Preparation, molecular structure and reactivity of mono- and di-nuclear sulfonato rhodium(I) complexes

Article abstract of DOI:10.1039/a805900d

The reaction of [Rh(η³-C₃H₅)(PPrⁱ ₃)₂] 1 or [Rh(η³-CH₂Ph)(PPrⁱ₃) ₂] 2 with an equimolar amount of RSO₃H (R = Me, p-tolyl, CF₃, F, Camph) led to the formation of the monomeric sulfonatorhodium(I) complexes [Rh{η²-O₂S(O)R}(PPrⁱ₃) ₂] 3-7 in excellent yield. An alternative route for the preparation of 4 (R = p-tolyl) and 5 (R = CF₃) is based on the reaction of PPrⁱ₃ with the dinuclear compounds [{Rh(C₈H₁₄)₂[μ-O₂S(O)R]} ₂], which were obtained either from [{Rh(C₈H₁₄)₂(μ-Cl)}₂] 8 or [{Rh(C₈H₁₄)₂(μ-OH)}₂] 9 as starting materials. Compounds 3-7 react smoothly with hydrogen by oxidative addition to give the dihydridorhodium(III) complexes [RhH₂{η²-O₂S(O)R}(PPrⁱ ₃)₂]. Moreover, on treatment of 3-6 with CO and C₂H₄ the chelating bond of the sulfonate ligand is partially opened and the carbonyl and ethene complexes trans-[Rh{η¹-OS(O)₂R}(L)(PPrⁱ ₃)₂] (L = CO or C₂H₄) are formed. The bis(stibine)-rhodium(I) derivative trans-[Rh{η¹-OS(O)₂CF₃}(C₂H ₄)(SbPrⁱ₃)₂] was obtained from [{Rh(C₂H₄)₂[μ-O₂S(O)CF ₃]}₂] and SbPrⁱ₃. Reaction of the compounds [Rh{η2-O₂S(O)CF₃}(olefin)(PPrⁱ ₃)] (olefin = C₈H₁₄ or C₂H₄) with benzene led to the displacement of the sulfonate ligand and to the formation of the half-sandwich-type complexes [Rh{η⁶-C₆H₆)-(olefin)(PPrⁱ ₃)][CF₃SO₃] containing a rather labile benzene-rhodium bond. The preparation of the vinylidene complex trans-[Rh{η¹-OS(O)C₆H ₄Me-p}(=C=CHPh)(PPrⁱ₃)₂] is also described and the crystal and molecular structures of three compounds have been determined. The four-co-ordinate sulfonato complexes 3-6 are active catalysts in the C-C coupling reaction of ethene and diphenyldiazomethane. Besides the three isomeric 1:1 adducts of C₂H₄ and CPh₂, quite unexpectedly also the 2:1 adduct 3,3-diphenylpent-1-ene is formed.

Full text of DOI:10.1039/a805900d

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Preparation, molecular structure and reactivity of mono- and
di-nuclear sulfonato rhodium(I) complexes
Helmut Werner, Marco Bosch, Michael E. Schneider, Christine Hahn, Frank Kukla,
Matthias Manger, Bettina Windmüller, Birgit Weberndörfer and Matthias Laubender
Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, D-97074 Würzburg,
Germany. E-mail: helmut.werner@mail.uni-wuerzburg.de
Received 28th July, Accepted 7th September 1998
The reaction of [Rh(η3-C3H5)(PPri3)2] 1 or [Rh(η3-CH2Ph)(PPri3)2] 2 with an equimolar amount of RSO3H (R = Me,
p-tolyl, CF3, F, Camph) led to the formation of the monomeric sulfonatorhodium() complexes [Rh{η2-O2S(O)R}-
(PPri3)2] 3–7 in excellent yield. An alternative route for the preparation of 4 (R = p-tolyl) and 5 (R = CF3) is based on
the reaction of PPri3 with the dinuclear compounds [{Rh(C8H14)2[µ-O2S(O)R]}2], which were obtained either from
[{Rh(C8H14)2(µ-Cl)}2] 8 or [{Rh(C8H14)2(µ-OH)}2] 9 as starting materials. Compounds 3–7 react smoothly with
hydrogen by oxidative addition to give the dihydridorhodium() complexes [RhH2{η2-O2S(O)R}(PPri3)2]. Moreover,
on treatment of 3–6 with CO and C2H4 the chelating bond of the sulfonate ligand is partially opened and the
carbonyl and ethene complexes trans-[Rh{η1-OS(O)2R}(L)(PPri3)2] (L = CO or C2H4) are formed. The bis(stibine)-
rhodium() derivative trans-[Rh{η1-OS(O)2CF3}(C2H4)(SbPri3)2] was obtained from [{Rh(C2H4)2[µ-O2S(O)CF3]}2]
and SbPri3. Reaction of the compounds [Rh{η2-O2S(O)CF3}(olefin)(PPri3)] (olefin = C8H14 or C2H4) with benzene led
to the displacement of the sulfonate ligand and to the formation of the half-sandwich-type complexes [Rh{η6-C6H6)-
(olefin)(PPri3)][CF3SO3] containing a rather labile benzene–rhodium bond. The preparation of the vinylidene
complex trans-[Rh{η1-OS(O)C H Me-p}(᎐C᎐CHPh)(PPri ) ] is also described and the crystal and molecular
᎐ ᎐
6
4
3 2
structures of three compounds have been determined. The four-co-ordinate sulfonato complexes 3–6 are active
catalysts in the C–C coupling reaction of ethene and diphenyldiazomethane. Besides the three isomeric 1:1 adducts
of C2H4 and CPh2, quite unexpectedly also the 2:1 adduct 3,3-diphenylpent-1-ene is formed.
One of the most noteworthy discoveries, which we made in
recent years, was that in the presence of catalytic amounts
of chlororhodium() complexes such as [{RhCl(PPri3)2}2] or
[{RhCl(C2H4)2}2], ethene and diphenyldiazomethane react to
give almost selectively 1,1-diphenylprop-1-ene Ph C᎐CHMe.1
The present paper describes the preparation of mono- and
di-nuclear sulfonatorhodium() complexes, the reactivity of
these species toward H2, CO, C2H4, phenylacetylene and ben-
zene, and the use of the bis(phosphine) complexes [Rh{η2-
O2S(O)R}(PPri3)2] as catalysts for the reaction of ethene and
diphenyldiazomethane. Some preliminary results of these stud-
ies have been communicated.7
᎐
2
This trisubstituted olefin is formally built up by the coupling of
ؒ
ؒ
two carbene fragments CPh2 and CHMe, of which the latter is
ؒ
ؒ
generated from the isomeric ethene. It was previously known
that dinuclear rhodium() compounds such as [Rh2(µ-O2-
CMe)4] and derivatives thereof are active catalysts for the
synthesis of cyclopropanes from olefins and diazoalkanes,2 but
Results and discussion
Preparation of mono- and di-nuclear sulfonate complexes
the formation of Ph C᎐CHMe from Ph CN and C2H4 was
᎐
2
2
2
The most convenient synthetic routes leading to the mono-
nuclear sulfonatorhodium() compounds 3–7 are shown in
Scheme 1. The reactions of the starting materials 1 and 2 with
without precedent. Following our initial studies, we also found
that, if the acetylacetonato complex [Rh(acac)(C2H4)2] was
used instead of [{RhCl(C2H4)2}2] as the catalyst, 1,1-diphenyl-
cyclopropane and not the isomeric 1,1-diphenylprop-1-ene
was formed from ethene and diphenyldiazomethane. In con-
trast, the hexafluoroacetylacetonato derivative [Rh(acac-F6)-
(C2H4)2] behaves similarly to the chloro complex [{RhCl-
(C2H4)2}2] and with C2H4–Ph2CN2 generates catalytically
(although with low turnover numbers) 1,1-diphenylprop-1-
ene.3,4
It was this apparent influence of the anionic ligand of the
rhodium() complexes on both the reactivity and selectivity of
the C–C coupling reaction that prompted us to prepare a series
of compounds of the general composition [Rh{η2-O2S(O)R}-
(PPri3)2]. The main reason why we chose the sulfonate deriv-
Scheme 1 L = PPri3.
sulfonic acids were carried out in diethyl ether at Ϫ78 ЊC
and gave propene and toluene, respectively, as by-products.
Similarly, Stuhl and Muetterties8 prepared the sulfonato-
manganese() derivative [Mn{η2-O2S(O)CF3}(CO)2{P(OPri)3}2]
by protonation of [Mn(η3-C3H5)(CO)2{P(OPri)3}2] with CF3-
SO3H. The rhodium complexes 3–7 are red or violet air-
sensitive solids which have been characterized by elemental
analysis and spectroscopic techniques. While the IR spectra of
Ϫ
atives was that the low nucleophilicity of the RSO3 anions
makes this ligand an excellent leaving group, and we assumed
that this could be an important aspect for the catalytic activity.
Moreover, the sulfonate ligand may adopt either a bridging,
a η1- or a η2-bonding mode upon co-ordination to a metal
centre as was recently reported for carboxylato rhodium()
compounds of a similar type.5,6
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Scheme 2
= C8H14, L = PPri3.
Fig. 1 An ORTEP plot of complex 4.
of 10 and 11. It reacted with 2 equivalents of MeSO3H or p-
MeC6H4SO3HؒH2O in CH2Cl2 to afford the µ-sulfonato deriva-
tives almost quantitatively. Compound 9 was prepared by reac-
tion of 8 with an excess of NaOH in a two-phase system of
C6H6–water following the procedure described by Alper and co-
workers12 for the synthesis of [{Rh(PPh3)2(µ-OH)}2]. Along
a similar route, the related triisopropylphosphine complex
[{Rh(PPri3)2(µ-OH)}2] was prepared in our laboratory and
characterized by crystal structure analysis.13 The µ-sulfonato
compounds 10–12 are yellow or orange-yellow, only moderately
air-sensitive solids which are soluble in CH2Cl2, thf or ether and
in the case of 12 even in saturated hydrocarbons. The reactions
of 11 and 12 with triisopropylphosphine in ether at Ϫ78 ЊC
proceed rather quickly and afford 4 and 5 in 75–90% yield.
Table 1 Selected bond lengths (Å) and angles (Њ) for complex 4
Rh–O(1)
Rh–O(2)
Rh–P(1)
Rh–P(2)
2.217(2)
2.227(2)
2.206(1)
2.218(1)
S–O(1)
S–O(2)
S–O(3)
S–C(19)
1.476(2)
1.475(2)
1.429(2)
1.761(3)
P(1)–Rh–P(2)
P(1)–Rh–O(1)
P(1)–Rh–O(2)
P(2)–Rh–O(1)
P(2)–Rh–O(2)
O(1)–Rh–O(2)
Rh–O(1)–S
106.31(3)
93.85(6)
157.86(6)
159.79(6)
95.70(6)
64.21(7)
94.8(1)
Rh–O(2)–S
94.5(1)
106.3(1)
114.8(1)
114.4(2)
107.7(1)
105.9(1)
107.2(2)
O(1)–S–O(2)
O(1)–S–O(3)
O(2)–S–O(3)
O(1)–S–C(19)
O(2)–S–C(19)
O(3)–S–C(19)
Addition reactions of ç2-sulfonato and ì-sulfonato rhodium(I)
complexes
the related carboxylato compounds [Rh(η2-O2CR)(PPri3)2]
clearly support the chelate structure,5,6 the IR data of 3–7 are
less informative and do not distinguish between a η1- and η2-
bonding mode of the sulfonato unit.9 As far as compounds 3–6
are concerned, the cis disposition of the two phosphine ligands
is indicated by the appearance of one signal for the CH3 pro-
The chelate complexes 3–7 are quite labile and react smoothly
at room temperature with H2 as well as with CO and C2H4.
On treatment with hydrogen, the dihydridorhodium()
compounds 13–17 (Scheme 3) are obtained as white, nearly
1
tons of the isopropyl groups in the H NMR spectrum which
due to P–H and H–H coupling is split into a doublet of doub-
lets in the case of 3, 5 and 6. For 7, which contains a chiral
substituent at the sulfur atom, two doublets of doublets are
observed. The 31P NMR spectra of 3–7 display one doublet, the
Rh–P coupling of which (210–220 Hz) is also consistent with a
cis disposition of the PPri3 ligands.5,10
To confirm the structural proposal for the complexes 3–7, a
single-crystal X-ray diffraction study of 4 was carried out. The
ORTEP11 plot (Fig. 1) reveals that the ligand sphere around the
metal centre is distorted square planar with the two phosphorus
and the two oxygen atoms O(1) and O(2) lying exactly in the
same plane as rhodium. The symmetrical arrangement of the
ligands is illustrated by almost identical Rh–P and Rh–O dis-
tances (see Table 1), the latter [Rh–O(1) and Rh–O(2)] being
about 0.05 Å longer than in the analogous acetato compound
[Rh(η2-O2CMe)(PPri3)2]. However, the bite angle O–Rh–O in 4
[64.21(7)Њ] and in [Rh(η2-O2CMe)(PPri3)2] [60.2(1)Њ] is quite
similar which could be due to the steric requirements of the
bulky phosphine groups. The angle O(1)–S–O(2) [106.3(1)Њ] is
only slightly smaller than would be anticipated for an ideal
tetrahedral geometry.
Scheme 3 L = PPri3.
An alternative synthetic pathway to compounds 4 and 5 is
outlined in Scheme 2. Treatment of the well known cyclooctene
complex 8 with 2 equivalents of RSO3Ag (R = p-Tol or CF3) in
CH2Cl2 or CH2Cl2–Et2O led to a displacement of the bridging
chlorides by p-toluene- or trifluoromethane-sulfonates and
gave compounds 11 and 12 as yellow solids in excellent yield.
Instead of 8, the corresponding dimeric µ-hydroxo complex
9 could also be used as starting material for the preparation
air-stable solids in excellent yield. The hydrido complexes are
soluble in most organic solvents and can be stored under H2 at
Ϫ78 ЊC for weeks. In vacuo they slowly lose hydrogen and
regenerate the starting materials 3–7. The 31P NMR spectra
of 13–17 display at room temperature only one resonance
(doublet in 31P-{1H} and doublet of triplets in off-resonance)
with a 103Rh–31P coupling which is typical for trans disposed
1
triisopropylphosphine ligands.14 In the H NMR spectra there
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J. Chem. Soc., Dalton Trans., 1998, 3549–3558

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is also only one set of signals at δ Ϫ25.3 to Ϫ25.8 for the
hydride ligands. Since for a rigid six-co-ordinate structure as
shown in Scheme 3 two stereoisomers should exist, we assume
that at 25 ЊC these isomers rapidly interconvert. If the 31P NMR
spectra are measured in CD2Cl2 at Ϫ90 ЊC or in [2H8]toluene at
Ϫ80 ЊC, a slight broadening of the single resonance is observed
indicating that even under these conditions the interconversion
of the two isomers is very fast on the NMR timescale. The same
seems to be true in the case of the four-co-ordinate complex
7 for which the NMR data equally suggest an effective C2
symmetry. It should be mentioned that compound 4 catalyses
the hydrogenation of phenylactylene to styrene and we assume
that the dihydrido derivative 14 is involved in this process.15
Like 13–17, the carbonyl complexes 18–21 are formed almost
quantitatively by passing a slow stream of CO through a
solution of 3–6 in hexane at room temperature. As far as the
properties of 18–21 are concerned, a special feature is that while
18 and 19 are soluble in benzene or ether, the related species
20 and 21 are not. Conductivity measurements in nitromethane
indicate that in this solvent the neutral compounds 20 and 21
are in equilibrium with the ionic species 20a and 21a (see
Scheme 3). This can be understood by the general behaviour
unstable under nitrogen and even under ethene. In contrast, the
mass spectrum of 27 revealed that this compound (obtained
from 12) is a dimer and not a monomer in the solid state.
Treatment of 26 and 27 with triisopropylphosphine led both to
bridge cleavage and partial displacement of ethene to give the
complexes 23 and 24 almost quantitatively.
The dinuclear triflato derivative 12 reacts with triisopropyl-
stibine in pentane even at Ϫ40 ЊC yielding a labile species that
presumably contains both SbPri3 and cyclooctene as ligands.17
Treatment of this intermediate with ethene affords compound
28 which was isolated as an analytically pure solid in 86%
yield. The same product is also obtained from 27 and an equi-
molar amount of SbPri3. We would like to point out that,
recently, we described the synthesis of the corresponding
chlorobis(stibine) complex trans-[RhCl(C2H4)(SbPri3)2] which is
an excellent starting material for the preparation of a whole
series of carbene rhodium() derivatives.18,19
The mixed cyclooctene–triisopropylphosphine rhodium()
complex 29 containing a chelating triflate ligand is accessible
from compound 12 and 2 equivalents of PPri3 (Scheme 5).
Ϫ
Ϫ
of CF3SO3 and FSO3 as good leaving groups. Owing to
these results we assume that the NMR data measured for the
carbonyl derivatives of the trifluoromethanesulfonato and the
fluorosulfato rhodium complexes in nitromethane correspond
to 20a and 21a and not to 20 and 21, respectively.
Treatment of complexes 3–6 with C2H4 led to the formation
of 22–25 the structure of which is probably quite similar to that
of the carbonyl compounds 18–21 (see Scheme 4). Since the
Scheme 5 L = PPri3.
If this reaction is monitored at room temperature a change
from orange to violet-brown initially occurs which is smoothly
reversed after ca. 2 h. The 31P NMR measurements revealed
that in the first stage of the process the bis(phosphine)
complex 5 is formed which in the presence of unchanged
starting material 12 (and cyclooctene) affords the mixed olefin–
phosphine derivative 29. The same product is obtained from
12 and 5 in the molar ratio of 1:2 in pentane. Treatment of
29 with C2H4 led to the formation of the ethene–phosphine
complex 30 which was isolated in ca. 70% yield as an analytic-
ally pure yellow solid. The 1H NMR spectrum of 30 in CD2Cl2
at room temperature displays a broad singlet at δ 2.75 for the
C2H4 protons indicating that under these conditions rotation of
the olefinic ligand around the Rh–C2H4 bond is only slightly
hindered. In the 13C NMR spectrum of 30 the resonance for
the C2H4 carbon atoms appears at δ 43.7 as a doublet with a
103Rh–13C coupling constant of 15.3 Hz.
Scheme 4 L = PPri3.
ethene complexes in analogy to the dihydrido derivatives are
also unstable in vacuo, undergoing loss of C2H4, the NMR
spectra of 22–25 were recorded in C6D6 which was saturated
with ethene. The mass spectrum of 23 confirmed that the
compound is monomeric in the solid state.
The ethene complexes 23 and 24 are not only formed from
4 and 5 but also from the sulfonato-bridged compounds 11
and 12 as starting materials. In the initial step the cyclooctene
ligands of 11 and 12 are displaced by ethene to afford the
corresponding dinuclear intermediates 26 and 27 both of
which were isolated as yellow solids in excellent yield. While
compound 26 is stable (and thus could be characterized by
elemental analysis), the triflato derivative 27 is rather labile and
decomposes rapidly in solution. We note that Aresta et al.16
reported the preparation of monomeric [Rh(O3SCF3)(C2H4)2]
from [{RhCl(C2H4)2}2] and CF3SO3Ag which was found to be
The molecular structure of compound 29 was determined by
X-ray crystallography. There are two independent molecules A
and B in the unit cell, of which A is shown in Fig. 2. As the
ORTEP plot reveals, the configuration around rhodium is
slightly distorted square planar and therefore to some extent
analogous to that of the tosylate complex 4. However, the bond
angle between phosphorus, rhodium and the centre of the C᎐C
᎐
double bond for 29 (molecule A) is 97.15Њ (94.59Њ for B) and
thus somewhat smaller than the bond angle P(1)–Rh–P(2) in
compound 4. The atoms S, O(1), O(2), Rh, P and the centre of
the C᎐C bond lie almost in the same plane, the dihedral angle
᎐
between the planes [O(1), S, O(2)] and [O(1), Rh, O(2)] for
molecule A being 11.1(1)Њ and for molecule B 10.7(1)Њ. The
corresponding dihedral angles between [O(1), Rh, O(2)] and (P,
J. Chem. Soc., Dalton Trans., 1998, 3549–3558
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Rh, centre of C᎐C) are 7.9(1)Њ for A and 8.0(1)Њ for B, respect-
which could be due to the cationic nature and the closed-shell
electron configuration of the half-sandwich-type molecule. The
᎐
ively. While the Rh–O bond lengths in 4 are nearly identical,
those in 29 are not (see Table 2); due to the different ligands
(C8H14 and PPri3) in trans position they differ by ca. 0.13 Å. In
contrast, the distances Rh–P(1) and Rh–P(2) in 4 and Rh–P in
29 are almost the same.
angle between P, Rh and the centre of the C᎐C bond in 31 is
᎐
92.69Њ for molecule A and 93.27Њ for molecule B, respectively.
The distances between rhodium and the carbon atoms of the
benzene ligand lie between 2.313(3) and 2.361(4) Å for A and
between 2.296(4) and 2.365(4) Å for B, and this range is typical
also for other arenerhodium() compounds.20
The reactivity of complex 4 as a representative of four-
co-ordinate bis(triisopropylphosphine)rhodium() sulfonato
compounds toward a terminal alkyne such as phenylacetylene
is illustrated in Scheme 6. In toluene solution at room tem-
Dissolving either compound 29 or 30 in benzene leads to
the displacement of the triflate ligand and to the formation
of the cationic half-sandwich-type complexes 31 and 32 in
virtually quantitative yield. Both 31 and 32 are yellow, only
moderately air-sensitive solids which have been characterized
by elemental analysis, IR, NMR and (in the case of 31) FAB
mass spectroscopy. In solution in the absence of benzene they
are quite labile and regenerate the starting materials 29 and 30,
respectively. Despite this lability, a crystal structure analysis
of 31 could be carried out, and the result of this study is sum-
marized in Fig. 3 and Table 3. Similar to compound 29, there
are two independent molecules A and B in the unit cell which
differ in the conformation of the cyclooctene ligand. The bond
length Rh–P as well as the distances Rh–C(30) and Rh–C(31)
are somewhat longer than in the square-planar complex 29
Scheme 6 L = PPri3.
᎐
perature a smooth reaction between 4 and PhC᎐CH takes place
᎐
which gives the vinylidene complex 33 as a violet crystalline
solid in 91% isolated yield. The most typical spectroscopic
Fig. 2 An ORTEP plot of complex 29.
Fig. 3 An ORTEP plot of the cation of complex 31.
Table 2 Selected bond lengths (Å) and angles (Њ) for complex 29 (there are two independent molecules A and B in the unit cell)
A
B
A
B
Rh–P
2.192(1)
2.219(3)
2.351(2)
2.091(4)
2.074(4)
2.194(1)
2.205(3)
2.339(2)
2.091(4)
2.073(4)
C(20)–C(21)
S–O(1)
S–O(2)
S–O(3)
S–C(1)
1.413(5)
1.477(3)
1.458(3)
1.422(3)
1.820(5)
1.404(5)
1.471(3)
1.456(3)
1.424(3)
1.820(4)
Rh–O(1)
Rh–O(2)
Rh–C(20)
Rh–C(21)
P–Rh–O(1)
P–Rh–O(2)
P–Rh–C(20)
P–Rh–C(21)
Rh–O(1)–S
Rh–O(2)–S
98.41(7)
160.55(7)
94.9(1)
96.9(1)
95.8(1)
97.64(7)
160.16(7)
95.3(1)
96.3(1)
96.2(1)
O(1)–Rh–O(2)
O(1)–S–O(2)
O(1)–S–O(3)
O(2)–S–O(3)
O(1)–S–C(1)
O(2)–S–C(1)
63.02(9)
109.1(2)
116.5(2)
117.3(2)
104.0(2)
103.6(2)
63.00(9)
108.6(2)
116.5(2)
117.6(2)
103.9(2)
103.9(2)
90.9(1)
91.1(1)
Table 3 Selected bond lengths (Å) and angles (Њ) for cationic complex 31 (there are two independent molecules A and B in the unit cell)
A
B
A
B
Rh–P
2.294(1)
2.141(3)
2.138(3)
2.330(3)
2.313(3)
2.290(1)
2.141(3)
2.143(3)
2.332(4)
2.346(4)
Rh–C(52)
Rh–C(53)
Rh–C(54)
Rh–C(55)
C(30)–C(31)
2.338(4)
2.361(4)
2.320(3)
2.328(3)
1.403(4)
2.324(3)
2.365(4)
2.362(4)
2.296(4)
1.396(5)
Rh–C(30)
Rh–C(31)
Rh–C(50)
Rh–C(51)
P–Rh–C(30)
P–Rh–C(31)
Rh–C(30)–C(31)
94.43(9)
90.43(8)
70.7(2)
93.92(9)
91.35(9)
71.0(2)
Rh–C(31)–C(30)
C(30)–C(31)–C(32)
C(31)–C(30)–C(37)
71.0(2)
122.8(3)
123.0(3)
70.9(2)
124.8(3)
122.6(3)
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J. Chem. Soc., Dalton Trans., 1998, 3549–3558

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Table 4 Catalytic cycles and composition of the mixture of products
obtained from ethene and diphenyldiazomethane in methylcyclohexane
according to Scheme 7
the metal centre) is an intramolecular C–H activation to give
a RhH(CH᎐CH ) intermediate which could then react with a
᎐
2
second molecule of C2H4 to afford a Rh(C H )(CH᎐CH )
᎐
2
5
2
species. However, the reason why we consider this mechanistic
route as less likely is that we failed to observe the generation
of a hydrido(vinyl)rhodium() compound on photolysis of
24 or 25, respectively.
Product (%)
[Rh]-cat
Cyclesa
Ia
Ib
Ic
Id
With regard to the conversion of two ethene molecules into
two σ-bonded ligands in the co-ordination sphere of a d8 metal
centre it should be pointed out that Carmona and co-workers22
recently showed that the iridium complex [IrTp*(C2H4)2]
[Tp* = tris(3,5-dimethylpyrazol-1-yl)hydroborate] rearranges
3
24
11
47
37
2
2
7
5
86
87
37
29
4
2
1
0
8
9
55
66
4
5b
6b
a Cycle = mmol product/mmol catalyst. b In toluene.
thermally or photochemically to the isomer [IrTp*(H)(CH᎐
᎐
CH2)(C2H4)]. On treatment with acetonitrile this compound
features of 33 are the doublet of triplets at δ 1.51 for the
1
yields the ethyl–vinyl derivative [IrTp*(CH᎐CH )(C H )-
᎐
2
2
5
᎐CHPh proton in the H NMR and the low-field resonance
᎐
(NCMe)], which in the presence of catalytic amounts of water
undergoes an intramolecular coupling of the vinyl and
acetonitrile ligands to afford a five-membered iridapyrrole
ring.23 With [RhTp*(C2H4)2] as the starting material a related
(also a doublet of triplets) at δ 301.1 for the α-carbon atom
of the vinylidene unit in the 13C NMR spectrum. These data are
in good agreement with those of the corresponding chloro
and acetato derivatives trans-[RhX(᎐C᎐CHPh)(PPri ) ] (X = Cl
᎐ ᎐
3
2
conversion into [RhTp*(CH᎐CH )(C H )(L)] (L = NCMe or
᎐
2
2
5
or MeCO2) which have recently been prepared in our
py) takes place.24
laboratory.5,14
In order to find out whether olefins other than ethene would
also react with diphenyldiazomethane by C–C coupling, the
Catalytic studies
reaction of Ph CN with methyl acrylate and CH ᎐CHCH -
᎐
2
2
2
2
In the same way as the dimeric chloro derivative [{RhCl-
(PPri3)2}2], the new monomeric sulfonatorhodium() complexes
3–6 are also active catalysts in the C–C coupling reaction of
ethene and diphenyldiazomethane. The most noteworthy
feature is that the selectivity depends significantly on the
substituent R of the sulfonate ligand. While in the reaction with
either 3 or 4 as catalyst 1,1-diphenylprop-1-ene Ib (Scheme 7)
CO2Me in the presence of the triflato complex 5 as the catalyst
was also investigated. As is shown in Scheme 8, only cyclo-
Scheme 8
propanation occurs and the corresponding esters IIa and IIb
are formed. Whereas for IIa the number of cycles is 55, the yield
of IIb is rather low and could not be increased by using an
excess of the diazoalkane.
Scheme 7
Current work in our laboratory is aimed at the further
exploration of the use of the sulfonatorhodium() as well as the
related carboxylatorhodium() complexes in other types of C–C
coupling reactions among which the cyclooligomerization of
butadiene is of particular interest.7
is the major product, in the presence of 5 and 6 3,3-diphenyl-
pent-1-ene Id is the dominating species (see Table 4). This 2:1
adduct of C2H4 and Ph2CN2 is formed in only minor quantities
if 3, 4 or the chlororhodium() dimer [{RhCl(PPri3)2}2] is
used as catalyst. In all C–C coupling reactions of ethene
and diphenyldiazomethane, which are catalysed by bis(triiso-
propylphosphine)rhodium() compounds of the general type
[{RhX(PPri3)2}n] (n = 1 or 2), only trace amounts of 3,3-
diphenylprop-1-ene Ic (which is generated selectively in the
Experimental
All reactions were carried out under an atmosphere of argon
by Schlenk-tube techniques. Solvents were dried by the usual
procedures and distilled under argon prior to use. The starting
materials 1, 25 and 825 were prepared by published methods.
The NMR spectra were recorded on Bruker AC 200 and AMX
400 instruments and the IR spectra on a Perkin-Elmer 1420
spectrometer. Abbreviations used: s, singlet; d, doublet; t,
triplet; q, quartet; m, multiplet; vt, virtual triplet; N =
3J(PH) ϩ 5J(PH) or 1J(PC) ϩ 3J(PC), respectively. Conduc-
tivity data (Λ) in nitromethane.
stoichiometric reaction of trans-[{RhCl(᎐CPh )(SbPri ) } ] with
᎐
2
3 2 2
ethene)19 are obtained.
The mechanism for the formation of compound Id is not
clear as yet. We assume that in analogy to the reaction of ethene
and diphenyldiazomethane with [{RhCl(PPri3)2}2] as catalyst,1
in the initial stage of the catalytic process both C2H4 and CPh2
are co-ordinated to rhodium, and that subsequently a rhoda-
cyclobutane is formed. The next step could be either an inser-
tion of ethene into one of the Rh–C bonds of the metalla-
cyclobutane to give a six-membered RhC5 cycle or a β-H shift
to generate a RhH(CH2CHCPh2) intermediate. Addition of
C2H4 to this intermediate followed by the insertion of the olefin
into the Rh–H bond could afford a Rh(C2H5)(CH2CHCPh2)
species which by metal-mediated C–C coupling yields Id. If
the catalytic cycle involves the above mentioned RhC5 ring
Preparations
[Rh{ç2-O2S(O)Me}(PPri3)2] 3. (a) A solution of compound 1
(0.219 g, 0.47 mmol) in ether (15 cm3) was treated dropwise with
MeSO3H (0.031 cm3, 0.48 mmol) at Ϫ78 ЊC. After the addition
a white suspension was formed which was warmed to room
temperature to give an orange-red solution. The solution was
stirred for 1 h, the solvent removed in vacuo and the residue
extracted twice with pentane (40 cm3). The combined extracts
were brought to dryness in vacuo, the remaining red solid was
washed with small portions of pentane (Ϫ20 ЊC) and dried:
yield 0.153 g (63%).
system, then upon a β-H shift a RhH(CH CH CPh CH᎐CH )
᎐
2
2
2
2
intermediate could be formed which by reductive elimination
generates Id. Precedence for the postulated insertion of ethene
into the metal–carbon bond of a metallacyclobutane can be
found in the work of Binger and Schuchardt,21 who argue that
the palladium(0)-catalysed cycloaddition of methylenecyclo-
propane and olefins presumably proceeds through a PdC5
intermediate. We cannot rule out that one of the initial steps in
the formation of Id (following the co-ordination of ethene to
(b) A solution of compound 2 (0.241 g, 0.47 mmol) in ether
(15 cm3) was treated dropwise with MeSO3H (0.031 cm3, 0.48
mmol) at Ϫ78 ЊC. A red solution formed which was warmed to
J. Chem. Soc., Dalton Trans., 1998, 3549–3558
3553

View Article Online
room temperature. After it was stirred for 30 min, the solvent
was removed in vacuo and the residue washed twice with small
portions of pentane (Ϫ20 ЊC) to give a red solid: yield 0.130 g
(54%); mp 110 ЊC (decomp.) (Found: C, 43.71; H, 8.94; S, 5.88.
C19H45O3P2RhS requires C, 44.02; H, 8.75; S, 6.18%). IR (KBr):
ν(O3S) 1201, 1190 and 1049 cmϪ1. NMR (C6D6): δH (200 MHz)
2.68 (3 H, s, SCH3), 1.80 (6 H, m, CHCH3) and 1.23 [36 H,
dd, J(PH) 13.0, J(HH) 7.1 Hz, CHCH3]; δC (50.3 MHz) 40.0
(s, SCH3), 25.5 (vt, N 21.3 Hz, CHCH3) and 20.3 (s, CHCH3);
δP (81.0 MHz) 70.2 [d, J(RhP) 212.2 Hz].
materials. Red solid: yield 0.134 g (82%); mp 45 ЊC (decomp.)
(Found: C, 51.12; H, 8.67; S, 4.64. C28H57O4P2RhS requires C,
51.37; H, 8.78; S, 4.90%). NMR (C6D6): δH (400 MHz) 4.14,
3.18 [2 H, both d, J(HH) 15.1, CH2SO3], 2.10–1.45 (7 H, br m,
7 H of C10H15), 1.85 (6 H, m, CHCH3), 1.28 [18 H, dd, J(PH)
12.8, J(HH) 5.6, CHCH3], 1.27 [18 H, dd, J(PH) 12.8, J(HH)
5.5 Hz, CHCH3], 1.15, 0.59 (6 H, both s, CH3 of C10H15);
δP (162.0 MHz) 69.8 [d, J(RhP) 213.0 Hz].
[{Rh(C8H14)2}2(ì-OH)2] 9. A two phase system of complex
8 (0.315 g, 0.44 mmol) in C6H6 (15 cm3), NaOH (0.12 g,
3.0 mmol) and [PhCH2NEt3]Cl (0.050 g) in water (10 cm3)
was stirred at room temperature for 4 h. The C6H6 layer
was decanted and the aqueous phase extracted with 10 cm3 of
C6H6. The combined benzene fractions were dried over Na2SO4
and then filtered. From the filtrate the solvent was removed in
vacuo to give a yellow solid. The solid was washed three times
with 5 cm3 portions of pentane and dried in vacuo. Pale yellow
solid: yield 0.265 g (89%); mp 70 ЊC (decomp.) (Found: C,
56.66; H, 8.29. C32H58O2Rh2 requires C, 56.47; H, 8.58%). IR
(KBr): ν(OH) 3676 cmϪ1. NMR (C6D6): δH (200 MHz) 2.44
[Rh{ç2-O2S(O)C6H4Me-p}(PPri3)2] 4. A solution of com-
pound 1 (0.116 g, 0.25 mmol) in toluene (2 cm3) was treated
with p-MeC6H4SO3H (0.048 g, 0.25 mmol) and stirred for 1 h
at room temperature. A change from yellow to red occurred.
The solvent was removed in vacuo, the residue extracted with
acetone (20 cm3) and the extract concentrated to ca. 2 cm3 in
vacuo. Red crystals precipitated which were filtered off, washed
twice with small portions of acetone (0 ЊC) and dried: yield
0.131 g (88%); mp 80 ЊC (decomp.) (Found: C, 50.62; H, 8.63.
C25H49O3P2RhS requires C, 50.50; H, 8.31%). NMR (C6D6):
δH (200 MHz) 8.34, 6.86 (4 H, both m, C6H4), 1.90 (3 H, s,
C6H4CH3), 1.83 (6 H, m, CHCH3) and 1.24 (36 H, m, CHCH3);
δC (50.3 MHz) 141.3 [d, J(RhC) 15.8 Hz, ipso-C of C6H4],
129.5, 129.0, 127.2 (all s, C6H4), 25.7 (vt, N 21.0 Hz, CHCH3),
21.1 (s, C6H4CH3) and 20.4 (s, CHCH3); δP (81.0 MHz) 70.3
[d, J(RhP) 212.5 Hz].
(8 H, m, ᎐CH of C H ), 2.48–1.13 (48 H, br m, CH of C H )
᎐
8
14
2
8
14
and Ϫ1.23 (2 H, br s, OH); δC 72.49 (br m, ᎐CH of C H ),
᎐
8
14
30.24, 28.64, 28.59 (all s, CH2 of C8H14).
[{Rh(C8H14)2}2{ì-O2S(O)Me}2] 10. A solution of complex 9
(0.455 g, 0.67 mmol) in CH2Cl2 (30 cm3) was treated at room
temperature with MeSO3H (0.087 cm3, 1.34 mmol). The
mixture was stirred for 2 h and then the solvent was removed
in vacuo. The resulting yellow solid was washed three times
with 5 cm3 portions of Et2O and dried: yield 0.416 g (74%);
mp 124 ЊC (decomp.) (Found: C, 48.49; H, 7.27; S, 7.87.
C34H62O6Rh2S2 requires C, 48.80; H, 7.47; S, 7.66%). IR (KBr):
Alternatively, compound 4 was prepared on treatment of a
solution of 11 (0.040 g, 0.04 mmol) in ether (4 cm3) with PPri3
(0.031 cm3, 0.16 mmol) at Ϫ78 ЊC. After the solution was stirred
for 5 min the solvent was removed in vacuo. The oily residue was
dissolved in pentane (1.5 cm3) and the solution stored for 12 h
at Ϫ78 ЊC to give a red solid: yield 0.066 g (72%).
ν(O3S) 1276, 1207, 1070 and 1012, ν(CF3) 1260 and 1170 cmϪ1
NMR (C6D6): δH (200 MHz) 2.47 (6 H, s, CH3), 2.14 (16 H, m,
᎐CH and CH of C H ), 1.78, 1.52, 1.38 (40 H, all br m, CH
.
[Rh{ç2-O2S(O)CF3}(PPri3)2] 5. This compound was prepared
as described for 3, using either 1 (0.088 g, 0.19 mmol) and
CF3SO3H (0.017 cm3, 0.19 mmol) or 2 (0.160 g, 0.31 mmol) and
CF3SO3H (0.028 cm3, 0.32 mmol) as starting materials. Violet
solid: yield 0.102 g (95%) from 1 and 0.103 g (58%) from 2;
mp 80 ЊC (decomp.) (Found: C, 39.60; H, 7.48; S, 5.36.
C19H42F3O3P2RhS requires C, 39.87; H, 7.40; S, 5.60%). MS
(70 eV): m/z 573 (Mϩ). IR (KBr): ν(O3S) 1263 and 1030, ν(CF3)
1253 and 1161 cmϪ1. NMR (C6D6): δH (200 MHz) 1.70 (6 H, m,
CHCH3) and 1.13 [36 H, dd, J(PH) 13.5, J(HH) 7.3 Hz,
CHCH3]; δC (50.3 MHz) 121.4 [q, J(FC) 316.9 Hz, CF3], 25.7
(vt, N 23.1 Hz, CHCH3) and 20.0 (s, CHCH3); δF (188.2 MHz)
Ϫ77.1 (s); δP (81.0 MHz) 69.9 [d, J(RhP) 219.5 Hz].
Alternatively, compound 5 was prepared on treatment of a
solution of 12 (0.038 g, 0.04 mmol) in ether (4 cm3) with PPri3
(0.031 cm3, 0.16 mmol) at Ϫ78 ЊC. After the solution was stirred
for 5 min the solvent was removed in vacuo, the violet residue
washed twice with 2 cm3 portions of pentane (Ϫ40 ЊC) and
dried: yield 0.041 g (89%).
᎐
2
8
14
2
of C8H14); δC (50.3 MHz) 73.6 [d, J(RhC) 15.7 Hz, ᎐CH of
᎐
C8H14], 39.4 (s, CH3), 29.7, 28.2, 26.6 (all s, CH2 of C8H14).
[{Rh(C8H14)2}2{ì-O2S(O)C6H4Me-p}2] 11. A suspension of
compound 8 (0.520 g, 0.72 mmol) and p-MeC6H4SO3Ag
(0.420 g, 1.45 mmol) in CH2Cl2 (35 cm3) was stirred for 2 d at
room temperature. A white solid precipitated and a change of
the solution from orange-red to orange-yellow occurred. The
solvent was removed in vacuo, the residue extracted with ether
(40 cm3) and the extract brought to dryness in vacuo. A yellow
solid was isolated which was repeatedly washed with 5 cm3
portions of pentane and dried: yield 0.570 g (80%); mp 168 ЊC
(decomp.) (Found: C, 55.81; H, 6.95; Rh, 20.62; S, 6.54.
C46H70O6Rh2S2 requires C, 55.87; H, 7.13; Rh, 20.81; S, 6.48%).
IR (CH2Cl2): ν(O3S) 1190, 1115, 1068 and 1022 cmϪ1. NMR
(CDCl3): δH (200 MHz) 8.03 (4 H, m, ortho-H of SC6H4), 7.27
(4 H, m, meta-H of SC H ), 2.56 (8 H, m, ᎐CH of C H ), 2.39
᎐
6
4
8
14
(6 H, s, C6H4CH3), 2.32–1.17 (48 H, br m, CH2 of C8H14);
δC (50.3 MHz) 142.6 (s, ipso-C of SC6H4), 137.4, 129.1, 126.4
[Rh{ç2-O2S(O)F}(PPri3)2] 6. This compound was prepared as
described for 3, using either 1 (0.154 g, 0.33 mmol) and FSO3H
(0.019 cm3, 0.33 mmol) or 2 (0.251 g, 0.49 mmol) and FSO3H
(0.028 cm3, 0.49 mmol) as starting materials. Violet solid: yield
0.152 g (88%) from 1 and 0.256 g (81%) from 2; mp 64 ЊC
(decomp.) (Found: C, 41.02; H, 8.02; S, 6.62. C18H42FO3P2RhS
requires C, 41.38; H, 8.10; S, 6.14%). MS (70 eV): m/z 522 (Mϩ).
IR (KBr): ν(O3S) 1312, 1240 and 1062, ν(SF) 775 cmϪ1. NMR
(C6D6): δH (200 MHz) 1.69 (6 H, m, CHCH3) and 1.14 [36 H,
dd, J(PH) 13.4, J(HH) 7.2 Hz, CHCH3]; δC (50.3 MHz) 25.8
(vt, N 22.2 Hz, CHCH3) and 20.1 (s, CHCH3); δF (188.2 MHz)
40.7 (s); δP (81.0 MHz) 70.5 [d, J(RhP) 220.1 Hz].
(all s, C H ), 73.9 [d, J(RhC) 15.7 Hz, ᎐CH of C H ], 29.2,
᎐
6
4
8
14
28.0, 26.1 (all s, CH2 of C8H14) and 21.4 (s, C6H4CH3).
Alternatively, compound 11 was prepared on treatment of
a solution of 9 (0.352 g, 0.519 mmol) in CH2Cl2 (30 cm3) with
p-MeC6H4SO3HؒH2O (0.247 g, 1.30 mmol). The mixture was
stirred for 4 h at room temperature, the solvent removed in
vacuo and the residue extracted twice with 15 cm3 portions of
C6H6. The benzene layers were dried over Na2SO4 and filtered.
Removal of the solvent in vacuo afforded a yellow solid which
was washed three times with 5 cm3 portions of ether and dried:
yield 0.375 g (72%).
[Rh{ç2-O2S(O)C10H15O}(PPri3)2] 7. This compound was
prepared as described for 4, using 1 (0.116 g, 0.25 mmol) and
(1S)-camphor-10-sulfonic acid (0.058 g, 0.25 mmol) as starting
[{Rh(C8H14)2}2{ì-O2S(O)CF3}2] 12. A solution of compound
8 (0.340 g, 0.47 mmol) in CH2Cl2–ether (2:1, 25 cm3) was
treated with a solution of CF3SO3Ag (0.234 g, 0.91 mmol) in
3554
J. Chem. Soc., Dalton Trans., 1998, 3549–3558

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ether (15 cm3) and stirred for 2 h at room temperature. A white
solid precipitated and a gradual change of the solution from
orange-yellow to yellow occurred. The solvent was removed in
vacuo and the residue extracted with hexane (40 cm3). The
extract was slowly concentrated in vacuo until an orange-yellow
solid began to precipitate. The solution was then stored for 24 h
at Ϫ78 ЊC, the precipitate separated from the mother-liquor,
washed twice with 3 cm3 portions of pentane (Ϫ40 ЊC) and
dried: yield 0.318 g (71%); mp 73 ЊC (decomp.) (Found: C,
42.86; H, 5.95; S, 6.64. C34H56F6O6Rh2S2 requires C, 43.22; H,
5.97; S, 6.79%). IR (CH2Cl2): ν(CF) 1245, ν(O3S) 1195, 1135,
C18H44FO3P2RhS requires C, 41.22; H, 8.46; S, 6.11%). IR
(KBr): ν(RhH) 2180 and 2158, ν(O3S) 1285, 1252 and 1078,
ν(SF) 740 cmϪ1. NMR (C6D6): δH (200 MHz) 2.07 (6 H, m,
CHCH3), 1.10 [36 H, dvt, N 13.7, J(HH) 6.7, CHCH3]
and Ϫ25.60 [2 H, dt, J(RhH) 33.0, J(PH) 14.8 Hz, RhH];
δC (50.3 MHz) 25.2 (vt, N 22.1 Hz, CHCH3) and 20.2 (s,
CHCH3); δF (188.2 MHz) 41.6 (s, SF); δP (81.0 MHz) 60.6 [d,
dt in off-resonance, J(RhP) 114.5 Hz].
[RhH2{ç2-O2S(O)C10H15O}(PPri3)2] 17. This compound was
prepared as described for 13, using 7 (0.059 g, 0.09 mmol) in
CH2Cl2 (5 cm3) as starting material. White solid: yield 0.054 g
(92%); mp 42 ЊC (decomp.) (Found: C, 50.70; H, 9.05; S, 4.47.
C28H59O3P2RhS requires C, 51.21; H, 9.06; S, 4.88%). IR (KBr):
ν(RhH) 2120 cmϪ1. NMR (C6D6): δH (200 MHz) 3.86, 3.04 [2 H,
both d, J(HH) 16.0 Hz, CH2SO3], 2.32 (6 H, m, CHCH3), 2.07–
1.40 (7 H, m, 7 H of C10H15), 1.25 [36 H, dvt, N 13.1, J(HH) 5.8,
CHCH3], 1.21, 0.57 (6 H, both s, CH3 of C10H15) and Ϫ25.31
[2 H, dt, J(RhH) 30.5, J(PH) 14.4 Hz, RhH]; δP (81.0 MHz)
61.4 [d, dt in off-resonance, J(RhP) 114.8 Hz].
1
1045 and 1005 cmϪ1. NMR (CDCl3 for H and 13C): δH (200
MHz) 2.63 (8 H, m, ᎐CH of C H ), 2.24–1.32 (48 H, br m, CH
᎐
8
14
2
of C8H14); δC (50.3 MHz) 119.3 [q, J(FC) 318.8 Hz, CF3], 74.1
[d, J(RhC) 15.7 Hz, ᎐CH of C H ], 29.1, 27.4, 26.1 (all s, CH
᎐
8
14
2
of C8H14); δF (188.3 MHz, CD2Cl2) Ϫ77.1 (s).
[RhH2{ç2-O2S(O)Me}(PPri3)2] 13. A slow stream of hydro-
gen was passed for ca. 5 s through a solution of complex 3
(0.064 g, 0.12 mmol) in ether (8 cm3). A rapid change from red
to almost white occurred. After the solution was stirred for
15 min at room temperature the solvent was removed in vacuo.
The remaining white solid was washed with small quantities of
pentane (Ϫ78 ЊC) and quickly dried: yield 0.057 g (88%): mp
41 ЊC (decomp.) (Found: C, 43.60; H, 9.18; S, 5.99. C19H47O3-
P2RhS requires C, 43.84; H, 9.10; S, 6.16%). IR (KBr): ν(RhH)
2165 and 2135, ν(O3S) 1207, 1193 and 1043 cmϪ1. NMR (C6D6):
δH (200 MHz) 2.60 (3 H, s, SMe), 2.18 (6 H, m, CHCH3), 1.25
[36 H, dvt, N 14.3, J(HH) 7.1, CHCH3] and Ϫ25.30 [2 H, dt,
J(RhH) 29.1, J(PH) 14.8 Hz, RhH]; δC (100.6 MHz) 39.5
(s, SCH3), 25.7 [vt, N 21.4 Hz, CHCH3] and 20.4 (s, CHCH3);
δP (162.0 MHz) 60.9 [d, dt in off-resonance, J(RhP) 115.0 Hz].
trans-[Rh{ç1-OS(O)2Me}(CO)(PPri3)2] 18. A slow stream
of CO was passed for ca. 5 s through a solution of complex
3 (0.067 g, 0.13 mmol) in hexane (2 cm3). The resulting pale
yellow suspension was stirred for 15 min at room temperature.
After the solvent was removed in vacuo, the remaining white
solid was washed three times with pentane (2 cm3) and dried:
yield 0.063 g (88%); mp 122 ЊC (decomp.) (Found: C, 43.69;
H, 8.05; S, 5.90. C20H45O4P2RhS requires C, 43.94; H, 8.30; S,
5.87%). MS (70 eV): m/z 546 (Mϩ). IR (KBr): ν(CO) 1964,
ν(O3S) 1265 and 1033 cmϪ1. NMR (C6D6): δH (200 MHz) 2.61
(3 H, s, SCH3), 2.54 (6 H, m, CHCH3) and 1.25 [36 H, dvt,
N 14.1, J(HH) 7.2 Hz, CHCH3]; δC (50.3 MHz) 191.1 [dt,
J(RhC) 76.7, J(PC) 16.4 Hz, CO], 40.1 (s, SMe), 24.9 (vt,
N 20.3 Hz, CHCH3) and 20.3 (s, CHCH3); δP (81.0 MHz) 51.4
[d, J(RhP) 119.2 Hz].
[RhH2{ç2-O2S(O)C6H4Me-p}(PPri3)2] 14. This compound
was prepared as described for 13, using 4 (0.059 g, 0.10 mmol)
in CH2Cl2 (5 cm3) as starting material. After the white solid was
washed with small quantities of pentane (Ϫ78 ЊC) it was dried
in vacuo for not more than 5 min: yield 0.057 g (95%); mp
112 ЊC (decomp.) (Found: C, 49.90; H, 8.79; S, 5.30. C25H51O3-
P2RhS requires C, 50.33; H, 8.62; S, 5.37%). NMR (C6D6): δH
(200 MHz) 8.01–6.77 (4 H, m, C6H4), 2.14 (6 H, m, CHCH3),
1.89 (3 H, s, C6H4CH3), 1.18 [36 H, dvt, N 13.1, J(HH) 7.3,
CHCH3] and Ϫ25.26 [2 H, dt, J(RhH) 30.5, J(PH) 14.5 Hz,
RhH]; δP (81.0 MHz) 61.8 [d, dt in off-resonance, J(RhP) 114.8
Hz].
Alternatively, compound 18 was prepared on treatment of
a solution of 13 (0.068 g, 0.13 mmol) in hexane (2 cm3). The
resulting suspension was worked up as described above. White
solid: yield 0.060 g (85%).
trans-[Rh{ç1-OS(O)2C6H4Me-p}(CO)(PPri3)2] 19. This com-
pound was prepared as described for 18, using 4 (0.071 g, 0.12
mmol) as starting material. Light yellow solid: yield 0.066 g
(89%); mp 117 ЊC (decomp.) (Found: C, 49.69; H, 8.00; S, 5.18.
C26H49O4P2RhS requires C, 50.16; H, 7.93; S, 5.15%). IR (KBr):
ν(CO) 1945 cmϪ1. NMR (C6D6): δH (200 MHz) 7.99–6.83 (4 H,
m, C6H4), 2.46 (6 H, m, CHCH3), 1.95 (3 H, s, C6H4CH3) and
1.23 [36 H, dvt, N 13.9, J(HH) 7.3 Hz, CHCH3]; δP (81.0 MHz)
51.7 [d, J(RhP) 119.1 Hz].
[RhH2{ç2-O2S(O)CF3}(PPri3)2] 15. A slow stream of hydro-
gen was passed for ca. 5 s through a solution of complex 5
(0.117 g, 0.21 mmol) in ether (5 cm3). A rapid change from
violet to pale yellow occurred. After the solution was stirred
for 15 min at room temperature the solvent was removed in
vacuo. The residue was extracted with pentane (30 cm3), the
extract filtered and the filtrate brought to dryness in vacuo.
The remaining white solid was washed with small quantities
of pentane (Ϫ78 ЊC) and quickly dried: yield 0.085 g (68%);
mp 52 ЊC (decomp.) (Found: C, 39.84; H, 7.64; S, 5.17.
C19H44F3O3P2RhS requires C, 39.71; H, 7.72; S, 5.57%). MS
(70 eV): m/z 574.8 (Mϩ). IR (KBr): ν(RhH) 2194 and 2135,
ν(CF3) 1258 and 1171, ν(O3S) 1270 and 1032 cmϪ1. NMR
(C6D6): δH (200 MHz) 2.16 (6 H, m, CHCH3), 1.08 [36 H, dvt,
N 13.9, J(HH) 6.9, CHCH3] and Ϫ25.80 [2 H, dt, J(RhH)
33.5, J(PH) 14.5 Hz, RhH]; δC (50.3 MHz) 121.0 [q, J(CF)
319.5 Hz, CF3], 24.9 (vt, N 21.9 Hz, CHCH3) and 20.2
(s, CHCH3); δF (188.2 MHz) Ϫ77.3 (s); δP (81.0 MHz) 60.9
[d, dt in off-resonance, J(RhP) 114.1 Hz].
trans-[Rh{ç1-OS(O)2CF3}(CO)(PPri3)2] 20. This compound
was prepared as described for 18, using either 5 (0.089 g, 0.16
mmol) or 15 (0.090 g, 0.16 mmol) as starting material. Light
yellow solid: yield 0.087 g (93%) from 5 or 0.083 g (90%) from
15; mp 112 ЊC (decomp.) (Found: C, 39.69; H, 7.11; S, 5.39.
C20H42F3O4P2RhS requires C, 40.01; H, 7.05; S, 5.34%). Λ 35
ΩϪ1 cm2 molϪ1. MS (70 eV): m/z 600 (Mϩ). IR (KBr): ν(CO)
1964, ν(O3S) 1273 and 1042, ν(CF3) 1253 and 1171 cmϪ1. NMR
(CD3NO2): δH (400 MHz) 2.69 (6 H, m, CHCH3) and 1.44
[36 H, dvt, N 15.6, J(HH) 7.2 Hz, CHCH3]; δC (100.6 MHz)
191.6 [dt, J(RhC) 65.4, J(PC) 13.6, CO], 122.4 [q, J(CF) 320.9
Hz, CF3], 28.7 (vt, N 24.8 Hz, CHCH3) and 20.6 (s, CHCH3);
δF (376.4 MHz) Ϫ78.4 (s); δP (162.0 MHz) 57.4 [d, J(RhP) 100.4
Hz]. Since the NMR spectra were measured in CD3NO2 the
signals probably correspond to the ionic species 20a (see
Scheme 3).
[RhH2{ç2-O2S(O)F}(PPri3)2] 16. This compound was pre-
pared as described for 13, using 6 (0.136 g, 0.26 mmol) in ether
(3 cm3) as starting material. White solid: yield 0.105 g (77%);
mp 45 ЊC (decomp.) (Found: C, 40.98; H, 8.42; S, 6.11.
trans-[Rh{ç1-OS(O)2F}(CO)(PPri3)2] 21. This compound was
prepared as described for 18, using either 6 (0.108 g, 0.21 mmol)
J. Chem. Soc., Dalton Trans., 1998, 3549–3558
3555

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or 16 (0.116 g, 0.21 mmol) as starting material. Pale yellow
solid: yield 0.110 g (95%) from 6 or 0.105 g (91%) from 16;
mp 121 ЊC (decomp.) (Found: C, 41.21; H, 7.36; S, 5.91.
C19H42FO4PRhS requires C, 41.46; H, 7.69; S, 5.82%). Λ 31 ΩϪ1
cm2 molϪ1. MS (70 eV): m/z 550 (Mϩ). IR (KBr): ν(CO) 1946,
ν(O3S) 1286 and 1063, ν(SF) 700 cmϪ1. NMR (CD3NO2):
δH (400 MHz) 2.68 (6 H, m, CHCH3) and 1.44 [36 H, dvt,
N 15.2, J(HH) 7.2 Hz, CHCH3]; δC (100.6 MHz) 191.6 [dt,
J(RhC) 65.4, J(PC) 13.6 Hz, CO], 28.7 (vt, N 24.8 Hz, CHCH3)
and 20.5 (s, CHCH3); δF (376.4 MHz) 36.5 (s); δP (162.0 MHz)
57.4 [d, J(RhP) 100.3 Hz]. Since the NMR spectra were
measured in CD3NO2 the signals probably correspond to the
ionic species 21a (see Scheme 3).
as starting material. Yellow microcrystalline solid: yield 0.102 g
(98%); mp 52 ЊC (decomp.) (Found: C, 43.22; H, 8.23; S, 5.74.
C20H46FO3P2RhS requires C, 43.64; H, 8.42; S, 5.82%). MS (70
eV): m/z 550 (Mϩ). IR (KBr): ν(O3S) 1332, 1231 and 1083,
ν(SF) 739 cmϪ1. NMR (C6D6): δH (200 MHz) 2.38 [4 H, dd,
J(RhH) 6.7, J(PH) 4.0, C2H4], 2.01 (6 H, m, CHCH3) and 1.15
[36 H, N 13.1, J(HH) 6.8 Hz, CHCH3]; δC (50.3 MHz) 34.8
[d, J(RhC) 17.7 Hz, C2H4], 21.6 (vt, N 17.6 Hz, CHCH3) and
19.6 (s, CHCH3); δF (188.2 MHz) 42.8 (s); δP (81.0 MHz) 35.8
[d, J(RhP) 117.3 Hz].
[{Rh(C2H4)2}2{ì-O2S(O)C6H4Me-p}2] 26. A slow stream of
ethene was passed through a suspension of complex 11 (0.110 g,
0.11 mmol) in hexane (4 cm3) for 1 min at room temperature.
After the reaction mixture was stirred for 5 min it was stored
until the pale yellow solid and the solution were separated. The
mother-liquor was decanted, the pale yellow solid repeatedly
washed with 5 cm3 portions of pentane and dried: yield 0.062 g
(85%); mp 134 ЊC (decomp.) (Found: C, 39.75; H, 4.62; S,
9.28. C22H30O6Rh2S2 requires C, 40.01; H, 4.58; S, 9.71%). IR
(CH2Cl2): ν(O3S) 1195, 1132, 1048 and 1015 cmϪ1. NMR
(CDCl3, 60 ЊC): δH (200 MHz) 7.82 (4 H, m, ortho-H of SC6H4),
6.80 (4 H, m, meta-H of SC6H4), 3.00 (12 H, s, C2H4) and 1.93
(6 H, s, C6H4CH3); δC (50.3 MHz) 141.5 (s, ipso-C of SC6H4),
140.7, 129.1, 126.7 (all s, C6H4), 60.6 (br m, C2H4) and 21.0
(s, C6H4CH3).
trans-[Rh{ç1-OS(O)2Me}(C2H4)(PPri3)2] 22. A slow stream
of ethene was passed through a suspension of complex 3 (0.102
g, 0.20 mmol) in pentane (5 cm3). After the reaction mixture
was stirred for 30 min at room temperature it was concentrated
to ca. 1 cm3 by passing a stream of ethene through the solution.
After the solution was stored for 12 h at Ϫ78 ЊC a yellow micro-
crystalline solid precipitated which was separated from the
mother-liquor, washed twice with small portions of pentane
(Ϫ78 ЊC) and dried with a stream of ethene: yield 0.104 g
(97%); mp 74 ЊC (decomp.) (Found: C, 45.71; H, 9.15; S, 5.56.
C21H49O3P2RhS requires C, 46.14; H, 9.04; S, 5.85%). IR (KBr):
ν(O3S) 1252, 1162 and 1039 cmϪ1. NMR (C6D6, saturated with
C2H4): δH (400 MHz) 2.70 (3 H, s, SCH3), 2.47 (4 H, m, C2H4),
2.26 (6 H, m, CHCH3) and 1.21 [36 H, N 13.2, J(HH) 6.4 Hz,
CHCH3]; δC (100.6 MHz) 40.2 (s, SCH3), 33.3 [d, J(RhC) 16.5
Hz, C2H4], 22.8 (vt, N 16.3 Hz, CHCH3) and 20.5 (s, CHCH3);
δP (162.0 MHz) 35.2 [d, J(RhP) 119.1 Hz].
[{Rh(C2H4)2}2{ì-O2S(O)CF3}2] 27. This compound was pre-
pared as described for 26, using 12 (0.080 g, 0.08 mmol) as
starting material. Yellow solid: yield 0.040 g (76%); mp 131 ЊC
(decomp.). MS (70 eV): m/z (%) 616 (0.4) [Mϩ], 5.88 (1.0)
[Mϩ Ϫ C2H4], 560 (2.3) [Mϩ Ϫ 2C2H4], 532 (0.4) [Mϩ Ϫ 3C2H4],
504 (2.8) [Mϩ Ϫ 4C2H4], 252 (12.3) [RhO3SCF3ϩ] and 103 (33)
[Rhϩ].
trans-[Rh{ç1-OS(O)2C6H4Me-p}(C2H4)(PPri3)2] 23. This
compound was prepared as described for 22, using 4 (0.075 g,
0.13 mmol) as starting material. Yellow microcrystalline solid:
yield 0.067 g (85%); mp 58 ЊC (decomp.) (Found: C, 52.14;
H, 8.86; S, 5.16. C27H53O3P2RhS requires C, 52.09; H, 8.58; S,
5.15%). MS (70 eV): m/z 622 (Mϩ). IR (KBr): ν(O3S) 1259 and
1032 cmϪ1. NMR (C6D6, saturated with C2H4): δH (200 MHz)
8.02, 6.85 (4 H, both m, C6H4), 2.51 (4 H, m, C2H4), 2.17 (6 H,
m, CHCH3), 1.99 (3 H, s, C6H4CH3) and 1.20 [36 H, N 13.2,
J(HH) 6.6 Hz, CHCH3]; δC (50.3 MHz) 144.2 (s, ipso-C of
SC6H4), 139.3, 128.3, 127.0 (all s, C6H4), 33.2 [d, J(RhC) 16.6
Hz, C2H4], 22.9 (vt, N 16.6 Hz, CHCH3), 21.1 (s, C6H4CH3)
and 20.4 (s, CHCH3); δP (162.0 MHz) 35.6 [d, J(RhP) 119.2
Hz].
trans-[Rh{ç1-OS(O)2CF3}(C2H4)(SbPri3)2] 28. A suspension
of complex 12 (0.122 g, 0.12 mmol) in pentane (5 cm3) was
treated at Ϫ40 ЊC with SbPri3 (0.105 cm3, 0.49 mmol). A red
solution was formed which was stirred for 10 min at Ϫ40 ЊC.
A slow stream of ethene was then passed through the solution
(ca. 1 min) and a yellow solid precipitated. The mother-liquor
was decanted, the solid washed three times with 2 cm3 portions
of pentane (Ϫ40 ЊC) and dried: yield 0.171 g (86%); mp 47 ЊC
(decomp.) (Found: C, 40.35; H, 6.41; S, 3.98. C27H53O3RhSSb2
requires C, 40.33; H, 6.64; S, 3.99%). IR (C6H6): ν(O3S) 1263,
1153 and 1105 cmϪ1. NMR: δH (200 MHz, C6D6) 8.05, 6.88
(4 H, both m, C6H4), 3.59 (4 H, br s, C2H4), 2.11 (6 H, m,
CHCH3), 1.95 (3 H, s, C6H4CH3) and 1.30 [36 H, d, J(HH) 7.0
Hz, CHCH3]; δC (50.3 MHz, CDCl3) 143.4 (br s, ipso-C of
SC6H4), 139.6, 128.7, 126.8 (all s, C6H4), 29.5 (m, C2H4), 22.1
(s, CHCH3) and 19.0 (br s, CHCH3).
Alternatively, compound 23 was prepared on treatment of a
suspension of 26 (0.028 g, 0.04 mmol) in C6D6 (0.5 cm3) with
PPri3 (0.030 cm3, 0.16 mmol). The 1H NMR spectrum displayed
only the signals of 23 and of free ethene.
trans-[Rh{ç1-OS(O)2CF3}(C2H4)(PPri3)2] 24. This compound
was prepared as described for 22, using 5 (0.077 g, 0.14 mmol)
as starting material. Yellow microcrystalline solid: yield 0.065 g
(80%); mp 76 ЊC (decomp.) (Found: C, 41.90; H, 7.53; S, 5.27.
C21H46F3O3P2RhS requires C, 41.99; H, 7.72; S, 5.33%). IR
Alternatively, compound 28 was prepared on treatment of a
suspension of 27 (0.098 g, 0.10 mmol) and SbPri3 (0.098 cm3,
0.40 mmol) in pentane (15 cm3) at Ϫ40 ЊC. Yellow solid: yield
0.142 g (89%).
(KBr): ν(O3S) 1305 and 1026, ν(CF3) 1230 and 1165 cmϪ1
.
[Rh{ç2-O2S(O)CF3}(C8H14)(PPri3)] 29. A solution of com-
plex 12 (0.529 g, 0.56 mmol) in pentane (25 cm3) was treated at
0 ЊC with PPri3 (0.148 cm3, 1.12 mmol) to give a violet-brown
reaction mixture which was stirred for 2 h at room temperature.
The resulting orange solution was concentrated to ca. 2 cm2
in vacuo which led to the precipitation of an orange-red micro-
crystalline solid. The mother-liquor was decanted, the residue
washed three times with 5 cm3 portions of pentane (Ϫ78 ЊC)
and dried in vacuo: yield 0.380 g (65%); mp 36 ЊC (decomp.)
(Found: C, 41.78; H, 6.51; S, 6.01. C18H35F3O3PRhS requires C,
41.38; H, 6.75; S, 6.14%). MS (70 eV): m/z 522 (Mϩ). IR (KBr):
NMR (C6D6): δH (200 MHz) 2.54 (4 H, m, C2H4), 2.13 (6 H, m,
CHCH3) and 1.15 [36 H, N 13.2, J(HH) 6.9 Hz, CHCH3];
δC (100.6 MHz) 120.8 [q, J(FC) 321.0 Hz, CF3], 33.7 (br s,
C2H4), 22.9 (vt, N 17.3 Hz, CHCH3) and 20.3 (s, CHCH3);
δF (188.2 MHz) Ϫ76.7 (s); δP (188.2 MHz) 34.6 [d, J(RhP) 117.5
Hz].
Alternatively, compound 23 was prepared on treatment of
a suspension of 27 (0.040 g, 0.06 mmol) in C4D8O (0.5 cm3)
1
at Ϫ20 ЊC with PPri3 (0.045 cm3, 0.24 mmol). The H NMR
spectrum displayed only the signals of 24 and of free ethene.
ν(O3S) 1259, 1249 and 1021, ν(CF3) 1244, 1179 and 1169 cmϪ1
.
trans-[Rh{ç1-OS(O)2F}(C2H4)(PPri3)2] 25. This compound
was prepared as described for 22, using 6 (0.098 g, 0.19 mmol)
NMR (CD2Cl2): δH (400 MHz) 3.01 [2 H, m, J(HH) 9.8, ᎐CH
᎐
of C8H14], 2.13 [2 H, dd, J(HH) 12.3, 3.1, CH2 of C8H14], 1.75
3556
J. Chem. Soc., Dalton Trans., 1998, 3549–3558

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(3 H, m, CHCH3), 1.55 (2 H, m, CH2 of C8H14), 1.38 (8 H, br m,
CH2 of C8H14) and 1.23 [18 H, dd, J(PH) 13.9, J(HH) 7.2 Hz,
CHCH3]; δC (100.6 MHz) 120.0 [q, J(CF) 319.4, CF3], 61.1 [d,
and dried: yield 0.095 g (91%); mp 74 ЊC (decomp.) (Found: C,
56.61; H, 8.01; S, 4.53. C33H55O3P2RhS requires C, 56.89; H,
7.96; S, 4.60%). MS (ES): m/z (%) 605 (2.7) [Mϩ Ϫ C6H4CH3].
NMR (C6D6): δH (200 MHz) 7.99–6.85 (9 H, m, C6H5 and
C6H4), 2.61 (6 H, m, CHCH3), 1.97 (3 H, s, C6H4CH3), 1.51
J(RhC) 18.3, ᎐CH of C H ], 29.7, 28.5, 26.8 (all s, CH of
᎐
8
14
2
C8H14), 23.8 [d, J(PC) 26.4 Hz, CHCH3) and 19.7 (s, CHCH3);
δF (376.4 MHz) Ϫ78.5 (s); δP (162 MHz) 78.7 [d, J(RhP)
212.8 Hz].
[1 H, dt, J(RhH) 1.5, J(PH) 2.9, ᎐CHPh] and 1.24 [36 H, dvt,
᎐
N 13.9, J(HH) 7.3 Hz, CHCH3]; δC (100.6 MHz) 301.1 [dt,
J(RhC) 61.0, J(PC) 17.3 Hz, Rh᎐C], 143.6, 139.7, 135.2, 128.6,
᎐
[Rh{ç2-O2S(O)CF3}(C2H4)(PPri3)] 30. A solution of complex
29 (0.197 g, 0.38 mmol) in pentane (10 cm3), prepared in situ
from 12 (0.178 g, 0.19 mmol) and PPri3 (0.074 cm3, 0.38 mmol),
was treated at room temperature for 10 s with a stream of
ethene which afforded a yellow suspension. The solvent was
decanted, the yellow microcrystalline residue washed three
times with 5 cm3 portions of pentane and dried in vacuo: yield
0.114 g (69%); mp 50 ЊC (decomp.) (Found: C, 32.54; H, 5.72;
S, 7.05. C12H25F3O3PRhS requires C, 32.74; H, 5.72; S, 7.28%).
NMR (CD2Cl2): δH (400 MHz) 2.75 (4 H, br s, C2H4), 1.83 (3 H,
m, CHCH3) and 1.33 [18 H, J(PH) 13.8, J(HH) 7.0 Hz,
CHCH3]; δC (100.6 MHz) 119.0 [q, J(FC) 318.5, CF3], 43.7
[d, J(RhC) 15.3, C2H4], 23.1 [d, J(PC) 25.8 Hz, CHCH3] and
19.8 (s, CHCH3); δF (376.4 MHz) Ϫ78.4 (s); δP (162 MHz) 69.5
[d, J(RhP) 189.7 Hz].
128.5, 126.7, 125.7, 125.5 (all s, C6H5 and C6H4), 112.2 [dt,
J(RhC) 17.3, J(PC) 6.1, =CHPh], 24.1 [vt, N 19.6 Hz, CHCH3],
21.1 (s, C6H4CH3) and 20.3 (s, CHCH3); δP (81.0 MHz) 44.8
[d, J(RhP) 136.6 Hz].
Catalytic studies
Reactions of Ph2CN2 and C2H4 with complexes 3–6 as catalysts.
A solution of a complex (ca. 20 mg, ca. 0.04 mmol) in methyl-
cyclohexane (6 cm3) for 3, 4 or toluene (6 cm3) for 5, 6 was
treated dropwise at 40 ЊC with a 0.5 mol dmϪ3 solution of
diphenyldiazomethane in methylcyclohexane while bubbling
ethene through the solution. The catalytic reaction was finished
when the violet colour of the diazoalkane solution did not dis-
appear on further addition to the reaction mixture. The solvent
was removed in vacuo, and the oily residue dissolved in 2–3 cm3
of hexane. In order to destroy the excess of Ph2CN2 and separ-
ate the catalyst, the mixture was filtered through Al2O3 (neutral,
activity grade III, height of column 3 cm). After evaporation
of the solvent, an oil containing a mixture of Ia–Id was
isolated from the eluate. The ratio of the products was deter-
[Rh(ç6-C6H6)(C8H14)(PPri3)][O3SCF3] 31.
A solution of
compound 29 (0.089 g, 0.17 mmol) in C6H6 (5 cm3) was stirred
for 12 h at room temperature. A yellow solution was formed,
which was filtered and the filtrate concentrated to ca. 1 cm3
in vacuo. Addition of pentane (5 cm3) afforded a yellow suspen-
sion which was stored for 2 h. The solvent was then decanted,
the yellow microcrystalline residue washed twice with 5 cm3
portions of pentane and dried in vacuo: yield 0.093 g (92%);
mp 67 ЊC (decomp.) (Found: C, 48.06; H, 6.90; Rh, 17.48; S,
5.15. C24H41F3O3PRhS requires C, 47.99; H, 6.89; Rh, 17.15; S,
5.33%). MS-FAB: m/z (%) 451 (0.7) [Mϩ Ϫ O3SCF3], 373 (1.0)
[Rh(C8H14)(PPri3)]ϩ and 263 (4.0) [Rh(PPri3)]ϩ. IR (KBr):
ν(O3S) 1276 and 1059, ν(CF3) 1183 cmϪ1. NMR (CD2Cl2):
δH (400 MHz) 6.70 (6 H, s, C6H6), 3.09 [2 H, d, J(RhH) 9.4,
1
mined by integration of characteristic signals in the H NMR
spectra and by GC-MS analysis. The results are summarized in
Table 4.
Reaction of Ph2CN2 and methyl acrylate with complex 5 as
catalyst. In an analogous manner to the catalytic reaction of
Ph2CN2 and ethene, a solution of complex 5 (17 mg, 0.03
mmol) and methyl acrylate (2.6 cm3, 3.0 mmol) in methyl-
cyclohexane (6 cm3) was treated dropwise at 40 ЊC with a 0.1
mol dmϪ3 solution of diphenyldiazomethane in toluene. After
work-up, a clear oil was isolated and characterized by 1H NMR
data and GC-MS analysis as IIa: yield 390 mg (1.55 mmol).
᎐CH of C H ], 2.38 [2 H, dd, J(HH) 9.7, 3.0, CH of C H ],
᎐
8
14
2
8
14
1.87 (3 H, m, CHCH3), 1.49 (2 H, m, CH2 of C8H14), 1.39 (8 H,
br m, CH2 of C8H14) and 1.32 [18 H, dd, J(PH) 14.1, J(HH) 7.4
If instead of methyl acrylate the corresponding ester CH ᎐
᎐
2
Hz, CHCH ]; δ (100.6 MHz) 67.9 [d, J(RhC) 14.3 Hz, ᎐CH of
᎐
3
C
CHCH2CO2Me was used as the substrate, a small quantity
(11 mg, 0.04 mmol) of an off-white oil was isolated. It was
characterized by 1H NMR data and GC-MS analysis as IIb.
C8H14], 34.2, 32.4, 26.4 (all s, CH2 of C8H14), 25.5 [d, J(PC) 23.8
Hz, CHCH3] and 19.9 (s, CHCH3); δF (376.4 MHz) Ϫ78.0 (s);
δP (162 MHz) 63.7 [d, J(RhP) 182.4 Hz].
[Rh(ç6-C6H6)(C2H4)(PPri3)][O3SCF3] 32. This compound
was prepared as described for 31, using 30 (0.264 g, 0.60 mmol)
as starting material. Pale yellow solid: yield 0.281 g (90%);
mp 82 ЊC (decomp.) (Found: C, 40.81; H, 5.85; S, 6.02.
C18H31F3O3PRhS requires C, 41.71; H, 6.03; S, 6.19%). IR
(KBr): ν(O3S) 1270 and 1028, ν(CF3) 1156 cmϪ1. NMR
(CD2Cl2): δH (400 MHz) 6.77 (6 H, s, C6H6), 3.33, 2.23 (4 H,
both m, C2H4), 1.84 (3 H, m, CHCH3) and 1.20 [18 H, dd,
J(PH) 14.1, J(HH) 7.0 Hz, CHCH3]; δC (100.6 MHz) 121.2
[q, J(FC) 321.1 Hz, CF3], 104.5 (br s, C6H6), 40.6 [d, J(RhC)
13.2, C2H4], 25.3 [d, J(PC) 24.4 Hz, CHCH3] and 19.6 (s,
CHCH3); δF (376.4 MHz) Ϫ78.5 (s); δP (162 MHz) 65.8 [d,
J(RhP) 176.3 Hz].
Crystallography
Single crystals of complex 4 were grown from acetone (8 ЊC),
those of 29 from pentane (20 ЊC) and those of 31 from benzene
(20 ЊC). Crystal data collection parameters are summarized in
Table 5. Intensity data were corrected for Lorentz-polarization
effects. Data reduction were performed for 4 and 31 with SDP26
and for 29 with Stoe IPDS software. The structures were solved
by direct methods (SHELXS 86).27 For 29 and 31 two
independent molecules (A and B) were found in the asymmetric
units with different conformations of the cyclooctene ligand. In
Figs. 1 and 2 only molecule A of 29 and 31, respectively, is
shown. Table 5 contains the crystallographic data of each whole
asymmetric unit (molecule A and B), the chemical formula and
the formula weight, however, belong to one molecule only.
Atomic coordinates and anisotropic displacement parameters
of the non-hydrogen atoms were refined anisotropically by full-
matrix least squares on F2 (SHELXL 93).28 The positions of the
hydrogen atoms [except of H(20), H(21), H(40) and H(41) in 29
and C(30), H(31), H(40) and H(41) in 31] were calculated
according to ideal geometry using the riding method.
[Rh{ç1-OS(O )C H Me-p}(C᎐CHPh)(PPri ) ] 33. A solution
᎐
2
6
4
3 2
of complex 4 (0.089 g, 0.15 mmol) in toluene (2 cm3) was
treated with phenylacetylene (0.017 cm3, 0.15 mmol) and stirred
for 6 h at room temperature. A smooth change from red to
violet occurred. The solvent was removed, the residue extracted
with ether (20 cm3) and the extract brought to dryness in vacuo.
The remaining solid was dissolved in acetone (2 cm3) and the
solution stored for 12 h at Ϫ78 ЊC. Violet crystals precipitated
which were washed twice with 2 cm3 portions of acetone (0 ЊC)
CCDC reference number 186/1157.
See http://www.rsc.org/suppdata/dt/1998/3549/ for crystallo-
graphic files in .cif format.
J. Chem. Soc., Dalton Trans., 1998, 3549–3558
3557

View Article Online
Table 5 Crystal data for complexes 4, 29 and 31
4
29
31a
Formula
M
C25H49O3P2RhS
594.55
C18H35F3O3PRhS
522.40
C24H41F3O3PRhS
600.51
Crystal system
Space group
a/Å
b/Å
c/Å
α/Њ
β/Њ
Monoclinic
P21/c (no. 14)
10.498(4)
14.104(3)
20.276(7)
—
92.89(2)
—
2998(2)
293
Monoclinic
P21/c (no. 14)
14.177(3)
17.626(6)
19.038(6)
—
103.61(3)
—
4624(2)
173
Triclinic
P1 (no. 2)
¯
14.042(4)
15.347(4)
15.532(2)
63.12(2)
73.03(2)
70.98(2)
2781(1)
293
γ/Њ
U/Å3
T/K
Z
4
8
4
Dc/g cmϪ3
1.317
1.501
1.434
λ(Mo-Kα)/Å
0.71073
0.761
0.71073
0.928
0.71073
0.782
µ/mmϪ1
No. reflections measured
No. unique reflections (Rint
R1b
4422
4156 (0.0127)
0.0266
36543
8695 (0.0746)
0.0334
9104
)
8703 (0.0096)
0.0294
0.0751
wR2c
0.0717
0.0683
a For complex 31 an extinction parameter was refined to (5.98 0.23) × 10Ϫ3 b R = Σ|Fo Ϫ Fc|/ΣFo [for Fo > 2σ(Fo)] for the number of observed
.
¹
2
2
2
reflections [I > 2σ(I)], respectively. c wR2 = [Σw(Fo2 Ϫ Fc2)2/Σw(Fo )2]²; wϪ1 = [σ2(Fo ) ϩ (0.0377P)2 ϩ 1.1100P] (4), [σ2(Fo ) ϩ (0.0289P)2 ϩ 0.0000P]
(29), [σ2(Fo ) ϩ (0.0347P)2 ϩ 2.5370P] (31), where P = (Fo2 ϩ 2Fc2)/3; for all data reflections, respectively.
2
13 O. Gevert, J. Wolf and H. Werner, Organometallics, 1996, 15, 2806.
14 H. Werner, F. J. Garcia Alonso, H. Otto and J. Wolf, Z. Natur-
Acknowledgements
We thank the Deutsche Forschungsgemeinschaft (SFB 347)
and the Fonds der Chemischen Industrie for financial support,
the latter in particular for Ph.D. grants to M. E. S. and M. M.
We are also grateful to Mrs R. Schedl and Mr C. P. Kneis
(DTA measurements and elemental analyses), to Dr G. Lange
and Dr M. Herderich (mass spectra), to Degussa AG and
BASF AG (chemicals), and to Dr J. Wolf for numerous
valuable discussions.
forsch., Teil B, 1988, 43, 722; H. Werner and U. Brekau, Z. Natur-
forsch., Teil B, 1989, 44, 1438; T. Rappert, O. Nürnberg, N. Mahr,
J. Wolf and H. Werner, Organometallics, 1992, 11, 4156.
15 U. Möhring, M. Schäfer, F. Kukla, M. Schlaf and H. Werner,
J. Mol. Catal. A, 1995, 99, 55.
16 M. Aresta, E. Quaranta and A. Albinati, Organometallics, 1993, 12,
2032.
17 For a recent review on stibine transition-metal complexes see N. R.
Champness and W. Levason, Coord. Chem. Rev., 1994, 133, 115.
18 P. Schwab, N. Mahr, J. Wolf and H. Werner, Angew. Chem., 1993,
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Paper 8/05900D
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J. Chem. Soc., Dalton Trans., 1998, 3549–3558