Synthesis of rhodium(i) and rhodium(iii) perfluoroalkyl complexes from [Rh(μ-OH)(COD)]2

Article abstract of DOI:10.1039/b822738a

Complexes [Rh(R_F)(PMe_xPh_3-x)₃] (R_F = CF₃, x = 1 (2); R_F = n-C ₃F₇, x = 1 (3), x = 2 (4)) are quantitatively generated in situ when [Rh(μ-OH)(COD)]₂ (1) is reacted with the corresponding Me₃SiR_F and PMe_xPh_3-x. In contrast, the reaction of 1 with Me₃SiCF₃ and PMe₂Ph gives mixtures containing [Rh(CF₃)(PMe₂Ph)₃] (5), [Rh(CF₃)(PMe₂Ph)₄] (6), [Rh(CF ₃)(COD)(PMe₂Ph)₂] (7) and [Rh(CF ₃)(COD)(PMe₂Ph)] (8), the relative amounts of which depend on the Rh:PMe₂Ph molar ratio. [Rh(CF₃)(η²- O₂)(PMePh₂)₃] (9) was isolated after bubbling air through a solution of 2 in THF. Reactions of in situ generated 2-5 with L = CO, XyNC (Xy = 2,6-dimethylphenyl) gives pentacoordinate complexes [Rh(R _F)L(PMe_xPh_3-x)₃] (L = CO, x = 1, R_F = CF₃ (10), n-C₃F₇ (11); L = XyNC, R_F = CF₃, x = 1 (12), 2 (13); L = XyNC, R _F = n-C₃F₇, x = 2 (14)). Oxidative addition of MeI (i) to 2 gives (PMe₂Ph₂)[OC-6-43]-[Rh(CF ₃)(Me)I₂(PMePh₂)₂] (15), which reacts with Tl(acac) (acac = acetylacetonato) to give [OC-6-14]-[Rh(CF ₃)(Me)(acac)(PMePh₂)₂] (16), (ii) to 5 gives [Rh(CF₃)(Me)I(PMe₂Ph)₃] as a ca. 5: 1 mixture of the isomers OC-6-34 (17) and OC-6-43 (17′), and (iii) to 12 or 14 leads to [OC-6-52]-[Rh(CF₃)(Me)I(CNXy)(PMePh₂)₂] (18) or [OC-6-52]-[Rh(n-C₃F₇)(Me)I(CNXy)(PMe ₂Ph)₂] (19), respectively. Oxidative addition of iodotrifluoroethene to 12 affords [OC-6-32]-[Rh(CFCF₂)(CF ₃)I(CNXy)(PMePh₂)₂] (20). The crystal structures of 10, 15 and 19 were determined.

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Synthesis of rhodium(I) and rhodium(III) perfluoroalkyl complexes
from [Rh(l-OH)(COD)]2†
Jose´ Vicente,*a Juan Gil-Rubio,*a Juan Guerrero-Leala and Delia Bautistab
Received 19th December 2008, Accepted 20th February 2009
First published as an Advance Article on the web 31st March 2009
DOI: 10.1039/b822738a
Complexes [Rh(RF)(PMexPh3-x)3] (RF = CF3, x = 1 (2); RF = n-C3F7, x = 1 (3), x = 2 (4)) are
quantitatively generated in situ when [Rh(m-OH)(COD)]2 (1) is reacted with the corresponding Me3SiRF
and PMexPh3-x. In contrast, the reaction of 1 with Me3SiCF3 and PMe2Ph gives mixtures containing
[Rh(CF3)(PMe2Ph)3] (5), [Rh(CF3)(PMe2Ph)4] (6), [Rh(CF3)(COD)(PMe2Ph)2] (7) and [Rh(CF3)-
(COD)(PMe2Ph)] (8), the relative amounts of which depend on the Rh:PMe2Ph molar ratio. [Rh(CF3)-
2
(h -O2)(PMePh2)3] (9) was isolated after bubbling air through a solution of 2 in THF. Reactions of
in situ generated 2–5 with L = CO, XyNC (Xy = 2,6-dimethylphenyl) gives pentacoordinate complexes
[Rh(RF)L(PMexPh3-x)3] (L = CO, x = 1, RF = CF3 (10), n-C3F7 (11); L = XyNC, RF = CF3, x = 1 (12),
2 (13); L = XyNC, RF = n-C3F7, x = 2 (14)). Oxidative addition of MeI (i) to 2 gives (PMe2Ph2)[OC-
6-43]-[Rh(CF3)(Me)I2(PMePh2)2] (15), which reacts with Tl(acac) (acac = acetylacetonato) to give
[OC-6-14]-[Rh(CF3)(Me)(acac)(PMePh2)2] (16), (ii) to 5 gives [Rh(CF3)(Me)I(PMe2Ph)3] as a ca. 5 : 1
mixture of the isomers OC-6-34 (17) and OC-6-43 (17¢), and (iii) to 12 or 14 leads to [OC-6-52]-
[Rh(CF3)(Me)I(CNXy)(PMePh2)2] (18) or [OC-6-52]-[Rh(n-C3F7)(Me)I(CNXy)(PMe2Ph)2] (19),
=
respectively. Oxidative addition of iodotrifluoroethene to 12 affords [OC-6-32]-[Rh(CF CF2)(CF3)-
I(CNXy)(PMePh2)2] (20). The crystal structures of 10, 15 and 19 were determined.
very mild conditions is an appropriate way to prepare perfluo-
Introduction
roalkyl metal complexes including unstable or low valent ones,
with the limitations imposed by the availability of the starting
material.3,11,12 In addition, Pd and Pt trifluoromethyl complexes
have been prepared by reaction of chloro or bromo complexes
with Me3SiCF3/F-.2,13
Recently, we observed that [Rh(CF3)(CNXy)3] can be obtained
by reacting [Rh(m-OH)(COD)]2 (1) with XyNC and Me3SiCF3
in the absence of fluoride.14 Herein, we show that this reaction
can be extended to prepare the first family of perfluoroalkyl
Wilkinson-type complexes [Rh(RF)Lx] from 1, Me3SiRF (CF3,
There is current interest in the study of transition metal perfluo-
roalkyl complexes due to the demand for metal-mediated C–F
bond breaking and C–C bond formation reactions involving
highly fluorinated substrates.1–3 Although transition metal perfluo-
roalkyl complexes are known since the early times of organometal-
lic chemistry,4,5 the synthesis of new families of such complexes is
still challenging, since the known synthetic methods (decarbony-
lation of perfluoroacyl complexes, transmetalation and oxidative
addition reactions) present important limitations, particularly to
prepare unstable or low valent complexes. Thus, decarbonylation
reactions are quite specific and frequently require high temper-
atures or irradiation.5,6 The use of (perfluoroalkyl)lithium and
-magnesium reagents is limited by their instability, especially for
the trifluoromethyl derivatives.7 Stable M(CF3)2 (M = Cd or Hg)
have also been used as trifluoromethyl-transfer reagents,6,8 but they
are disliked due to their toxicity.9 Finally, the oxidative addition
of RF–I does not lead to low valent metal perfluoroalkyls.4–6,10
Huang, Taw and us have previously reported that the reaction
of fluoro complexes with Me3SiRF (RF = perfluoroalkyl) under
n-C3F7) and a phosphine L. A few complexes of the same general
15
=
formula but containing unsaturated RF groups like CF CFCF3,
4-tetrafluoropyridyl or pentafluorophenyl16 are known. The ad-
vantages of our method include working under mild condicions,
using more readily availabe hydroxo- instead of fluoro- complexes,
and the potential application to other metals.
Our perfluoroalkyl complexes are very reactive and could not
be isolated but they were quantitatively generated in solution and
made to react in situ with different reagents to give stable and
fully characterized Rh(I) and Rh(III) derivatives in up to 91%
yield. These include new types of Rh(III) perfluoroorganometallic
complexes, as those containing a perfluoroalkyl and a methyl
ligand, or the first transition metal complex containing a triflu-
oromethyl and a trifluorovinyl ligand bonded to the same metal
center. Although trifluorovinyl complexes of Ir, Ni, Pd and Pt have
aGrupo de Qu´ımica Organometa´lica, Departamento de Qu´ımica Inorga´nica,
Facultad de Qu´ımica, Universidad de Murcia, E-30071, Murcia, Spain.
E-mail: jvs1@um.es; Web: http://www.um.es/gqo/; Fax: +34 868 887 785;
Tel: +34 868 884 143
bSACE, Universidad de Murcia, E-30071, Murcia, Spain
=
been obtained by oxidative addition reactions using CF2 CFX
(X = Cl, Br or I),17–20 only one Rh trifluorovinyl complex has
† Electronic supplementary information (ESI) available: Variable-
temperature 19F and 31P{ H} NMR spectra of 15. CCDC reference
1
=
been previously reported, namely [Rh(CF CF2)(CO)2(PPh3)2],
numbers 714350–714352. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/b822738a
-
prepared from [Rh(CO)2(PPh3)2] and CF2 CFCl.21 Interestingly,
=
3854 | Dalton Trans., 2009, 3854–3866
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=
several Rh(I) complexes containing p-bonded CF2 CFX (X =
Complexes 2–8 were characterized by NMR spectroscopy. In
the NMR time scale they undergo fast dynamic processes which
were studied by variable-temperature NMR spectroscopy (see
below).
Cl, Br),22 have been described, but no oxidative addition of the
halotrifluoroethenes to Rh(I) was reported.
The attempts to isolate 2 under a N2 atmosphere using
standard Schlenk techniques led to a mixture of 2, OPMePh2
and [Rh(CF3)(O2)(PMePh2)3] (9), which was isolated pure after
bubbling air through a solution of 2 in THF (Scheme 2).
The NMR spectra of 9 show the presence of three meridional
phosphine ligands disposed cis to the CF3 ligand. In addition,
the C and H analyses and the high-resolution mass spectrum of
9 agree with the proposed stoichiometry. However, the bonding
mode of the O2 ligand could not be unambiguously established
because, after repeated attempts, we could not grow single crystals
for an X-ray structure determination. We tentatively propose
Results and discussion
Synthesis of Rh(I) complexes
The reaction of [Rh(m-OH)(COD)]2 (1) with Me3SiRF and
PMexPh3-x in a Rh:Si:P molar ratio of 1 : 2 : 3, gave complexes
[Rh(RF)(PMexPh3-x)3] (RF = CF3, x = 1 (2); RF = n-C3F7, x =
1 (3), x = 2 (4)) (Scheme 1). Apart from the Wilkinson-type
complexes, no significant amounts of other Rh complexes were
detected in the 19F and 31P{ H} NMR spectra of the reaction
1
mixtures. However, the NMR spectra of the reaction mixture of
1, Me3SiCF3 and PMe2Ph in the same molar ratio showed that,
although the expected complex [Rh(CF3)(PMe2Ph)3] (5) was the
main product, a 4.5 : 1 : 1.8 mixture of 5, [Rh(CF3)(PMe2Ph)4]
(6) and [Rh(CF3)(COD)(PMe2Ph)2] (7) was obtained (Scheme 1).
A decrease in the PMe2Ph ratio (Rh : Si : P = ca. 1 : 2 : 2), gave
a ca. 1 : 2.1 : 0.2 mixture of 5, 7 and [Rh(CF3)(COD)(PMe2Ph)]
(8), while an increase (Rh : Si : P = ca. 1 : 2 : 4) afforded complex
6 and small amounts of 7. Pentacoordinate complexes (6 and 7)
were only detected when RF = CF3 and L = PMe2Ph, which can
be attributed to the smaller cone angle of these ligands.23
2
an h -O2 (peroxo) coordination like that established by X-ray
diffraction for the related complex [Rh(CF3)(O2)(CNXy)2(PPh3)],
which we prepared similarly by bubbling air through a solution of
[Rh(CF3)(CNXy)2(PPh3)].12 In the IR spectrum of 9, a medium-
intensity band at 854 cm-1 is assigned to the O–O stretching
mode.24 In [Rh(CF3)(O2)(CNXy)2(PPh3)] it appears at 882 cm-1.12
As the attempts to isolate 3–5 were also unsuccessful due to their
high sensitivity to oxygen, we decided to study the reactivity of
2–5 using their solutions. Mixtures of 1 + Me3SiCF3 + 3 PMe2Ph
(Scheme 1) behave as if they only contain 5, in spite the presence
of significant amounts of 6 and 7.
Scheme 2
The reactions of in situ generated complexes 2–5 with excess of
CO or with one equiv of XyNC in THF afforded pentacoordinate
complexes [Rh(RF)L(PMexPh3-x)3] (L = CO, x = 1, RF = CF3
(10), n-C3F7 (11); L = XyNC, RF = CF3, x = 1 (12), 2
(13); L = XyNC, RF = n-C3F7, x = 2 (14)) (Scheme 2), which
were isolated and characterized by analytical and spectroscopic
means. In addition, the structure of 10 was determined by single-
crystal X-ray diffraction and shows (Fig. 1) the Rh atom in a
slightly distorted bipyramidal trigonal coordination with the three
phosphine ligands in the equatorial positions. The CF3 group is
in a staggered conformation with respect to the P atoms. The
Rh–CF3 and C–F bond distances, as well as the Rh–C–F and the
F–C–F angles are similar to those previously reported for Rh(I)
trifluoromethyl complexes.12,14
Scheme 1
In all cases, free COD, (Me3Si)2O and CHF3 (or CHF2CF2CF3,
in the reactions with Me3Si(n-C3F7)) were detected in the reaction
mixtures by NMR spectroscopy and GC-MS. Since we have
checked that compound 1 does not react with Me3SiCF3, the
formation of the perfluoroalkyl complexes should proceed by
reaction of 1 with PMexPh3-x to give a phosphino(hydroxo) species,
which would react with Me3SiRF to give Me3SiOH and the
perfluoroalkyl complex. The detected (Me3Si)2O and HRF could
arise from the reaction of Me3SiOH with the excess Me3SiRF or
from the condensation of two molecules of Me3SiOH to give H2O
that could react with Me3SiRF to give HRF.
The NMR spectroscopic data of trifluoromethyl complexes 12
and 13 (see below) suggest that they have bipyramidal structures
similar to that of 10, i.e., with three equatorial phosphine
ligands. However, for the heptafluoropropyl complexes 11 and
14, it was not possible to distinguish between the four possible
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Scheme 3
Fig. 1 Molecular structure of 10 (50% thermal ellipsoids). Hydrogen
˚
atoms have been omitted for clarity. Selected bond lengths (A) and angles
(◦): Rh–C(1) 1.886(2), Rh–C(2) 2.087(2), Rh–P(1) 2.3339(5), Rh–P(2)
2.3750(5), Rh–P(3) 2.3412(5), C(1)–Rh–C(2) 174.75(8), C(1)–Rh–P(1)
87.87(6), C(1)–Rh–P(2) 97.05(6), C(1)–Rh–P(3) 89.46(6), C(2)–Rh–P(1)
90.96(6), C(2)–Rh–P(2) 88.06(6), C(2)–Rh–P(3) 86.94(6), P(1)–Rh–P(3)
123.912(18), P(1)–Rh–P(2) 115.735(18), P(3)–Rh–P(2) 120.184(18).
diastereoisomers represented in Chart 1 (See “Spectroscopic
Characterization and Dynamic Behaviour” section).
Fig. 2 Structure of the cation of 15 (50% thermal ellipsoids) showing
the disordered I and CF3 ligands. Hydrogen atoms have been omitted
◦
˚
for clarity. Selected bond lengths (A) and angles ( ): Rh–C(1) 2.052(6),
Rh–C(1¢) 2.08(2), Rh–C(2) 2.103(3), Rh–P(2) 2.3591(7), Rh–P(5)
2.3684(7), Rh–I(1¢) 2.6482(10), Rh–I(1) 2.7425(4), Rh–I(2) 2.8757(3),
C(1)–Rh–C(2) 83.87(17), C(1)–Rh–P(2) 90.60(14), C(2)–Rh–P(2) 91.99(8),
C(1)–Rh–P(5) 93.04(14), C(2)–Rh–P(5) 91.18(8), P(2)–Rh–P(5) 175.42(3),
C(1¢)–Rh–I(1¢) 165.0(4), C(1)–Rh–I(1) 169.71(15), C(2)–Rh–I(1) 85.85(9),
P(2)–Rh–I(1) 90.058(19), P(5)–Rh–I(1) 86.864(19), C(1)–Rh–I(2)
100.52(15), C(2)–Rh–I(2) 175.25(9), P(2)–Rh–I(2) 89.790(18),
P(5)–Rh–I(2) 86.802(18), I(1)–Rh–I(2) 89.749(10), C(1)–Rh–I(1¢)
4.28(15), C(1¢)–Rh–I(1) 2.9(4).
Chart 1
Oxidative addition reactions
The reaction of a THF solution of 2 with MeI gave com-
plex (PMe2Ph2)[OC-6-43]-[Rh(CF3)(Me)I2(PMePh2)2] (15) and
(PMe2Ph2)I (Scheme 3). The structure of 15 was determined by
single-crystal X-ray diffraction (Fig. 2) and shows the Rh atom in
a pseudo-octahedral coordination geometry, with the phosphine
ligands mutually trans and the iodo ligands located cis to each
other. The ESI-MS spectra of 15 show the masses corresponding
to the cation and the anion of 15 in the positive and negative modes,
respectively. The room temperature NMR spectra of 15 are well-
resolved and agree with its solid state structure but, on decreasing
the temperature, the signals broaden and split into several signals
which gave little information because of their broadness (see
ESI).† This, together with the detection of the dinuclear anion
[Rh2(CF3)2(Me)2I3(PMePh2)2]- in the ESI-MS spectrum and the
precipitation of (PMe2Ph2)I in the reaction mixture suggests that
15 would be in equilibrium with other species.
with MeI to give (PMe2Ph2)I. The resulting 16-electron complex
[Rh(CF3)(Me)I(PMePh2)2] could coordinate I- to give 15.
Addition of Tl(acac) to the reaction mixture between 2 and MeI
(Scheme 4) led to precipitation of TlI and formation of [OC-6-
14]-[Rh(CF3)(Me)(acac)(PMePh2)2] (16), which was isolated and
characterized by analytical and spectroscopic means.
Scheme 4
The reaction of
5 with MeI afforded [Rh(CF3)(Me)-
The formation of 15 can be explained by oxidative addition of
MeI to 2 to generate the intermediate [Rh(CF3)(Me)I(PMePh2)3],
from which a molecule of PMePh2 could dissociate and react
(I)(PMe2Ph)3] (Scheme 5), which was obtained in high yield as
a ca. 5 : 1 mixture of the isomers OC-6-34 (17) and OC-6-43
(17¢) that could not be separated by recrystallization. Smaller
3856 | Dalton Trans., 2009, 3854–3866
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Scheme 5
amounts (≤4%) of other unidentified compounds were observed.
The mixture of isomers was characterized by analytical and
spectroscopic means. In order to determine their structures,
their 13C-labelled analogues were prepared using 13CH3I. In both
isomers, the phosphines are in a mer disposition. In the main
isomer (17), the methyl ligand is located trans to a PMe2Ph ligand
while in the other one (17¢) it is trans to the I ligand. The lower steric
hindrance and the higher basicity of PMe2Ph, which disfavour its
dissociation, with respect to PMePh2 can account for the isolation
of 17, while its homologue with PMePh2 easily dissociates one
equiv. of phosphine to finally afford 15 (Scheme 3).
Scheme 6
Complexes 10 and 11 react with MeI to give (PMePh2)I and
mixtures of complexes which could neither be separated nor char-
acterized. Their NMR spectra suggest that they contain the ex-
pected oxidative addition products [Rh(RF)(Me)I(CO)(PMePh2)2]
(RF = CF3, n-C3F7) together with other unidentified prod-
ucts. In contrast, complex 12 or 14 (Scheme 6) reacts
with MeI to afford (PMexPh4-x)I (x = 2 or 3) and com-
plex [Rh(CF3)(Me)I(CNXy)(PMePh2)2] (18) or [OC-6-52]-[Rh(n-
C3F7)(Me)I(CNXy)(PMe2Ph)2] (19), respectively, which were iso-
lated in high yield and characterized by analytical and spectro-
scopic means. The crystal structure of complex 19 was determined
by X-ray diffraction (Fig. 3 and Scheme 6) showing mutually trans
phosphines and Me to I ligands.
Scheme 7
Coordination of the iodide anion generates the final octahedral
complex, in which the methyl and iodo ligands are mutually trans.
In our case, the reactions of 12 and 14 with MeI give only the trans-
addition products 18 and 19, but complex 5 gives a 1 : 5 mixture
of trans- (17¢) and cis- (17) addition products (Scheme 7), which is
reached very fast (<5 min) and does not changes in a 24 h period.
In order to explain the different stereochemistry of the reaction
using 5, we propose that in this case, an equilibrium between A
and its isomer B is established. The obtained molar ratio 17/17¢ =
5 must result from the greater rate of iodide addition to B than to
A. Thus, the product distribution would be determined by kinetic
control.
Fig.
3
Molecular structure of 19◦ (50% thermal ellipsoids). Se-
˚
lected bond lengths (A) and angles ( ): Rh–C(5) 1.9810(16), Rh–C(2)
2.1061(16), Rh–C(1) 2.1160(16), Rh–P(3) 2.3526(4), Rh–P(4) 2.3660(4),
Rh–I(2) 2.80090(18), C(5)–Rh–C(2) 177.70(6), C(5)–Rh–C(1) 86.58(6),
C(2)–Rh–C(1) 95.71(6), C(5)–Rh–P(3) 90.46(5), C(2)–Rh–P(3) 89.62(5),
C(1)–Rh–P(3) 84.89(5), C(5)–Rh–P(4) 87.40(5), C(2)–Rh–P(4) 92.63(5),
C(1)–Rh–P(4) 92.25(5), P(3)–Rh–P(4) 176.529(15), C(5)–Rh–I(2)
86.37(5), C(2)–Rh–I(2) 91.33(4), C(1)–Rh–I(2) 172.52(5), P(3)–Rh–I(2)
92.650(11), P(4)–Rh–I(2) 89.943(12).
We have attempted to prepare the first trifluorovinyl Rh(III)
=
complexes by oxidative addition of CF2 CFI to Rh(I) perflu-
oroalkyl complexes 10–12. The carbonyl complexes 10 and 11
did not appreciably react at room temperature. In contrast, the
isonitrile complex 12, which has a more electron rich Rh(I)
center, reacts with trifluoroiodoethene to give complex [OC-
=
6-32]-[Rh(CF CF2)(CF3)I(CNXy)(PMePh2)2] (20) in high yield
Kinetic studies on the MeI oxidative addition to square-
planar Rh(I) complexes25 suggest that this reaction follows a
SN2 mechanism (Scheme 7) involving the attack of the metal
to the methylic carbon atom, to give a cationic intermediate A.
(Scheme 6). In this reaction free PMePh2 is detected in the
1
31P{ H} NMR spectrum of the reaction mixture, instead of the
corresponding phosphonium salt observed in the reaction between
=
2 or 12 and MeI, because PMePh2 does not react with CF2 CFI
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as we have checked independently (room temperature, C6D6, 1 : 1
molar ratio, 26 h).
Although a single-crystal X-ray diffraction study of the struc-
ture of 20 could not be fully refined due to irresoluble disorder
between the CF3 and I positions, it shows unambiguously that the
of olefinic protons of the diene become equivalent in the presence
of catalytic amounts of L.27 The fact that the 103Rh–31P coupling
is still observed at 70 ◦C suggests that the exchange between free
and coordinated phosphine is slow on the NMR time scale. In
agreement with this, addition of an excess of PMePh2 (ca. 1 equiv.
per Rh) accelerates the exchange between free and coordinated
phosphine, giving a broad singlet instead of a broad doublet in the
=
CF2 CF and I ligands are cis to each other as confirmed by the
NMR data (see below). 20 is the first transition-metal complex
containing both a trifluorovinyl and an alkyl ligand bonded to the
same metal center.
1
fast exchange limit. The room temperature 19F and 31P{ H} NMR
spectra of 3 and 4 suggest that phosphine exchange processes are
slow on the NMR time scale.
The NMR spectra of the various mixtures containing complexes
5, 6, 7 and 8 show broad resonances and are simpler than
expected at room temperature, but at -60 ◦C the signals for all the
components were resolved, allowing for their identification. Thus,
Oxidative addition reactions using CF2=CFX to give isolable
trifluorovinyl complexes are limited to Ir(I)17 and group 10 M(0)
complexes.18,19 Only one article has reported the use of CF2 CFI as
=
an oxidative addition reagent, which by reaction with [Ni(COD)2]
20
=
and PEt3 led to trans-[NiI(CF CF2)(PEt3)2]. It has been shown
2
1
1
that these reactions proceed through h intermediates, which have
1H, 19F and 31P{ H} NMR spectra (see Fig. 5 for the 31P{ H}
NMR spectra at various PMe2Ph concentrations) of 5 and 8 are
similar to those of 2 and, respectively, [Rh(CF3)(COD)(PR3)].12
In addition, the NMR spectra of 6 and 7 (see Fig. 5 and 6 and
the Experimental) agree with the proposed trigonal bipyramidal
structures, being the observed 1JRhP value similar to those reported
been isolated only in the case of Pt(0). Although other reaction
pathways can not be discarded, we propose that the reaction
=
between CF2 CFI and 12 proceeds through a pentacoordinate
complex A (Scheme 6), which would evolve to the cis addition
product 20 through an intramolecular process.19 Rh(I) derivatives
2
22
28
of type A with h -CF2 CFX ligands, X = Cl, Br, are known.
for [Rh(Me)(COD)L2] (L = PMe3 or PMe2Ph).29 The 19F NMR
=
spectrum of 6 (Fig. 6) is remarkable because at -60 ◦C the trifluo-
romethyl fluorine become inequivalent, giving two multiplets with
relative intensities 1 : 2, which suggests that the CF3, and PMe2Ph
ligands rotate slowly on the NMR time scale.
Spectroscopic characterization and dynamic behaviour
The IR spectra of the carbonyl complexes display the n(CO)
bands in the range 1954–1974 cm-1. In the IR spectra of the Rh(I)
∫
complexes containing the XyNC ligand, the n(C N) band appears
at 2057–2096 cm-1, while in the Rh(III) compounds the same band
appears at 2156–2182 cm-1 in agreement with the lower p-donor
=
ability of Rh(III). The n(C C) band of the trifluorovinyl ligand of
compound 20 appears at 1706 cm-1.26
1
In the 19F and 31P{ H} NMR spectra of 2, the expected signals
were only observed at low temperature. Thus, at -40 ◦C, the
1
31P{ H} NMR spectrum (Fig. 4) displays a doublet of doublets of
quartets and a doublet of triplets of quartets, which on increasing
the temperature, broaden and coalesce into a broad doublet,
suggesting that both types of phosphine ligands become equivalent
on the NMR time scale. The exchange of both types of phosphine
ligands could be catalyzed by a small excess of phosphine through
a pentacoordinate intermediate, as described for [RhCl(diene)L]
(diene = COD or NBD, L = PPh3 or AsPh3), in which the two types
◦
1
Fig. 5 31P{ H} NMR spectra at -60 C of the reaction mixture between 1,
Me3SiCF3 and various amounts of PMe2Ph. The small doublet of quartets
around -8.5 ppm corresponds to traces of an unidentified complex.
◦
◦
As the temperature is increased from -60 C to 0 C (Fig. 6),
the 31P{ H} NMR signals of 5 and 6 broaden, and coalesce into
1
a doublet of quartets and a broad singlet, while the doublet
1
Fig. 4 31P{ H} NMR signals of 2 at different temperatures.
of quartets of 7 is still observable. On increasing the temperature to
3858 | Dalton Trans., 2009, 3854–3866
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1
Fig. 6 19F (top) and 31P{ H} (bottom) NMR spectra at different temperatures of the reaction mixture between 1, Me3SiCF3 and PMe2Ph (Rh:PMe2Ph =
1
1 : 3). The small doublet of quartets around -8.5 ppm in the 31P{ H} spectra corresponds to traces of an unidentified complex.
25 ◦C, only a sharp doublet of quartets and a broad singlet
are observed, which suggests that at this temperature the
dissociation of the phosphine in trans to the CF3 ligand is slow on
the NMR time scale, while that of the others is fast. Accordingly,
in the 19F NMR spectra (Fig. 6) the coalescence of the signals of
5 and 6 is observed at 0 ◦C, while the signal of 7 is still visible,
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and, as the temperature is increased to 50 ◦C, an unique doublet
equivalent on the NMR time scale, and fast dissociation would
make the 103Rh–31P and 31P–19F couplings disappear, giving rise
3
of doublets is observed, which JPF value (48.4 Hz) agrees with
1
1
that of the doublet of quartets observed in the 31P{ H} spectra
to a broad singlet in both the room temperature 19F and 31P{ H}
at 25 and 50 ◦C. The 19F signals move toward high field on
increasing the temperature, being the chemical shift of the signals
spectra. The different behaviour of the perfluoropropyl complexes
11 and 14 with respect to the trifluoromethyl complexes 10, 12
and 13 could be attributed to the higher steric requirement of the
n-C3F7 ligand.
◦
observed at 50 and 90 C similar to that of 5. This suggests that
on increasing the temperature, the equilibrium shifts toward 5
3
2
at the expense of 6 and 7. Accordingly, the JPF, JRhF (17.4 Hz)
The 31P NMR spectra of complexes 17 and 17¢ suggest that in
both of them the PMe2Ph ligands are in a mer disposition. The
1
1
and JRhP (113.3 Hz) values determined from the 31P{ H} and
◦
19F NMR spectra at 50 C are similar to those of 5 (3JPAF
=
values of JPF in 17¢ agree with the presence of two cis (15.6 Hz)
3
48.5 Hz, JRhF = 18.5 Hz and JRhPA = 111.6 Hz). At 90 ◦C a
and one trans phosphine (53.2 Hz) with respect to the CF3 ligand,
while in 17 the similar 3JPF values (18.9 and 21.0 Hz) suggest a cis
disposition of both types of phosphine ligand and the CF3 ligand.
Similarly, the 2JPC values of the Rh-bonded Me group suggest that
in 17 (8.1 and 80.2 Hz) there are two cis and one trans phosphine
ligand respect to the methyl ligand and in 17¢ (6.5 and 7.3 Hz),
both types of phosphine ligand are disposed in cis with respect to
the methyl ligand.
2
1
broad singlet is observed in both the 31P{ H} and 19F NMR
1
spectra.
The low temperature (-60 to -70 ◦C) 31P{ H} and 19F NMR
1
spectra of complexes 10, 12, and 13 display the expected signals for
bipyramidal trigonal structures with the three phosphine ligands
placed in equatorial position. However, at room temperature, both
the 19F and 31P{ H} NMR spectra show a broad singlet, which
1
suggests that phosphine-dissociation to give the square planar
complexes trans-[Rh(CF3)L(PMexPh3-x)2] (L = CO, x = 1; L =
XyNC, x = 1 or 2) is rapid on the NMR time scale. Weak signals
assignable to these tetracoordinate species12 are observed in the
low temperature NMR spectra of 12 and 13 (see Experimental).
The NMR spectra of complexes 18 and 19 show that the
phosphine ligands are placed mutually in trans, which is in
accordance with the crystal structure of 19 (Fig. 3). The relative
position of the Me and I ligands in 18 could not be unambiguously
established, but we tentatively propose that they are mutually in
trans, like in 19, because the 1JRhC and 3JFC values for the methyl
ligand (23.6 and 4.4 Hz, respectively), are very similar to those of
17¢ (23.8 and 4.8 Hz, respectively), in which the methyl ligand is
trans to I and cis to CF3.
The 31P{ H} NMR spectra of 11 and 14 show a broad singlet at
1
room temperature that, on decreasing the temperature, transforms
into two signals with a 2 : 1 intensity ratio: two extremely broad
signals for 11 (measured at -40 and -65 ◦C), and two broad
multiplets for 14 (observed at -80 ◦C, Fig. 7). In the 19F NMR
spectra, the a-CF2 gave a broad singlet in both cases. Assuming
that in 11 and 14 the three phosphine ligands are placed in
equatorial positions (Chart 1, structure I), freezing the rotation
around the Rh–C3F7 bond would make one of them inequivalent
to the two others at low temperature.
In compound 20, the d and JFF values of the vinylic 19F nuclei
are typical for trifluorovinyl compounds (3Jtrans = 106.8 Hz, 2Jgem
=
84.2 Hz, 3Jcis = 41.3 Hz).17,26,30,31 In addition, the Rh–CF fluorine
=
nucleus is coupled with 31P and with the CF3 19F nuclei (3JPF
=
4
14.3 Hz, JFF = 13.8 Hz). Interestingly, a long-range coupling is
=
observed between the CF2 fluorine nucleus, which is in cis with
respect to Rh (FC in Scheme 6) and the CF3 19F nuclei (5JFF = 10.3
Hz). This coupling is likely originated by the mutual cis disposition
=
of the CF3 and CF CF2 ligands, which favours the through-space
coupling between FC and the CF3 nuclei.
Conclusions
The first Wilkinson-type perfluoroalkyl complexes [RhRFL3] have
been obtained in solution by reaction of Me3SiCF3 or Me3Si(n-
C3F7) with [Rh(m-OH)(COD)]2 (1) in the presence of PMe2Ph
or PMePh2. The reactions are quantitative, take place at room
temperature and do not require the use of a fluoro complex or
the presence of fluoride to activate the silane. When RF = CF3
and L = PMe2Ph, equilibrium mixtures of [RhRFL4], [RhRFL3],
[RhRF(COD)L2] and [RhRF(COD)L] form, which composition
depends on the 1 : L ratio used However, when 1 : L =
3, the mixture behaves as if it were [RhRFL3]. The [RhRFL3]
species could not be isolated because they are very oxygen-
sensitive, but they could be converted into isolable pentacoordinate
compounds by reaction with CO or XyNC, or into perfluo-
ralkyl Rh(III) complexes ((PMe2Ph2)[Rh(CF3)(Me)I2(PMePh2)2],
[Rh(RF)(Me)(acac)L2], [Rh(RF)(Me)IL2L¢]) by oxidative addition
reactions using MeI. The first transition metal complex containing
both an alkyl an a trifluorovinyl ligand bonded to the same metal
1
Fig. 7 31P{ H} NMR spectrum of 14 at different temperatures. The
doublet at -7.7 ppm at -50 and -60 ◦C corresponds to an unidentified
component.
Alternatively, structures II, III or IV should be considered
(structures III and IV are less likely because of the observed
tendency of the RF and XyNC ligands to occupy the axial and
equatorial positions, respectively, in Rh(I) complexes12,14). In this
case, pseudo rotation could make the three phosphine ligands
=
center has been obtained using CF2 CFI.
3860 | Dalton Trans., 2009, 3854–3866
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◦
3
1
38.9, JPF = 46.9 Hz, PA); (21 C) 15.9 (br d, JRhP = 155.5 Hz,
Experimental
PX), 11.3 (br m, PA); (70 ◦C) 14.2 (br d, 1JRhP = 136.3 Hz).
General considerations
NMR data of [Rh(n-C3F7)(PMePh2)3] (3). 19F NMR
(282.4 MHz, THF, 25 ◦C): d -78.9 (t, JFF = 11.3 Hz, CF3), -79.3
Compounds 132 and Tl(acac)33 were prepared as previously
reported. Other reagents were obtained from commercial
sources and used without further purification: Me3SiCF3, 2,6-
dimethylphenylisocyanide (XyNC), PMePh2, PMe2Ph (Fluka),
(m, Rh–CF2), -112.2 (br s, CF2CF3). 31P{ H} NMR (121.5 MHz,
1
◦
THF, 25 C): d 11.7 (dq, 1JRhP = 171.3, 2JPP ~ JPF ~ 37 Hz, PX),
3
1
2
3
6.3 (dquint, JRhP = 118.2, JPP ~ JPF = 34 Hz, PA). On cooling
(-60 ◦C), the spectra did not vary.
=
Me3Si(n-C3F7) (Aldrich), MeI (Panreac) and CF2 CFI (ABCR).
All manipulations were carried out under an inert atmosphere of
nitrogen using standard Schlenk techniques. THF, toluene and
Et2O were distilled over sodium-benzophenone ketyl, n-hexane
and CDCl3 were passed through a basic alumina column and
deoxygenated, and n-pentane, CH2Cl2 and C6D6 were distilled over
CaH2. All solvents were stored under nitrogen over 4 A molecular
sieves. All reactions were carried out at room temperature unless
otherwise stated.
NMR data of [Rh(n-C3F7)(PMe2Ph)3] (4). 19F NMR
(188.3 MHz, C6D6, 25 ◦C): d -78.0 (t, JFF = 10.7 Hz, CF3), -80.2
1
(m, Rh–CF2), -115.2 (t, JFF = 11.6 Hz, CF2CF3). 31P{ H} NMR
◦
1
(162.3 MHz, D8-toluene, 25 C): d -0.92 (br dq, JRhP = 166.8,
2JPP ~ JPF ~ 31 Hz, PX), -2.52 (br dquint, JRhP = 116.8, JPP
~
3
1
2
˚
3JPF ~ 34 Hz, PA); on cooling, both signals approach to each other
and become second order multiplets.
Infrared spectra were recorded in the range 4000–200 cm-1 on a
Perkin-Elmer 16F PC FT-IR spectrophotometer with Nujol mulls
between polyethylene sheets. C, H, N and S analyses were carried
out with Carlo Erba 1108 and LECO CHS-932 microanalyzers.
NMR spectra were measured on Bruker Avance 200, 300, 400 and
NMR data of [Rh(CF3)(PMe2Ph)3] (5). 19F NMR (282.4 MHz,
D8-toluene, -40 ◦C): d -5.1 (ddt, JRhF = 18.5 Hz, JPF trans
=
2
3
3
1
48.5 Hz, JPF cis = 24.1 Hz). 31P{ H} NMR (162.3 MHz, D8-
toluene, -60 ◦C): d 0.8 (ddq, 2 P, 1JRhP = 157.0 Hz, 2JPP = 40.7 Hz,
3JPF = 24.2 Hz, PX), -2.3 (dtq, 1 P, 1JRhP = 111.6 Hz, 2JPP = 38.8 Hz,
3JPF = 46.8 Hz, PA).
1
600 instruments. H chemical shifts were referenced to residual
C6D5H (7.15 ppm), C6D5–CD2H (2.09 ppm), CHDCl2 (5.29 ppm)
NMR data of [Rh(CF3)(PMe2Ph)4] (6). 19F NMR (282.4 MHz,
1
or CHCl3 (7.26 ppm). 13C{ H} spectra were referenced to C6D6
◦
D8-toluene, -60 C): d 9.4 (m br, 1 F), 8.2 (m br, 2 F). 31P{ H}
1
(128.0 ppm), CDCl3 (77.1 ppm), CD2Cl2 (53.8 ppm), or external
NMR (162.3 MHz, D8-toluene, -60 ◦C): d 5.1 (dqq, 1 P, 1JRhP
=
1
(CD3)2SO (40.4 ppm). 19F NMR and 31P{ H} NMR spectra were
113.6 Hz, 2JPP = 41.3 Hz, 3JPF = 54.8 Hz, axial P), -15.3 (m br, 3
referenced to external CFCl3 and H3PO4, respectively. In cases
1
1
where 13C{ H}, 19F or 31P{ H} NMR spectra were measured in
P, equatorial P).
non-deuterated THF, an external (CD3)2SO capillary was used for
NMR data of [Rh(CF3)(COD)(PMe2Ph)2] (7). 1H NMR
(300.1 MHz, D8-toluene, -40 ◦C): d 3.88 (br m, CH, COD), 3.14
(br m, CH, COD), 2.24 (m, CH2, COD), 1.99 (m, CH2, COD); the
PMe2Ph signals could not be unambiguously assigned because
they overlap with a strong THF signal (Me3SiCF3 was used as a
2 M THF solution). 19F NMR (282.4 MHz, D8-toluene, -40 ◦C):
locking and referencing. In virtual triplets (vt) N = JPC + 3JPC or
1
2JPH or JPH. In complexes in which the three phosphorus of the
4
phosphine ligands constitute an AX2 spin system, the phosphorus
nuclei and their substituents will be denoted as PA, PX, MeA, MeX,
PhA and PhX. The temperature values in NMR experiments were
not corrected. ESI-MS and ESI HR-MS spectra were measured on
Agilent 5973 and 6620 spectrometers, respectively. Melting points
were determined on a Reichert apparatus in the air.
2
3
1
d -3.3 (dt, JRhF = 12.6 Hz, JPF = 23.4 Hz). 31P{ H} NMR
◦
1
(162.3 MHz, D8-toluene, -40 C): d -6.2 (dq, JRhP = 120.0 Hz,
3JPF = 23.5 Hz).
NMR data of [Rh(CF3)(COD)(PMe2Ph)] (8). 1H NMR
(300.1 MHz, D8-toluene, -40 ◦C): d 5.48 (br m, CH, COD), 3.67
(br m, CH, COD); the other signals could not be assigned because
they have low intensity and overlap with stronger signals. 19F NMR
General procedure for the in situ generation of complexes 2–8
In a typical experiment, PMePh2 or PMe2Ph was added to a
solution of [Rh(m-OH)(COD)]2 (1) (0.1–0.4 mmol for isolation;
ca. 0.02 mmol for NMR studies) and Me3SiCF3 in THF, C6D6 or
D8-toluene ([1] : [Me3SiCF3] : [phosphine] = 1 : 4 : 6). The resulting
solution was stirred for 2 h. In addition to 2–8, the following
products were observed in NMR tube reactions (C6D6): COD (1H
NMR: d 5.59 (m, 4 H, CH), 2.19 (m, 8 H, CH2)), (Me3Si)2O (1H
NMR: d 0.08 (s), it was also detected by GC-MS) and CHF3 (1H
◦
3
(282.4 MHz, D8-toluene, -40 C): d -20.8 (dd, 2JRhF = JPF = 21.0
◦
1
Hz). 31P{ H} NMR (162.3 MHz, D8-toluene, -40 C): d -0.6 (dq,
1JRhP = 171.5 Hz, 3JPF = 21.4 Hz).
[Rh(CF3)(g2-O2)(PMePh2)3] (9). A solution of 2 in THF
(10 mL) was prepared from 1 (0.104 g, 0.23 mmol), Me3SiCF3
(0.46 mL of a 2.0 M THF solution, 0.92 mmol) and PMePh2
(0.26 mL, 1.4 mmol). A stream of dry air (CaCl2) was bubbled
through the solution for 1 min. After stirring for 20 min, the
solution was concentrated to dryness under vacuum and the
residue was washed with Et2O (3 ¥ 5 mL) and dried under vacuum
to give 9 as an off-white solid. Yield: 0.139 g (38%). Analytically
pure 9·CH2Cl2 was obtained by recrystallisation from CH2Cl2–
Et2O. mp: 107–110 ◦C. Anal. calcd for C41H41Cl2F3O2P3Rh:
C 55.36, H 4.65. Found: C 55.52, H 4.86. 1H NMR (300.1 MHz,
CDCl3): d 7.70–7.64, 7.33–7.05 (m, 30 H, Ph), 1.58 (vt, N = 7.0 Hz,
2
NMR: d 5.79 (q, JFH = 79.3 Hz), 19F NMR: d -78.2 (d)) or
CHF2CF2CF3 (1H NMR: d 5.21 (tt, 2JFH = 51.7, 3JFH = 4.6 Hz),
19F NMR: d -82.5 (t, JFF = 7.1 Hz, CF3), -132.8 (m, CF2), -137.7
(dm, CHF2)).31
NMR data of [Rh(CF3)(PMePh2)3] (2). 19F NMR (282.4 MHz,
◦
2
3
D8-toluene, -40 C): d -5.4 (ddt, JRhF = 16.4, JPF trans = 46.7,
◦
◦
3JPF cis = 23.5 Hz); (22 C) -5.6 (br s); (70 C) -5.5 (br s). 31P{ H}
1
NMR (162.3 MHz, D8-toluene, -40 ◦C): d 16.4 (ddq, 1JRhP = 166.6,
2
1
2JPP = 39.4, 3JPF = 24.4 Hz, PX), 11.6 (dtq, 1JRhP = 116.7, 2JPP
=
6 H, MeX), 0.92 (d, JPH = 9.3 Hz, 3 H, MeA). 13C{ H} NMR
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(100.8 MHz, CD2Cl2): d 136.3 (d, 1JPC = 40.8 Hz, C1, PhA), 134.6
(vt, N = 46.2 Hz, C1, PhX), 134.1 (vt, N = 10.7 Hz, C2, PhX), 133.5
(vt, N = 50.2 Hz, C1, PhX), 133.3 (d, JPC = 11.1 Hz, C2, PhA), 132.7
(vt, N = 9.0 Hz, C2, PhX), 130.2 (s, C4, PhX), 130.1 (s, C4, PhA),
129.3 (s, C4, PhX), 128.3 (d, JPC = 9.9 Hz, C3, PhA), 128.1 (vt, N =
14.5 (very br m, 2 P), -2.9 (very br m, 1 P); (25 ◦C) 2.3 (br s).
n (Nujol)/cm : 1974 and 1954 (CO); n (CH2Cl2)/cm : 1994 (CO).
-1
-1
˜
˜
[Rh(CF3)(CNXy)(PMePh2)3] (12). To a solution of 2 in THF
(7 mL), prepared from 1 (0.135 g, 0.30 mmol), Me3SiCF3 (0.60 mL
of a 2.0 M THF solution, 1.2 mmol) and PMePh2 (0.34 mL,
1.8 mmol), XyNC (0.078 g, 0.59 mmol) was added and the solution
was stirred for 1 h. The resulting yellow-orange solution was
concentrated to dryness and the residue stirred with n-pentane
(5 mL) to give a yellow solid, which was washed with n-pentane
(3 ¥ 5 mL) and dried under vacuum. Yield: 0.490 g (91%). mp:
89–92 ◦C. Anal. calcd for C49H48F3NP3Rh: C 65.12, H 5.35, N
9.6 Hz, C3, PhX), 127.7 (vt, N = 8.7 Hz, C3, PhX), 13.3 (d, 1JPC
=
29.1 Hz, MeA), 10.8 (vt, N = 32.1 Hz, MeX); the signal of the CF3
carbon was not observed. 19F NMR (282.4 MHz, CDCl3): d 2.7
3
1
(q, 2JRhF = JPF = 12.4 Hz). 31P{ H} NMR (121.5 MHz, CDCl3):
d 25.6 (dt, 1JRhP = 127.5, 2JPP = 26.9 Hz, PA), 20.3 (ddq, 1JRhP
=
105.2, 2JPP = 26.7, 3JPF = 12.9 Hz, PX). n (Nujol)/cm : 854 (O–
O). ESI-MS (Me2CO) m/z 959 ([Rh(FHF)(OH)(PMePh2)4]+), 827
([Rh(CF3)(O2)(PMePh2)3]Na+), 803 ([Rh(CF3)(O2)(PMePh2)3]+ -
H), 503 ([Rh(PMePh2)2]+). Exact mass (ESI-MS) m/z 804.1166
(found), 804.1165 (calcd).
-1
˜
1
1.55. Found: C 64.76, H 5.46, N 1.59. H NMR (300.1 MHz,
C6D6): d 7.65–7.60 (m, 12 H, H2, Ph), 6.97 (m, 18 H, H3 and
2
H4, Ph), 6.59–6.42 (AB2 m, 3 H, Xy), 2.04 (d, JPH = 4.8 Hz,
1
9 H, Me), 1.38 (s, 6 H, Xy). 13C{ H} NMR (100.8 MHz, THF):
d 168.3 (br m, RhCN), 141.8 (br s, C1, Ph), 133.3 (s, C2, Xy),
[Rh(CF3)(CO)(PMePh2)3] (10). A solution of 2 in THF (5 mL)
was prepared from 1 (0.152 g, 0.33 mmol), Me3SiCF3 (0.67 mL
of a 2.0 M solution in THF, 1.3 mmol) and PMePh2 (0.38 mL,
2.0 mmol). CO was bubbled through the solution for 1 min and,
after stirring for 30 min, the solution was concentrated to dryness.
The oily residue was stirred at 0 ◦C for 4 h with n-pentane (5 mL) to
give a yellow solid which was washed with n-pentane (3 ¥ 5 mL) and
2
132.1 (d, JPC = 11.4 Hz, C2, Ph), 128.0 (br s, C4 Ph), 127.8
3
(s, C4, Xy), 127.3 (d, JPC = 7.5 Hz, C3, Ph), 126.5 (s, C3,
Xy), 125.9 (s, C1, Xy), 17.3 (s, Me, Xy), 17.0 (br s, PMe); the
CF3 carbon signal was not observed. 19F NMR (282.4 MHz, D8-
toluene, -60 ◦C): d 3.5 (br q, 3JPF = 28.8 Hz, 12), -9.9 (q, 2JRhF
=
3JPF = 20.3 Hz, trans-[Rh(CF3)(CNXy)(PMePh2)2]); (20 ◦C) -4.0
◦
1
(br s); (70 C) -10.8 (br s). 31P{ H} NMR (121.5 MHz, D8-toluene,
-60 ◦C): d 12.4 (dq, 1JRhP = 150.9, 3JPF = 29.7 Hz), the signal of
trans-[Rh(CF3)(CNXy)(PMePh2)2] was not detected due to its low
◦
dried under vacuum. Yield: 0.476 g (89%). mp: 83–86 C. Anal.
calcd for C41H39F3OP3Rh: C 61.51, H 4.91. Found: C 61.15, H
1
5.00. H NMR (400.9 MHz, CDCl3): d 7.42–7.38 (m, 12 H, H2,
◦
◦
-1
˜
concentration; (20 C) 8.8 (br s); (70 C) 6.7 (br s). n (Nujol)/cm :
Ph), 7.29–7.24 (m, 18 H, H3 and H4, Ph), 1.93 (d, 2JPH = 5.7 Hz,
∫
2096 (C N).
1
9 H, Me). 13C{ H} NMR (100.8 MHz, CD2Cl2): d 202.5 (br m,
CO), 140.9 (d, 1JPC = 28.2 Hz, C1, Ph), 132.2 (d, 2JPC = 12.6 Hz,
C2, Ph), 129.0 (s, C4, Ph), 128.3 (d, 3JPC = 8.6 Hz, C3, Ph), 18.2
[Rh(CF3)(CNXy)(PMe2Ph)3] (13). To a solution of 5 in THF
(7 mL), prepared from 1 (0.123 g, 0.27 mmol), Me3SiCF3 (0.50 mL
of a 2.0 M THF solution, 1.0 mmol) and PMe2Ph (0.24 mL,
1.7 mmol), XyNC (0.071 g, 0.54 mmol) was added and the solution
was stirred for 45 min. The resulting dark orange solution was
concentrated to dryness and the residue stirred with n-pentane
(5 mL) to give an orange solid, which was washed with n-pentane
(3 ¥ 5 mL) and dried under vacuum. Yield: 0.244 g (64%). mp:
75–77 ◦C. Anal. calcd for C34H42F3NP3Rh: C 56.91, H 5.90, N
1
(d, JPC = 15.7 Hz, Me); the signal of the CF3 carbon was not
observed. 19F NMR ◦(282.4 MHz, D8-toluene, -60 ◦C): d -0.3 (q,
3JPF = 28.0 Hz); (25 C) -2.0 (br s); (70 ◦C) -9.8 (br s); no 103Rh–
19F coupling was observed at low temperature due to the low 2JRhF
value.12 31P{ H} NMR (162.3 MHz, D8-toluene, -60 ◦C): d 11.1
1
(dq, 1JRhP = 145.2, 3JPF = 29.7 Hz); (25 ◦C) 8.6 (br s); (70 ◦C) 7.0
-1
˜
(s). n (Nujol)/cm : 1968 (CO).
1
1.95. Found: C 56.66, H 6.01, N 1.91. H NMR (300.1 MHz,
[Rh(n-C3F7)(CO)(PMePh2)3] (11). A solution of 3 in THF
(6 mL) was prepared from 1 (0.133 g, 0.29 mmol), Me3SiC3F7
(0.25 mL, 1.2 mmol) and PMePh2 (0.34 mL, 1.8 mmol). After
bubbling CO for 1 min, the solution was stirred for 1 h and
concentrated to dryness. The residue was stirred with n-pentane
(5 mL) to give an orange solid, which was washed with n-pentane
(3 ¥ 5 mL) and dried under vacuum. Yield: 0.383 g (73%). mp: 95–
97 ◦C. Anal. calcd for C43H39F7OP3Rh: C 57.35, H 4.36. Found: C
57.38, H 4.57. 1H NMR (300.1 MHz, C6D6): d 7.54–7.49 (m, 12 H,
H2, Ph), 7.01 (m, 18 H, H3 and H4, Ph), 1.77 (d, 2JPH = 4.2 Hz,
9 H, Me); on lowering the temperature, the only changes observed
in the 1H NMR spectrum were broadening and slight shifts of the
C6D6): d 7.56 (m, 6 H, H2, Ph), 7.05–6.93 (m, 9 H, H3 and H4,
Ph), 6.59–6.53 (AB2 m, 3 H, Xy), 1.68 (s, 18 H, PMe), 1.60 (br s,
1
6 H, Xy). 13 is too unstable in solution for its 13C{ H} NMR
spec◦trum to be measured. 19F NMR (282.4 MHz, D8-toluene,
3
-70 C): d 2.6 (br q, 3JPF = 32.5 Hz, 13), -11.2 (q, 2JRhF = JPF
=
19.9 Hz, trans-[Rh(CF3)(CNXy)(PMe2Ph)2]); (21 ◦C) 1.3 (br s).
◦
31P{ H} NMR (121.5 MHz, D8-toluene, -70 C): d 1.2 (dq, 1JRhP
=
1
3
144.2, JPF = 21.8 Hz, trans-[Rh(CF3)(CNXy)(PMe2Ph)2]), 8.1
◦
1
3
˜
(dq, JRhP = 145.3, JPF = 32.4 Hz, 13); (21 C) -8.6 (br s). n
-1
∫
(Nujol)/cm : 2057 (C N).
[Rh(n-C3F7)(CNXy)(PMe2Ph)3] (14). To a solution of 4 in
THF (7 mL), prepared from 1 (0.107 g, 0.24 mmol), Me3SiC3F7
(0.21 mL, 1.0 mmol) and PMe2Ph (0.21 mL, 1.43 mmol), XyNC
(0.066 mg, 0.50 mmol) was added and the solution was stirred
for 1 h. The resulting dark orange solution was concentrated to
dryness and the residue stirred with n-pentane (5 mL) to give a
brick red solid, which was washed with n-pentane (2 ¥ 5 mL) and
1
1
signals. 13C{ H} NMR (50.3 MHz, CD2Cl2): d 138.8 (d, JPC
=
24.3 Hz, C1, Ph), 132.6 (d, 2JPC = 14.1 Hz, C2, Ph), 129.7 (s, C4,
3
1
Ph), 128.7 (d, JPC = 8.7 Hz, C3, Ph), 15.5 (d, JPC = 11.5 Hz,
Me); the low stability of 11 in solution prevented the detectio◦n of
CO and C3F7 signals. 19F NMR (282.4 MHz, D8-toluene, -65 C):
d -73.5 (br s, Rh–CF2), -76.9 (br s, CF3), -112.1 (br s, CF2CF3);
(25 ◦C) -78.1 (t, JFF = 10.4 Hz, CF3), -86.4 (br s, Rh–CF2), -113.9
◦
dried under vacuum. Yield: 0.222 g (58%). mp: 71–73 C. Anal.
◦
1
(s, CF2CF3). 31P{ H} NMR (121.5 MHz, D8-toluene, -65 C): d
calcd for C36H42F7NP3Rh: C 52.89, H 5.18, N 1.71. Found: C
3862 | Dalton Trans., 2009, 3854–3866
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52.80, H 5.33, N 1.67. 1H NMR (200.1 MHz, C6D6): d 7.60–7.51
6.0 Hz, 6 H, PMe), 1.51 (s, 3 H, MeCO), 1.13 (s, 3 H, MeCO),
1
(m, 6 H, H2, Ph), 7.08–7.00 (m, 9 H, H3 and H4, Ph), 6.68–
0.79 (dt, 2JRhH = 2.1, 3JPH = 6.0 Hz, 3 H, RhMe). 13C{ H} NMR
2
=
6.54 (AB2 m, 3 H, Xy), 1.72 (br s, 6 H, Xy), 1.60 (d, JPH
=
(100.8 MHz, CD2Cl2): d 187.8, 186.4 (both s, C O), 134.3 (ABX
1
4.8 Hz, 18 H, PMe); the H NMR signals become broad at low
m, J = 54.8 Hz, C1, Ph), 133.6 (vt, N = 11.2 Hz, C2, Ph), 133.5
4
temperature (D8-toluene). 14 is too unstable in solution for its
(vt, N = 10.6 Hz, C2, Ph), 129.8 (d, JPC = 4.4 Hz, C4, Ph),
1
13C{ H} NMR spectrum to be measured. 19F NMR (282.4 MHz,
128.0 (vt, N = 8.6 Hz, C3, Ph), 100.0 (s, CH, acac), 28.6, 28.2
D8-toluene, -80 ◦C): d -70.8 (very br s, RhCF2), -76.8 (br s, CF3),
-111.9 (br s, CF2); (-60 ◦C) -70.6 (br q, 3JPF = 35.1 Hz, RhCF2),
-76.9 (br s, CF3), -111.9 (br q, 3JFF = 14.5 Hz, CF2); (25 ◦C) -77.5
(br s, RhCF2), -77.7 (br t, 3JFF = 9.5 Hz, CF3), -112.6 (br s, CF2).
(both s, Me, acac), 12.5 (vt, N = 29.0 Hz, PMe), -5.8 (dm, 1JRhC
=
25.0 Hz, RhMe); the CF3 carbon signal was not observed. 19F
NMR (282.4 MHz, CDCl3): d -5.22 (dt, 2JRhF = 13.2, 3JPF = 19.2
1
Hz). 31P{ H} NMR (121.5 MHz, CDCl3): d 16.8 (dq, 1JRhP = 119.4,
31P{ H} NMR (121.5 MHz, D8-toluene, -80 ◦C): d -4.0 (br m,
JPF = 19.2 Hz). n (Nujol)/cm 1586 and 1518 (CO of acac).
1
3
-1
˜
1JRhP = 142, 2JPP = 116 Hz, 2 P), -16.0 (br dtt, 1JRhP = 130, 2JPP
=
116, 3JPF = 70 Hz, 1 P); (-60 ◦C) -5.3 (very br m), -14.1 (very br
[OC-6-34]- and [OC-6-43]-[Rh(CF3)(Me)I(PMe2Ph)3] (17 and
◦
-1
∫
˜
m); (25 C) -11.7 (br s). n (Nujol)/cm : 2062 (C N).
17¢). To a solution of 5 in THF (10 mL), prepared from 1
(0.135 g, 0.30 mmol), Me3SiCF3 (0.60 mL of a 2.0 M THF
solution, 1.20 mmol) and PMe2Ph (0.26 mL, 1.8 mmol), MeI
(0.08 mL, 1.3 mmol) was added to the resulting solution and
stirred for 40 min. The suspension was filtered off to remove a small
amount of (PMe3Ph)I and the yellow filtrate was concentrated to
dryness. n-Pentane (5 mL) was added, the suspension was filtered
off and the yellow solid was washed with n-pentane (2 ¥ 5 mL)
and dried under vacuum. Yield: 0.351 g (81%). Anal. calcd for
(PMe2Ph2)[OC-6-43]-[Rh(CF3)(Me)I2(PMePh2)2] (15). A so-
lution of 2 in THF (12 mL), prepared from 1 (0.050 g, 0.11 mmol),
Me3SiCF3 (0.22 mL of a 2.0 M solution in THF, 0.44 mmol)
and PMePh2 (0.123 mL, 0.66 mmol) was stirred for 2 h and then
MeI (0.041 mL, 0.66 mmol) was added. After stirring for 3.5 h,
a suspension formed, which was filtered to remove (PMe2Ph2)I
(0.089 g, 0.26 mmol). The filtrate was concentrated to dryness
under vacuum. The resulting yellow solid was washed with Et2O
(3 ¥ 5 mL) and dried under vacuum. Yield: 0.109 g (47%). mp:
143–145 ◦C. Anal. calcd for C42H45F3I2P3Rh: C 47.75, H 4.29.
Found: C 47.62, H 4.45. 1H NMR (200.1 MHz, CDCl3): d 7.91–
1
C26H36F3IP3Rh: C 42.88, H 4.98. Found: C 42.89, H 5.20. H
NMR (400.9 MHz, CDCl3): d 7.64–7.06 (several m, Ph), 2.10 (vt,
N = 6.5 Hz, PMeX of 17¢), 1.88 (vt, N = 6.7 Hz, PMeX of 17¢), 1.71
(vt, N = 6.7 Hz, PMeX of 17), 1.66 (vt, N = 6.5 Hz, PMeX of 17),
1.31 (d, 2JPH = 7.7 Hz, PMeA of 17¢), 1.25 (d, 2JPH = 7.5 Hz, PMeA
of 17), 0.80 (ddt, 2JRhH = 2.3, 3JP(X)H = 5.3, 3JP(A)H = 6.8 Hz, RhMe
2
7.32 (several multiplets, 30 H, Ph), 2.85 (d, JPH = 13.8 Hz,
2
6 H, MeP+), 2.41 (vt, N = 6.3 Hz, 6 H, MeP) 1.30 (dt, JRhH
=
3
1
2
3
3
2.2, JPH = 6.1 Hz, 3 H, RhMe). 13C{ H} NMR (150.9 MHz,
of 17¢), 0.68 (ddt, JRhH = 1.7, JP(X)H = 7.6 Hz, JP(A)H = 5.6 Hz,
1
CDCl3): d 134.9 (s, C4, PhP+), 133.7, 133.6 (both br s, C2,
RhMe of 17). 13C{ H} NMR (100.8 MHz, CDCl3): d 142.1 (dt,
PMePh2), 132.2 (d, JPC = 10.7 Hz, C2, PhP+), 130.4 (d, JPC
=
1JPC = 25.8, 3JPC = 2.2 Hz, C1, PhA of 17), 138.1 (vt of d, N = 41.7,
3JPC = 3.7 Hz, C1, PhX of 17), 136.0 (vt, N = 38.1 Hz, C1, PhX of
17¢), 131.7 (vt, N = 8.4 Hz, C2, PhX of 17¢), 131.4 (vt, N = 7.9 Hz,
C2, PhX of 17), 130.9 (d, JPC = 7.4 Hz, C2, PhA of 17), 130.5 (d,
JPC = 7.4 Hz, C2, PhA of 17¢), 129.22 (s, C4, PhX of 17), 129.18 (s,
C4, PhX of 17¢), 128.72 (d, 4JPC = 1.5 Hz, C4, PhA of 17), 128.66 (d,
4JPC = 2.2 Hz, C4, PhA of 17¢), 128.5 (d, JPC = 7.4 Hz, C3, PhA of
17¢), 128.2 (d, JPC = 7.4 Hz, C3, PhA of 17), 128.0 (vt, N = 8.8 Hz,
C3, PhX of 17¢), 127.9 (vt, N = 8.2 Hz, C3, PhX of 17), 21.2 (vt,
N = 35.7 Hz, PMeX of 17¢), 17.6 (d, 1JPC = 21.7 Hz, PMeA of 17),
17.5 (vt, N = 35.3 Hz, PMeX of 17), 17.3 (d, 1JPC = 24.3 Hz, PMeA
of 17¢), 16.6 (vt, N = 35.6 Hz, PMeX of 17), 16.0 (vt, N = 33.1 Hz,
PMeX of 17¢), 4.5 (ddtq, 1JRhC = 18.5, 2JP(X)C = 8.1, 2JP(A)C = 80.2,
2
3
12.8 Hz, C3, PhP+), 129.7 (br s, C4, PMePh2), 127.9 (br s,
C3, PMePh2), 120.4 (d, JPC = 89.8 Hz, C1, PhP+), 16.7 (br s,
1
PMePh2), 11.1 (d, JPC = 56.2 Hz, MeP+); owing to the low
2
stability of 15 in solution, its 13C{ H} NMR spectrum could not
1
be acquired enough as to observe the lowest intensity signals.
19F NMR (188.3 MHz, CDCl3): d 1.4 (q, 2JRhF = JPF = 19.0 Hz).
3
1
+
31P{ H} NMR (81.0 MHz, CDCl3): d 21.2 (s, PMe2Ph2 ), 18.0 (dq,
1JRhP = 117.7, JPF = 21.2 Hz, RhP). ESI-MS (MeCN, positive
3
mode) m/z: 587 ([Rh(CF3)(Me)(PMePh2)2]+), 215 ([PMe2Ph2]+);
(negative mode) 1155 ([Rh2(CF3)2(Me)2I3(PMePh2)2]-), 841
([Rh(CF3)(Me)I2(PMePh2)2]-), 641 ([Rh(CF3)(Me)I2(PMePh2)]-),
442 ([RhH(CF3)(Me)I2]-), 127 (I-).
1
2
3JFC = 6.0 Hz, RhMe of 17), 0.8 (ddtq, JRhC = 23.8, JP(A,X)C
=
3
[OC-6-14]-[Rh(CF3)(Me)(acac)(PMePh2)2] (16). To a solution
of 2 in THF (13 mL), prepared from 1 (0.156 g, 0.34 mmol),
Me3SiCF3 (0.68 mL of a 2.0 M THF solution, 1.36 mmol)
and PMePh2 (0.39 mL, 2.07 mmol), was added MeI (0.09 mL,
1.4 mmol) and the solution stirred for 30 min. The resulting
suspension was filtered and Tl(acac) (0.208 g, 0,69 mmol) was
added to the filtrate. The suspension was stirred for 1 h and filtered
to remove TlI. The filtrate was concentrated to dryness and, on
addition of n-pentane (6 mL), a pale-yellow oil formed, which
solidified on standing at -33 ◦C for 15 h. The resulting pale-yellow
solid was washed with n-pentane (3 ¥ 5 mL) and dried under
vacuum. Yield: 0.244 g (52%). mp: 141–144 ◦C. Anal. calcd for
6.5 and 7.3, JFC = 4.8 Hz, RhMe of 17¢); the signals of C1 of
PhA in 17¢, and of CF3 carbons were not observed; the RhMe data
were obtained at 75.5 MHz from a 13C-labelled sample, which was
prepared using 13CH3I. 19F NMR (188.3 MHz, CDCl3): d -1.52
(dq, 2JRhF = 14.2, 3JP(A)F = JP(X)F = 19.4 Hz, 17), -8.0 (dq, 2JRhF
=
3
1
3JP(X)F = 14.9, 3JP(A)F = 53.2 Hz, 17¢). 31P{ H} NMR (162.3 MHz,
CDCl3): d -4.4 (ddq, 1JRhP = 107.7, 2JPP = 21.4, 3JPF = 18.9 Hz,
PX of 17), -6.6 (ddq, 1JRhP = 104.2, 2JPP = 32.2, 3JPF = 17.1 Hz, PX
1
2
3
of 17¢), -24.1 (dtq, JRhP = 75.0, JPP = 31.9, JPF = 53.2 Hz, PA
of 17¢), -26.3 (d of sextuplets, 1JRhP = 77.8, 2JPP = JPF = 21.0 Hz,
3
PA of 17).
1
C33H36F3O2P2Rh: C 57.34, H 5.29. Found: C 57.70, H 5.66. H
[OC-6-52]-[Rh(CF3)(Me)I(CNXy)(PMePh2)2]
(18). MeI
NMR (300.1 MHz, CDCl3): d 7.59–7.53 (m, 8 H, H2, Ph), 7.36–
7.27 (m, 12 H, H3 and H4, Ph), 4.64 (s, 1 H, CH), 1.86 (vt, N =
(0.092 mL, 1.5 mmol) was added to a solution of 12 (0.131 g,
0.14 mmol) in THF (10 mL) and stirred for 40 min. (PMe2Ph2)I
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was separated by filtration and the filtrate concentrated to
dryness. The oily residue was stirred with n-pentane (5 mL), at
0 ◦C, for 30 min to give a suspension that was filtered off and the
pale-yellow solid was washed with n-pentane (3 ¥ 5 mL) and dried
under vacuum. Yield: 0.113 g (91%). mp: 121–123 ◦C. Anal. calcd
for C37H38F3INP2Rh: C 52.56, H 4.53, N 1.66. Found: C 52.27, H
washed with n-pentane (2 ¥ 5 mL) and dried under vacuum. Yield:
197 mg, 96%. mp: 151–154 ◦C. Anal. calcd for C29H34F7INP2Rh:
1
C 42.41, H 4.17, N 1.71. Found: C , 42.70, H 4.21, N 1.75. H
NMR (300.1 MHz, CDCl3): d 7.48 (m, 4 H, H2, Ph), 6.89–6.13
(m, 9 H, H3 and H4 of Ph and Xy), 2.39 (br vt, 6 H, PMe), 1.98
(s, 6 H, Me, Xy), 1.79 (br vt, 6 H, PMe), 0.78 (td, 3 H, 2JRhH = 1.9,
1
1
4.66, N 1.96. H NMR (300.1 MHz, C6D6): d 7.91 (m, 4 H, H2,
3JPH = 5.5 Hz, RhMe). 13C{ H} NMR (100.8 MHz, CDCl3): d
Ph), 7.81 (m, 4 H, H2, Ph), 6.95–6.74 (m, 12 H, H3 and H4 of Ph),
6.65 (t, 3JHH = 7.5 Hz, 1 H, H4, Xy), 6.48 (d, 2 H, 3JHH = 7.7 Hz,
H3, Xy), 2.39 (vt, N = 6.6 Hz, 6 H, PMe), 1.82 (s, 6 H, Me, Xy),
154.4 (br m, RhCN), 137.9 (vt, N = 45.0 Hz, C1, Ph), 135.2 (br s,
C2, Xy), 129.5 (vt, N = 8.2 Hz, C2, Ph), 128.7 (s, C4, Ph), 128.6 (s,
C4, Xy), 127.7 (vt, N = 8.5 Hz, C3, Ph), 127.5 (s, C3, Xy), 126.0
(s, C1, Xy), 20.1 (vt, N = 35.4 Hz, PMe), 18.6 (s, Me, Xy), 12.2 (vt,
N = 32.0 Hz, PMe), -1.2 (dm, 1JRhC = 21.4 Hz, RhMe). 19F NMR
(282.4 MHz, CDCl3): d -78.8 (t, 4JFF = 13.2 Hz, CF3), -81.7 (br
1
1.22 (td, 3 H, 2JRhH = 2.2, 3JPH = 5.3 Hz, RhMe). 13C{ H} NMR
1
(100.8 MHz, CDCl3): d 155.1 (br s, RhCN), 137.8 (qdt, JFC
=
356.9, 1JRhC = 46.6, 2JPC = 10.1 Hz, CF3), 135.3 (vt, N = 48.1 Hz,
C1, Ph), 135.0 (s, C2, Xy), 133.7 (vt, N = 46.1 Hz, C1, Ph), 133.4
(vt, N = 9.4 Hz, C2, Ph), 133.1 (vt, N = 8.4 Hz, C2, Ph), 129.5,
129.4 (both s, C4, Ph), 128.6 (s, C4, Xy), 127.7 (vt, N = 9.0 Hz,
C3, Ph), 127.5 (s, C3, Xy), 127.4 (vt, N = 9.1 Hz, C3, Ph), 126.0
(s, C1, Xy), 18.6 (vt, J = 33.3 Hz, PMe), 18.5 (s, Me, Xy), 1.75
(dq, 1JRhC = 23.6, 4JFC = 4.4 Hz, RhMe). 19F NMR (282.4 MHz,
1
m, RhCF2), -114.3 (s, CF2). 31P{ H} NMR (121.5 MHz, CDCl3):
1
3
-1
˜
d -3.5 (dt, JRhP = 100.0, JPF = 28.5 Hz). n (Nujol)/cm : 2156
∫
(C N).
=
[OC-6-32]-[Rh(CF3)(CF CF2)I(CNXy)(PMePh2)2]
=
(20).
CF2 CFI (0.022 mL, 0.25 mmol) was added to a solution of 12
(0.109 g, 0.12 mmol) in THF (5 mL), and the pale-yellow solution
was stirred for 1 h and conce◦ntrated to dryness. The resulting
oil was stirred for 10 min at 0 C with n-pentane (5 mL) to give
a suspension that was filtered off and the pale-yellow solid was
washed with n-pentane (2 ¥ 5 mL) and dried under vacuum. Yield:
0.097 g (88%). mp: 173–175 ◦C. Anal. calcd for C38H35F6INP2Rh:
C6D6): d -6.5 (dt, JRhF = 13.5, JPF = 18.2 Hz). 31P{ H} NMR
2
3
1
(121.5 MHz, C6D6): d 10.2 (dq, 1JRhP = 103.9, 3JPF = 17.8 Hz). n
˜
-1
∫
(Nujol)/cm : 2176 (C N).
[OC-6-52]-[Rh(n-C3F7)(Me)I(CNXy)(PMe2Ph)2] (19). MeI
(0.15 mL, 2.4 mmol) was added to a solution of 14 (202 mg,
0.25 mmol) in THF (10 mL) and stirred for 30 min. (PMe3Ph)I
was separated by filtration and the filtrate was concentrated to
dryness. The residue was stirred with n-pentane (5 mL) to give
a suspension that was filtered off and the pale-orange solid was
1
C 50.08, H 3.87, N 1.54. Found: C 50.05, H 4.06, N 1.65. H
NMR (300.1 MHz, CDCl3): d 7.84 (m, 4 H, H2, Ph), 7.74 (m,
4 H, H2, Ph), 7.24–7.01 (m, 13 H, H4 of Xy + H3 and H4 of Ph),
6.82 (d, 2 H, 3JHH = 4.8 Hz, H3, Xy), 2.41 (vt, 6 H, N = 6.5 Hz,
Table 1 Crystal data for 10, 15 and 19
10
15
19
Empirical formula
Formula weight
Crystal size/mm3
Crystal system
Space group
C41H39F3OP3Rh
800.54
0.31 ¥ 0.27 ¥ 0.17
Orthorhombic
Pbca
19.3065(11)
10.2522(5)
37.1457(18)
90
90
90
7352.4(7)
8
1.446
3280
100(2)
2.32–29.09
-26 ≤ h ≤ 26
-13 ≤ k ≤ 13
-50 ≤ l ≤ 50
86 841
9488
0.0396
1.113
0.035
C42H45F3I2P3Rh
1056.40
0.35 ¥ 0.12 ¥ 0.12
Monoclinic
P21/n
10.2462(7)
17.9511(12)
22.2871(15)
90
99.995(2)
90
4037.1(5)
4
1.738
2080
100(2)
1.86–28.22
-13 ≤ h ≤ 13
-22 ≤ k ≤ 23
-29 ≤ l ≤ 29
46 031
9381
0.0219
1.153
0.032
0.075
2.457 and -0.433
C29H34F7INP2Rh
821.32
0.26 ¥ 0.15 ¥ 0.15
Triclinic
¯
P1
˚
a/A
11.4084(5)
11.6334(5)
13.1497(6)
88.019(2)
76.668(2)
69.908(2)
1592.92(12)
2
1.712
812
100(2)
1.59–28.18
-14 ≤ h ≤ 14
-14 ≤ k ≤ 15
-16 ≤ l ≤ 17
18 039
7093
0.0154
˚
b/A
˚
c/A
a/◦
b/◦
g /◦
3
˚
V/A
Z
D
calcd/Mg m-3
F(000)
T/K
q range/◦
Index ranges
Reflections collected
Independent reflections
Rint
GOF on F2
1.066
0.019
0.047
0.510 and -0.470
a
R1
b
wR2
0.085
1.289 and -0.354
-3
˚
Largest diffraction peak and hole/e A
a R1 = RꢀFo| - |Fcꢀ/R|Fo| for reflections with I > 2s(I). b wR2 = [R[w(Fo - Fc2)2]/R[w(Fo2)2]0.5 for all reflections; w-1 = s (F2) + (aP)2 + bP, where
2
2
2
P = (2Fc + Fo2)/3 and a and b are constants set by the program.
3864 | Dalton Trans., 2009, 3854–3866
This journal is
The Royal Society of Chemistry 2009
©

View Article Online
1
PMe), 1.83 (s, 6 H, Me, Xy). 13C{ H} NMR (100.8 MHz, CDCl3):
128, 7454; M. E. Van der Boom, Y. Ben-David and D. Milstein, J. Am.
Chem. Soc., 1999, 121, 6652; H. Torrens, Coord. Chem. Rev., 2005, 249,
1957; T. G. Richmond, Top. Organomet. Chem., 1999, 3, 243; M. M.
Kremlev, A. I. Mushta, W. Tyrra, D. Naumann, H. T. M. Fischer and
Y. L. Yagupolskii, J. Fluorine Chem., 2007, 128, 1385; J. Vela, J. M.
Smith, Y. Yu, N. A. Ketterer, C. J. Flaschenriem, R. J. Lachicotte and
P. L. Holland, J. Am. Chem. Soc., 2005, 127, 7857; R. P. Hughes, R. B.
Laritchev, L. N. Zakharov and A. L. Rheingold, J. Am. Chem. Soc.,
2004, 126, 2308; T. Braun and R. N. Perutz, Chem. Commun., 2002,
2749; T. Schaub, M. Backes and U. Radius, J. Am. Chem. Soc., 2006,
128, 15964.
2 V. V. Grushin and W. J. Marshall, J. Am. Chem. Soc., 2006, 128, 12644;
V. V. Grushin and W. J. Marshall, J. Am. Chem. Soc., 2006, 128, 4632.
3 D. Huang and K. G. Caulton, J. Am. Chem. Soc., 1997, 119, 3185; D.
Huang, P. R. Koren, K. Folting, E. R. Davidson and K. G. Caulton,
J. Am. Chem. Soc., 2000, 122, 8916.
d 161.8 (ddd, 1JFC = 273.5 and 302.2, 2JFC = 46.4 Hz, CF2), 149.4
(m, RhCN), 136.0 (s, C2, Xy), 135.5 (vt, N = 51.1 Hz, C1, Ph),
134.7 (vt, N = 48.1 Hz, C1, Ph), 132.8 (vt, N = 9.2 Hz, C2, Ph),
132.6 (vt, N = 10.1 Hz, C2, Ph), 129.8, 129.6 (both s, C4, Ph),
128.7 (s, C4, Xy), 127.7, 127.4 (both vt, N = 9.6 Hz, C3, Ph), 127.2
(s, C3, Xy), 125.5 (s, C1, Xy), 20.5 (vt, N = 35.7 Hz, PMe), 18.3
(s, Me, Xy); the CF3 and CF carbons signals were not observed.
19F NMR (282.4 MHz, CDCl3): d 2.9 (dddt, 2JRhF = 10.3, 3JPF
=
18.4, 5JFF = 10.3, 4JFF = 13.8 Hz, CF3), -88.3 (ddm, 2JFF (gem) =
3
=
84.2, JFF (cis) = 39.8 Hz, RhC CF trans to Rh), -114.8 (ddm,
JFF (gem) = 84.2, 3JFF (trans) = 106.8 Hz, RhC CF cis to Rh),
2
=
-140.6 (ddqt, 3JFF (cis) = 41.3, 3JFF (trans) = 107.9, 4JFF = 13.8,
4 P. M. Treichel and F. G. A. Stone, Adv. Organomet. Chem., 1964, 1,
143.
JPF = 14.3 Hz, RhCF C). 31P{ H} NMR (81.0 MHz, CDCl3): d
3
1
=
8.4 (ddq, 1JRhP = 95.6, 3JPF (CF3) = 17.8, 3JPF (RhCF C) = 14.3
=
5 M. I. Bruce, and F. G. A. Stone, in Preparative Inorganic Reactions, ed.
W. L. Jolly, Interscience Publishers, Bristol, 1968, vol. 4, pp. 177.
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perfluoroalkyl complexes.
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-1
∫
=
˜
Hz). n (Nujol)/cm : 2182 (C N), 1706(C C).
Crystallography
The crystal structures of 10, 15 and 19 were measured on a Bruker
Smart APEX diffractometer. Data (Table 1) were collected using
monochromated MoKa radiation in w scan mode. The structures
were solved by direct methods and refined anisotropically on F2.
The methyl groups were refined using rigid groups and the other
hydrogens were refined using a riding mode. Special features of
compound 15: the largest residual electron density peak (2.46
-3
˚
˚
e A ) is present at 0.79 A of I2. This peak may be due to
residual absorption or unidentified disorder effects. The CF3
ligand and the trans iodine atom are mutually disordered, and
the site occupancies of each contributing disordered position were
refined to 72/28%.
Acknowledgements
We thank Direccio´n General de Investigacio´n/FEDER (grant
CTQ2007-60808/BQU, C-Consolider and a “Ramo´n y Cajal”
contract to J. G.-R.) and Fundacio´n Se´neca (Ayudas a los Grupos
y Unidades de Excelencia Cient´ıfica de la Regio´n de Murcia 2007–
2010, grant 02992/PI/05, and a contract to J. G.-L) for financial
support.
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