H ±4-C F ) }] (11). A
6 13 3
2
2
3
6
4
2
Nujol) n(Pt±Cl) 330, 308 cm . MS (FAB) m/z 2759
1
(
(
slurry of [{PtCl(m-Cl)(PEt )} ] (0.067 g, 0.09 mmol) and
3 2
P(OC H ±4-C F ) (0.272 g, 0.22 mmol) in dichloro-
6 4 6 13 3
1
M2Cl ),
1
(M22Cl ).
2724
Anal.
calcd
for
3
C H Cl F O P Pt: C, 30.92; H, 0.86; Cl, 2.54; found: C,
78
methane (30 cm ) was heated under re¯ux under dinitrogen
for 10 min. to give a clear colourless solution. After cooling,
the solution was concentrated in vacuo, and petroleum ether
added to precipitate the product as a ®ne white solid, which
was ®ltered, washed with petroleum ether and dried in
vacuo. Yield 0.209 g, 73%. H NMR (CDCl ) d 7.73 (d,
7
2
24
2
6 2
2
9.25; H, 0.82; Cl, 2.60%.
4
.3. General procedure for the preparation of
p
[
Cp MCl L] (MˆRh, Ir)
2
1
3
3
3
p
6
2
1
H, JHHˆ8.7 Hz, 3,5-H's), 7.62 (d, 6H, JHHˆ8.7 Hz,
A slurry of the [Cp MCl ] (MˆRh, Ir) (0.24 mmol) and the
2
2
2
3
,6-H's), 2.21 (dq, 6H, J ˆ10.2 Hz, J ˆ7.6 Hz, CH ),
ligand (0.58 mmol) were re¯uxed in dichloromethane (Rh)
or benzene (Ir) under dinitrogen for 1 h to give a clear red
PH HH 2
3
3
19
1
.04 (m, 9H, J ˆ18.2 Hz, J ˆ7.6 Hz, CH ). F{ H}
PH
HH
3
3
4
NMR (CDCl ) d 281.33 (tt, 3F, J ˆ2.3 Hz, J ˆ
(
Rh) or clear orange (Ir) solution. After cooling, the solution
was concentrated in vacuo and petroleum ether added to
precipitate the product as an orange solid, which was
3
FF
FF
4
1
0.1 Hz, CF ), 2111.03 (t, 2F, J ˆ14.3 Hz, a-CF ),
3
FF
2
2
121.90 (m, 2F, CF ), 2122.23 (m, 2F, CF ), 2123.28
2 2
31 1
(
(
m, 2F, CF ), 2126.62 (m, 2F, CF ). P{ H} NMR
2 2
®
ltered, washed with petroleum ether and dried in vacuo.
1
2
CDCl ) d 66.3 (d, 1P, JPtPˆ6300 Hz, J ˆ19.9 Hz,
3
PP
1
2
p
.3.1. Cp RhCl {P(OC H ±2-C F ) }] (9a). Obtained in
P{OAr} ), 17.6 (d, 1P, JPtPˆ3105 Hz, J ˆ19.9 Hz,
4
4
6
3
PP
2
6
4
6 13 3
1
PEt ). MS (FAB) m/z 1613 (M2Cl ), 1577 (M22Cl ).
1
1
3
1% yield. H NMR (CDCl ) d 8.05 (d, 3H, J ˆ8.0 Hz,
3
3
HH
Anal. calcd for C H Cl F O P Pt: C, 30.58; H, 1.64; Cl,
3 2
-H), 7.39 (m, 6H), 7.21 (m, 3H), 1.36 (d, 15H, J ˆ6.2 Hz,
PH
42 27
2
39
1
9
1
4
4
.31; found: C, 30.60; H, 1.38; Cl, 4.15%.
CH ). F{ H} NMR (CDCl ) d 281.52 (tm, 3F, J ˆ
3
3
FF
11.3 Hz, CF ), 2107.52 (m, 2F, a-CF ), 2121.55 (m, 2F,
3 2
CF ), 2122.35 (m, 2F, CF ), 2123.53 (m, 2F, CF ),
126.90 (m, 2F, CF2). P{ H} NMR (CDCl ) d 109.8 (d,
3
2
2
2
3
1
1
4.4. General procedure for the preparation of [Rh(m-
Cl)L2]2
2
1
1
1
JRhPˆ251 Hz). MS (FAB) m/z 1572 (M ), 1537 (M2Cl ).
Anal. calcd for C H Cl F O PRh: C, 35.09; H, 1.72; P,
4
6
27
2
39
3
The addition of a colourless solution of the ligand
(
1
.97; found: C, 35.10; H, 1.68; P, 1.84%.
3
0.33 mmol) in dry PP3 (40 cm ) to a deep red solution of
p
.3.2. Cp RhCl {P(OC H ±3-C F ) }] (9b). Obtained in
[
Rh(CO) Cl] (0.08 mmol) in dry dichloromethane under
2
4
7
6
2
2
6
4
6 13 3
1
3
dinitrogen resulted in an almost instantaneous decolourisa-
tion of the upper organic layer and the ¯uorous layer turned
yellow. The lower ¯uorous layer was transferred, under
nitrogen, to a Schlenk ¯ask where the solvent was removed
in vacuo, to leave a yellow solid, which was recrystallized
from ethanol and dried in vacuo.
6% yield. H NMR (CDCl ) d 7.71 (d, 3H, J ˆ7.6 Hz,
3
HH
3
-H), 7.45 (t, 3H, JHHˆ7.9 Hz, 5-H), 7.38 (d, 3H,
3
JHHˆ7.9 Hz, 4-H), 7.21 (s, 3H, 2-H), 1.41 (d, 15H,
1
9
1
J ˆ6.3 Hz, CH ). F{ H} NMR (CDCl ) d 281.42 (tm,
PH
3
3
4
4
3
a-CF ), 2122.11 (m, 2F, CF ), 2122.34 (m, 2F, CF ),
F, J ˆ8.5 Hz, CF ), 2111.34 (tm, 2F, J ˆ14.2 Hz,
FF
3
FF
2 2 2
3
1
1
2
123.51 (m, 2F, CF ), 2126.78 (m, 2F, CF ). P{ H}
2 2
1
4.4.1. Rh(m-Cl){P(OC H ±2-C F ) } ] (12a). Was
prepared similarly using [Rh(h -C H ) (m-Cl)] in 39%
NMR (CDCl ) d 107.1 (d, J ˆ244 Hz). MS (FAB) m/z
6 4 6 13 3 2 2
2
3
RhP
1
537 (M2Cl ). Anal. calcd for C H Cl F O PRh: C,
1
2
4 2
2
4
6
27
2
39
3
1
yield. H NMR (D O) d 7.65 (m, 4H). F{ H} NMR
19
1
3
5.09; H, 1.72; P, 1.97; found: C, 35.30; H, 1.71; P, 1.24%.
2
4
(
D O) d 282.22 (tm, 3F, J ˆ8.5 Hz, CF ), 2108.42 (m,
2
FF
3
p
.3.3. Cp RhCl {P(OC H ±4-C F ) }] (9c). Obtained in
4
6
3
2F, a-CF
2123.77 (m, 2F, CF
2
), 2121.65 (m, 2F, CF
2
), 2122.60 (m, 2F, CF
2
),
) P{ H} NMR
2
6
4
6 13 3
1
3
31
1
6% yield. H NMR (CDCl ) d 7.32 (d, 6H, J ˆ8.8 Hz,
2
), 2126.26 (m, 2F, CF
2
3
HH
3
1
,5-H's), 7.22 (d, 6H, J ˆ8.8 Hz, 2,6-H's), 1.41 (d, 15H,
(D O) d 108.2 (d,
2
J
Rh: C, 32.40; H, 0.90; P, 2.33; found: C,
RhPˆ318 Hz). Anal. calcd for
HH
1
9
1
J ˆ6.3 Hz, CH ). F{ H} NMR (CDCl ) d 281.41 (tt, 3F,
C
72
H
24ClF78
O
32.22; H, 0.89; P, 3.20%.
6
P
2
PH
3
3
3
4
4
J ˆ2.2 Hz, J ˆ10.0 Hz, CF ), 2110.99 (tm, 2F,
FF
FF
3
J ˆ14.4 Hz, a-CF ), 2121.95 (m, 2F, CF ), 2122.43
FF
2
2
(
m, 2F, CF ), 2123.38 (m, 2F, CF ), 2126.71 (m, 2F,
2
4.4.2. Rh(m-Cl){P(OC
6
H
4
±3-C
in 39% yield. H NMR (D O) d 6.91 (m, 4H). F{ H}
NMR (D O) d 281.95 (m, 3F, CF ), 2111.85 (tm, 2F,
), 2122.36 (m, 2F, CF ), 2122.60
), 2126.91 (m, 2F,
6 13 3 2 2
F ) } ] (12b). Obtained
2
3
1
1
1
1
19
1
CF2). P{ H} NMR (CDCl ) d 106.5 (d, J ˆ245 Hz).
2
3
RhP
1
MS (FAB) m/z 1537 (M2Cl ), 1502 (M22Cl ). Anal.
1
2
3
4
J
calcd for C H Cl F O PRh: C, 35.09; H, 1.72; Cl, 4.51;
4
found: C, 35.90; H, 1.45; Cl, 4.15%.
FFˆ14.2 Hz, a-CF
2
2
6
27
2
39
3
(m, 2F, CF
), 2123.68 (m, 2F, CF
2
2
3
1
1
1
CF2). P{ H} NMR (CDCl ) d 113.6 (d, J ˆ309 Hz).
3
RhP
p
.3.4. Cp IrCl {P(OC H ±4-C F ) }] (10). Obtained in
4
5
Anal. calcd for C72
2.33; found: C, 32.45; H, 0.89; P, 2.64%.
H24ClF78
O
6
P
2
Rh: C, 32.40; H, 0.90; P,
2
6
4
6 13 3
1
3
2% yield. H NMR (CDCl ) d 7.47 (d, 6H, JHHˆ8.7 Hz,
3

D. J. Adams et al. / Tetrahedron 58 (2002) 3827±3834
3833
1
2
4
in 48% yield.
.4.3. Rh(m-Cl){P(OC H ±4-C F ) } ] (12c). Obtained
13 3 2 2
(dt, 1P, J ˆ286 Hz, J ˆ53 Hz, P trans-Cl), 113.6 (dd,
6
4
6
RhP
PP
1
1
2
H
NMR (D O)
2
d
7.21 (d, 2H,
2P, J ˆ225 Hz, J ˆ53 Hz, P trans-P). MS (FAB) m/z
3896 (M2Cl ). Anal. calcd for C H ClF O P Rh: C,
108 36 117 9 3
RhP
PP
3
3
1
JHHˆ8.3 Hz, 3,5-H's), 6.88 (d, 2H, JHHˆ8.3 Hz, 2,6-
1
9
1
4
H's). F{ H} NMR (D O) d 282.08 (tm, 3F, J ˆ
32.97; H, 0.92; Cl, 0.90; found: C, 32.83; H, 0.83; Cl,
1.10%.
2
FF
4
1
2
0.0 Hz, CF ), 2110.72 (tm, 2F, J ˆ14.2 Hz, a-CF ),
3
FF
2
122.05 (m, 2F, CF ), 2122.66 (m, 2F, CF ), 2123.56
2 2
31 1
p
4.6. Crystal data for [Cp RhCl
C F ) }].C H O (9c)
6 13 3 3 6
(
(
m, 2F, CF ), 2127.12 (m, 2F, CF ). P{ H} NMR
CDCl ) d 113.2 (d, JRhPˆ313 Hz). Anal. calcd for
2
{P(OC
6
H
4
±4-
2
2
1
3
C H ClF O P Rh: C, 32.40; H, 0.90; Cl, 1.33; found: C,
7
2
24
78
6 2
3
2.81; H, 0.88; Cl, 1.30%.
C
49
H
33Cl
2
F
39
O
4
PRh, Mˆ1631.53, monoclinic, space group
Ê
C2/c, aˆ38.221(4), bˆ15.676(2), cˆ22.579(2) A, bˆ
3
Ê
4.4.4. RhCl(CO){P(OC H ±2-C F ) } ] 13. The addition
of a colourless solution of the P(OC H ±2-C F ) (0.373 g,
0
119.641(1)8, Uˆ11758(3) A (by least squares re®nement
6
4
6 13 3 2
6
4
6 13 3
of the setting angles of 41 re¯ections in the 2u range
5.24±12.49),
3
.30 mmol) in dry PP3 (40 cm ) to a deep red solution of
Tˆ190(2) K,
graphite-monochromated
2
3
Ê
[
Rh(CO) Cl] (0.030 g, 0.08 mmol) in dry dichloromethane
2
Mo Ka radiation, lˆ0.71073 A, Zˆ8, D ˆ1.843 g cm ,
2
c
under dinitrogen resulted in an almost instantaneous
decolourisation of the upper organic layer and the ¯uorous
layer turned yellow. The lower ¯uorous layer was trans-
ferred, under nitrogen, to a Schlenk ¯ask where the solvent
was removed in vacuo, to leave a yellow solid, which was
recrystallized from ethanol and dried in vacuo. Yield
F(000)ˆ6432, dimensions 0.39£0.31£0.27 mm, m(Mo Ka)ˆ
2
1
0.577 mm , semi-empirical absorption correction based on
c scans, maximum and minimum transmission factors of
0.831 and 0.807 respectively, Siemens P4 diffractometer, v
scans, data collection range uˆ2.6±25.08, 21#h#45,
21#k#18, 226#l#23, no crystal decay was detected
from periodically measured check re¯ections; 10247 re¯ec-
1
6
0
.251 g, 50%. H NMR (d -benzene) d 7.55 (d, 1H,
3
3
JHHˆ8.2 Hz, 6-H), 7.22 (d, 1H, J ˆ7.6 Hz, 3-H), 6.98
tions were measured and 9429 were unique (R ˆ0.0336).
int
HH
3
3
(
t, 1H, J ˆ7.6 Hz, 5-H), 6.84 (t, 1H, J ˆ7.6 Hz, 4-H).
The data were corrected for Lorentz and polarisation effects.
HH
HH
1
9
1
6
4
F{ H} NMR (d -benzene) d 282.25 (tm, 3F, J ˆ9.9 Hz,
FF
4
CF ), 2108.64 (tm, 2F, J ˆ14.2 Hz, a-CF ), 2121.49 (m,
4.7. Structure solution and re®nement for
[Cp RhCl {P(OC H ±4-C F ) }].C H O (9c)
3
FF
2
p
2
2
F, CF ), 2122.44 (m, 2F, CF ), 2123.65 (m, 2F, CF ),
2
2
2
2
6
4
6
13 3
3
6
3
1
1
6
127.29 (m, 2F, CF ). P{ H} NMR (d -benzene) d
2
1
1
15.2
(d,
JRhPˆ223 Hz).
Anal.
calcd
for
Structure solution by Patterson methods and structure
re®nement on F employed SHELXTL/PC version 5.0.
2
31
C H ClF O P Rh: C, 32.51; H, 0.89; P, 2.30; found: C,
7 2
7
3
24
78
3
2
1.98; H, 0.84; P, 3.00%. IR (PP3 solution) n(CuO)
All hydrogen atoms were included in calculated positions
Ê
2
045 cm .
1
(C±Hˆ0.96 A) with isotropic displacement parameters set
to 1.5 U (C) for methyl H atoms and 1.2U (C) for all other
eq
eq
H atoms. All non-H atoms were re®ned with anisotropic
displacement parameters. Final, R ˆ0.102, wR ˆ0.288
4
.5. General procedure for the preparation of [RhClL3]
1
2
(0.163 and 0.363, respectively, for all data) for 829 vari-
ables. The ®nal residual Fourier map showed peaks of 1.960
The addition of a colourless solution of the ligand
3
0.32 mmol) in dry PP3 (40 cm ) to a deep red solution of
(
[
(
Ê
1.60 A from P1) and 21.708 eA .
Ê
23
(
Rh(h-C H ) Cl] (0.05 mmol) in dry dichloromethane
2
4 2
2
3
40 cm ) under dinitrogen resulted in an almost instanta-
neous decolourisation of the upper organic layer and the
uorous layer turned yellow. The lower ¯uorous layer was
5. Conclusion
¯
transferred, under nitrogen, to a Schlenk ¯ask where the
solvent was removed in vacuo, to leave a yellow solid,
which was recrystallized from ethanol and dried in vacuo.
The coordination of a series of ortho-, meta- and para-
per¯uoroalkyl-substituted triaryl phosphites to platinum
metal centres is readily achieved. Spectroscopic and struc-
tural data for the metal complexes indicate that complete
electronic insulation of the phosphorus(III) centres is not
achieved.
4
3
.5.1. RhCl{P(OC H ±3-C F ) } ] (14a). Obtained in
6 4 6 13 3 3
9% yield. H NMR (D O) d 8.20 (m, 4H). F{ H} NMR
2
6 4
1
19
1
(
d -acetone) d 281.89 (tm, 3F, J ˆ10.9 Hz, CF ),
FF
3
4
2
CF ), 2122.48 (m, 2F, CF ), 2123.67 (m, 2F, CF ),
111.27 (tm, 2F, J ˆ14.0 Hz, a-CF ), 2122.09 (m, 2F,
FF
2
2 2 2
Acknowledgements
3
1
1
2
126.90 (m, 2F, CF ). P{ H} NMR (CDCl ) d 119.0
2 3
1 2
(
2
3
dt, 1P, J ˆ276 Hz, J ˆ45 Hz, P trans-Cl), 113.6 (dd,
RhP
PP
We would like to thank the EPSRC (D. J. A., D. G.) and the
Royal Society (E. G. H., A. M. S.) for ®nancial support.
1
2
P, J ˆ227 Hz, J ˆ45 Hz, P trans-P). MS (FAB) m/z
RhP
PP
1
896 (M2Cl ).
.5.2. RhCl{P(OC H ±4-C F ) } ] (14b). Obtained in
4
7
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1
3
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3
HH
3
2
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