Synthesis, characterization and structures of cyclic organorhodium complexes of the type [Rh{CH(SO2Ph)CH2CH 2YR2-κC,κY}L2] (YR2 = PPh2, NMe2; L2 = diphosphine, cyclooctadiene)

Article abstract of DOI:10.1039/c001452d

Reactions of dinuclear chloridorhodium(i) complexes [(RhL₂) ₂(μ-Cl)₂] (L₂ = PP: Me₂P(CH ₂)₂PMe₂, dmpe, 7a; Ph₂PCH ₂PPh₂, dppm, 7b; Ph₂P(CH₂) ₂PPh₂, dppe, 7c; Ph₂P(CH₂) ₃PPh₂, dppp, 7d; L₂ = cycloocta-1,5-diene, cod, 5) with lithiated γ-phosphino- and γ-aminofunctionalized propyl phenyl sulfones (Li[CH(SO₂Ph)CH₂CH₂PPh ₂], 2; Li[CH(SO₂Ph)CH₂CH₂NMe ₂], 4) led to the formation of organorhodium inner complexes of the type [Rh{CH(SO₂Ph)CH₂CH₂PPh₂- κC,κP}(PP)] (8a-d), [Rh{CH(SO₂Ph)CH₂CH ₂NMe₂-κC,κN}(PP)] (9a-d), [Rh{CH(SO ₂Ph)CH₂CH₂PPh₂-κC,κP} (cod)]·LiCl (11·LiCl) and [Rh{CH(SO₂Ph)CH ₂CH₂NMe₂-κC,κN}(cod)]·LiCl (12·LiCl), respectively. Single-crystal X-ray diffraction analysis of 9c·THF, 11 and 12 exhibited in all three compounds a distorted square planar coordination of the rhodium atoms having bidentately coordinated neutral co-ligands (cod, 11, 12; dppe, 9c) and anionic α-phenylsulfonyl γ-phosphinopropyl (κC,κP; 11) and γ-aminopropyl ligands (κC,κN; 12, 9c), thus being typical organorhodium inner complexes. Furthermore, organorhodium inner complexes of type 8 were obtained in reactions of the dinuclear chloridobridged rhodium complexes [(RhL₂) ₂(μ-Cl)₂] (L₂ = PP, 7a-d; cod, 5; (C ₂H₄)₂, 6) with the (non-lithiated) γ-phosphinofunctionalized propyl phenyl sulfone PhSO₂CH ₂CH₂CH₂PPh₂ (1) resulting in the formation of complexes having the sulfone κP coordinated ([RhClL ₂(Ph₂PCH₂CH₂CH₂SO ₂Ph-κP)] (L₂ = PP, 10a-d; cod, 13; (C ₂H₄)₂, 14) which were deprotonated (10a-d, 13) at the α-C atom with lithium diisopropyl amide (LDA) in a subsequent reaction. Single-crystal X-ray diffraction analysis of 10c (PP = dppe) revealed the expected square-planar coordination geometry of Rh. The identities of all rhodium complexes have been unambiguously proved by microanalyses and NMR spectroscopy (¹H, ¹³C, ³¹P).

Full text of DOI:10.1039/c001452d

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PAPER
www.rsc.org/dalton | Dalton Transactions
Synthesis, characterization and structures of cyclic organorhodium complexes
of the type [Rh{CH(SO2Ph)CH2CH2YR2-jC,jY}L2] (YR2 = PPh2,
NMe2; L2 = diphosphine, cyclooctadiene)‡†
Michael Block,a Christoph Wagner,a Santiago Go´mez-Ruizb and Dirk Steinborn*a
Received 22nd January 2010, Accepted 25th March 2010
First published as an Advance Article on the web 23rd April 2010
DOI: 10.1039/c001452d
Reactions of dinuclear chloridorhodium(I) complexes [(RhL2)2(m-Cl)2] (L2 = P P: Me2P(CH2)2PMe2,
dmpe, 7a; Ph2PCH2PPh2, dppm, 7b; Ph2P(CH2)2PPh2, dppe, 7c; Ph2P(CH2)3PPh2, dppp, 7d; L2 =
cycloocta-1,5-diene, cod, 5) with lithiated g-phosphino- and g-aminofunctionalized propyl phenyl
sulfones (Li[CH(SO2Ph)CH2CH2PPh2], 2; Li[CH(SO2Ph)CH2CH2NMe2], 4) led to the formation of
organorhodium inner complexes of the type [Rh{CH(SO2Ph)CH2CH2PPh2-kC,kP}(P P)] (8a–d),
[Rh{CH(SO2Ph)CH2CH2NMe2-kC,kN}(P P)] (9a–d), [Rh{CH(SO2Ph)CH2CH2PPh2-kC,kP}(cod)]·
LiCl (11·LiCl) and [Rh{CH(SO2Ph)CH2CH2NMe2-kC,kN}(cod)]·LiCl (12·LiCl), respectively.
Single-crystal X-ray diffraction analysis of 9c·THF, 11 and 12 exhibited in all three compounds a
distorted square planar coordination of the rhodium atoms having bidentately coordinated neutral
co-ligands (cod, 11, 12; dppe, 9c) and anionic a-phenylsulfonyl g-phosphinopropyl (kC,kP; 11) and
g-aminopropyl ligands (kC,kN; 12, 9c), thus being typical organorhodium inner complexes.
Furthermore, organorhodium inner complexes of type 8 were obtained in reactions of the dinuclear
chloridobridged rhodium complexes [(RhL2)2(m-Cl)2] (L2 = P P, 7a–d; cod, 5; (C2H4)2, 6) with the
(non-lithiated) g-phosphinofunctionalized propyl phenyl sulfone PhSO2CH2CH2CH2PPh2 (1)
resulting in the formation of complexes having the sulfone kP coordinated ([RhClL2-
(Ph2PCH2CH2CH2SO2Ph-kP)] (L2 = P P, 10a–d; cod, 13; (C2H4)2, 14) which were deprotonated
(10a–d, 13) at the a-C atom with lithium diisopropyl amide (LDA) in a subsequent reaction.
Single-crystal X-ray diffraction analysis of 10c (P P = dppe) revealed the expected square-planar
coordination geometry of Rh. The identities of all rhodium complexes have been unambiguously
proved by microanalyses and NMR spectroscopy (1H, 13C, 31P).
intramolecular-coordination compounds) for metallacycles which
1. Introduction
are characterized by a M–C bond and a bond of the metal to a
Metallacycles are cyclic compounds having at least one metal–
neutral Lewis-basic heteroatom group like NR2, PR2, OR or SR
being also part of the cycle.11 In 1966 investigations of organotin
inner complexes having a coordinated oxygen or nitrogen atom
exhibited a very high stability of five-membered metallacycles.12
Organotransition metal inner complexes were broadly prepared by
cyclometallation (especially orthometallation) reactions resulting
in five-membered metallacycles in most cases. A prerequisite for
such metallations is that the C–H bonds to be activated are brought
in close vicinity to the metal centers mostly by pre-coordination of
the organic moiety onto a Lewis-basic heteroatom group YRn.13
The first report, the synthesis of an o-(phenylazo)phenyl nickel
complex, dated from 1963.14
Generally, such inner complexes are of importance in three
types of applications in organic syntheses:15 the first application
is to utilize the ease of synthesis of these compounds and
the chelate ring stability. These cyclometallation products are
then further used for the synthesis of organic derivatives by
manifold reactions such as insertion, substitution or rearrange-
ment – for example carbonylation,16 alkenylation,17 acylation18
or Diels-Alder reactions.19 If the cyclometallation products are
less stable the five-membered ring intermediates easily can react
with substrates in substitution reactions which represents the
second type of application. Such reactions are regiospecific since
carbon bond where both the carbon and the metal atom are
part of a ring system. In general, they are more stable than
their open-chain analogues because hydride elimination reac-
tions are hampered for stereoelectronic reasons. Metallacycles
play an important role as model compounds for investigations
of organometallic elementary steps.1,2 Furthermore, they are
intermediates in transition metal catalyzed reactions such as
oxidative coupling reactions,3,4 activation of C–H bonds5–8 and
olefin metathesis reactions.9,10 In 1955, Ba¨hr and Mu¨ller de-
scribed the two complexes [AlEt2(CH2CH2CH2CH2OEt-kC,kO)]
and [AlEt2(CH2CH2CH2NEt2-kC,kN)] and introduced the term
“organometallic inner complexes” (also named as organometallic
aInstitut fu¨r Chemie, Martin-Luther-Universita¨t Halle-Wittenberg, Kurt-
Mothes-Straße 2, D-06120, Halle, Germany. E-mail: dirk.steinborn@
chemie.uni-halle.de
bDepartamento de Qu´ımica Inorga´nica y Anal´ıtica, E.S.C.E.T., Universidad
Rey Juan Carlos, 28933, Mo´stoles, Madrid, Spain
† Electronic supplementary information (ESI) available: Preparation and
NMR spectroscopic data of starting materials. CCDC reference numbers
759014–759017. For ESI and crystallographic data in CIF or other
electronic format see DOI: 10.1039/c001452d
‡ Dedicated to Professor Uwe Rosenthal on the occasion of his 60th
birthday.
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they proceed at the metal bound carbon atom and they have
been reported on carbonylations,20 cross-coupling reactions,21 ring
expansions22 or carbocyclizations.23 The third kind of application
are metal-catalyzed reactions where inner complexes are involved.
These reactions include, in organic chemistry widely used, cross-
coupling reactions like the Stille, Suzuki or Heck reactions,24–26
rearrangements,27 metatheses,28–30 reductions31 and other reac-
tions.
found to proceed in THF as solvent but difficulties encountered
to obtain the complexes free of LiCl in this way. The yellowish to
orange air-sensitive complexes 8a–d/9a–d were obtained in yields
between 48 and 91%. All complexes were found to decompose
in methylene chloride and chloroform at room temperature and,
additionally, complex 9d also in THF.
Another route to obtain the organometallic inner com-
plexes of type
8
were the reactions of the dimeric
We are interested in a-sulfur functionalized propyl ligands
having an additional Lewis-basic heteroatom group (YR2 = PPh2,
NMe2) in g-position, being favorable for the formation of five-
membered MC3Y cycles. In the case of lithiated g-functionalized
propyl phenyl sulfides of the type [Li{CH(SPh)CH2-
CH2YRn}(tmeda)] (YRn = NMe2, Ot-Bu) the formation of
organolithium inner complexes by coordination of the YRn
group could be unambiguously proved by single-crystal X-ray
diffraction analysis.32,33 However, lithiated alkyl phenyl sulfones,
regardless whether they bear a Lewis-basic heteroatom group YRn
in g-position or not, are typically dimeric molecules in the solid
state having no metal–carbon bonds but “free” a-carbanionic
centers34 and only few examples with a lithium–carbon bond
could be structurally characterized.35–37 Here we report on
the formation of five-membered rhodacycles with the general
formula [Rh{CH(SO2Ph)CH2CH2YR2-kC,kY}L2] (YR2 = PPh2,
NMe2; L2 = diphosphine, cyclooctadiene), thus being cyclic
organorhodium complexes.
diphosphine-chloridorhodium complexes 7a–d with the (non-
lithiated) g-phosphinofunctionalized propyl phenyl sulfone
PhSO2CH2CH2CH2PPh2 (1) resulting in the formation of type
10 complexes [RhCl(P P)(Ph2PCH2CH2CH2SO2Ph-kP)] that
contain the sulfone in a kP coordination mode (Scheme 1).
These chloridorhodium complexes with PhSO2CH2CH2CH2PPh2-
kP ligands were isolated in 65–88% yield and proved to be air-
sensitive, too. In contrast to 10a and 10d, the complexes 10b
and 10c were found to be stable in methylene chloride. Type
10 complexes reacted with lithium diisopropylamide (LDA) in
toluene/THF under deprotonation neighboured to the sulfur cen-
ter (a-CH2 group) of the phosphinofunctionalized sulfone ligand
resulting in the formation of the inner complexes 8a–d. Using
MeLi or n-BuLi as deprotonating agent led to decomposition
which might be caused by the stronger nucleophilic character
of these bases. In contrast, the g-aminofunctionalized sulfone
PhSO2CH2CH2CH2NMe2 (3) did not react with type 7 complexes
at all (Scheme 1).
As the diphosphine complexes [{Rh(P P)}2(m-Cl)2] (7a–d),
the respective cyclooctadiene complex [{Rh(cod)}2(m-Cl)2] (5)
was found to react with the lithiated g-phosphino and
g-aminofunctionalized propyl phenyl sulfones 2 and 4 as
well, yielding the organorhodium inner complexes 11 and
12 (Scheme 2). Precipitation from the reaction mixtures
(toluene solutions) with n-pentane resulted in the forma-
tion of the LiCl adducts ([Rh{CH(SO2Ph)CH2CH2PPh2-
kC,kP}(cod)]·LiCl, 11·LiCl; [Rh{CH(SO2Ph)CH2CH2NMe2-
kC,kN}(cod)]·LiCl, 12·LiCl) as yellow powders. Recrystallisation
from THF/n-pentane and THF, respectively, gave well shaped
crystals of complexes 11 and 12 which were shown to be free of
LiCl by X-ray diffraction analyses.
2. Results and discussion
2.1. Synthesis
The reactions of dinuclear diphosphine-chloridorhodium com-
plexes 7a–d with lithiated g-phosphino- and g-aminofunction-
alized propyl phenyl sulfones 2 and 4 resulted in the formation
of organorhodium inner complexes of the type [Rh{CH(SO2Ph)-
CH2CH2PPh2-kC,kP}(P P)] (8a–d) and [Rh{CH(SO2Ph)-
CH2CH2NMe2-kC,kN}(P P)] (9a–d), respectively (Scheme 1).
In the sense of one-pot reactions, at first the requisite sulfones
PhSO2CH2CH2CH2PPh2 (1) and PhSO2CH2CH2CH2NMe2 (3)
were lithiated with n-BuLi in toluene followed by the reaction with
the rhodium complexes 7a–d at -78 ◦C. The same reactions were
The analogous reactions of the ethylene complex
[{Rh(C2H4)2}2(m-Cl)2] (6) with 2 and 4 led to decomposition. On
Scheme 1 Synthesis of organorhodium inner complexes 8a–d and 9a–d.
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Table 1 Selected NMR spectroscopic data (d in ppm, J in Hz) of [RhClL2(Ph2PCH2CH2CH2SO2Ph-kP)] (10a–d, 13, 14). The values for
PhSO2CH2CH2CH2PPh2 (1) are given for comparison
PhSO2CaH2–CbH2–Cg H2–PPh2
da-C (3JP,C db-C (2JP,C
Co-ligand L2
a
a
L2
)
)
dg-C (1JP,C
)
dP (1JRh,P
)
dP (1JRh,P
)
dP¢ (1JRh,P¢
)
10a
10b
10c
10d
13
dmpe
dppm
dppe
dppp
cod
(C2H4)2
—
58.2 (10.3)
56.8 (12.7)
57.6 (13.6)
58.2 (13.0)
57.1 (13.8)
56.7 (14.0)
56.7 (13.6)
20.7 (5.2)
19.7 (5.2)
20.1 (5.1)
21.3 (7.1)
20.0 (2.7)
19.9 (s, br)
19.5 (18.8)
27.6 (20.9)
26.3 (22.3)
26.9 (22.5)
28.0 (24.0)
26.6 (25.2)
27.9 (31.0)
26.7 (12.5)
23.7 (133.1)
23.3 (134.2)
23.7 (131.6)
25.6 (132.9)
27.8 (149.2)
48.7 (186.1)
-16.4
45.8 (137.7)
-41.5 (118.5)
58.9 (140.2)
12.9 (132.5)
—
—
—
43.3 (166.4)
-15.5 (156.0)
73.9 (184.7)
34.0 (174.9)
—
—
—
14
1
a P and P¢ are trans to P of the PhSO2CH2CH2CH2PPh2 ligand and Cl, respectively.
Scheme 2 Synthesis of organorhodium inner complexes 8a–d, 11, 12 and chloridorhodium phosphine complexes 13 and 14.
the other hand, the olefin complexes 5 and 6 reacted with the
non-lithiated g-phosphinofunctionalized propyl phenyl sulfone
1 yielding the chloridorhodium complexes 13 and 14 with
PhSO2CH2CH2CH2PPh2-kP ligands (Scheme 2). As for 7a–d,
neither 5 nor 6 was found to react with the g-aminofunctionalized
propyl phenyl sulfone 3.
9a–d but to the predominant formation (> 90%) of the cationic
bis(diphosphine)rhodium(I) complexes [Rh(P P)2]+ which have
been prepared by an alternative method before.38,39
2.2. Spectroscopic characterization
Complexes 11·LiCl, 12·LiCl, 13 and 14 were isolated with
yields between 66 and 83% as yellow to orange solids. While
[RhCl(cod)(Ph2PCH2CH2CH2SO2Ph-kP)] (13) was air-stable and
stable in chloroform as well as in methylene chloride, the com-
plexes 11·LiCl, 12·LiCl and 14 were sensitive against air and
moisture and decomposed in halogenated solvents. The identities
of all complexes have been confirmed by elemental analyses,
NMR (1H, 13C, 31P) spectroscopic investigations and single-crystal
X-ray diffraction analyses (9c·THF, 10c, 11, 12). Complex 11
could also be obtained by deprotonation of the cyclooctadiene-
chloridorhodium complex 13 with LDA. Complexes 11 and 13/14
opened up another route for the synthesis of the organorhodium
inner complexes 8a–d via ligand substitution (cod by P P) and
via ligand substitution (cod/C2H4 by P P) followed by reaction
with LDA, respectively (Scheme 2). Unexpectedly, addition of
diphosphines to the g-aminofunctionalized propyl inner complex
[Rh(cod){CH(SO2Ph)CH2CH2NMe2-kC,kN}] (12) did not lead
to the formation of the respective inner rhodium complexes
2.2.1. Rhodium complexes with PhSO2CH2CH2CH2PPh2-jP
ligands. Selected NMR spectroscopic parameters of the chlori-
dorhodium complexes with PhSO2CH2CH2CH2PPh2-kP ligands
(10a–d, 13 and 14) are given in Table 1. The 31P NMR spectra of
complexes 10b–d are of first order with an AEMX spin system
(A, E, M = 31P; X = 103Rh) whereas that of 10a is of higher order
(ABMX spin system) which was analyzed by using the PERCH
software package.40 Although in 10a the 13C atoms of the propyl
chain are part of a higher order spin systems, simulations with the
PERCH software exhibited that they can be treated as first order.
1
In type 10 complexes the differences in the two JRh,P coupling
constants of the P P co-ligand between DJ = 12.7 Hz (10a) and
DJ = 44.5 Hz (10c) allowed the assignment of the P atoms trans to
the PhSO2CH2CH2CH2PPh2 (1JRh,P = 118.5–141.4 Hz) and trans
to the chlorido ligand (1JRh,P = 154.1–184.7 Hz), respectively, as
given in Table 1. The kP coordination of the g-phosphinopropyl
phenyl sulfone ligand is clearly shown by the lowfield shift of
the 31P nucleus by about 40 ppm for type 10 complexes. The
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Table 2 Selected NMR spectroscopic data (d in ppm, J in Hz) of organorhodium inner complexes [Rh{CH(SO2Ph)CH2CH2YR2-kC,kY}L2] (8a–d,
9a–d, 11, 12). The values for PhSO2CH2CH2CH2PPh2 (1) and PhSO2CH2CH2CH2NMe2 (3) are given for comparison
PhSO2CaH–CbH2–Cg H2–YR2
Co-ligand L2
dP (1JRh,P
L2/YR2
da-C
db-C (2JP,C
)
dg-C (1JP,C
)
dP (1JRh,P
)
)
dP¢ (1JRh,P¢
)
8a
8b
8c
8d
9a
9b
9c
9d
11
12
1
dmpe/PPh2
dppm/PPh2
dppe/PPh2
dppp/PPh2
dmpe/NMe2
dppm/NMe2
dppe/NMe2
dppp/NMe2
cod/PPh2
cod/NMe2
—
61.0–61.8 (m)
61.6–62.6 (m)
61.1–63.0 (m)
66.1–67.0 (m)
57.0 (9.1/69.2)b
57.1 (7.0/68.8)b
60.9 (7.9/67.9)b
61.4 (8.9/67.0)b
63.0 (4.6)d
30.3 (19.5)
28.5 (17.3)
29.5 (24.0)
29.5 (14.4)
30.6
30.4
30.4
29.8
29.7 (13.3)
30.6
19.5 (18.8)
20.7
36.5 (22.9)
34.2 (23.3)
35.0 (22.2)
37.5 (23.8)
66.3
65.8
66.3
66.4
33.0 (26.9)
66.5
26.7 (12.5)
57.2
58.0 (144.3)
57.9 (154.8)
55.5 (153.1)
55.6 (156.0)
—
—
—
—
52.0 (172.0)
—
–16.4
—
35.8 (128.8)a
13.7 (113.5)a
59.3 (133.0)a
16.3 (127.1)a
28.3 (148.2)c
-17.2 (125.0)c
58.2 (150.5)c
14.2 (141.3)c
—
35.5 (144.8)a
-21.0 (133.7)a
61.1 (155.5)a
19.5 (150.1)a
47.1 (175.9)c
-1.7 (165.5)c
76.0 (188.1)c
37.8 (187.8)c
—
54.9
—
—
—
—
—
—
56.7 (13.6)e
54.0
3
—
a P and P¢ are trans to C and to P of the P
CHSO2Ph ligand, respectively. b 2JP,C coupling constants to the P atoms (cis/trans) of the P
P co-ligand L2.
2
e
c P and P¢ are trans to C and to N of the PhSO2CHCH2CH2NMe2 ligand, respectively. d JP,C
. .
3JP,C
1JRh,P couplings between 131.6 and 134.2 Hz are typical for
phosphorus atoms having another P atom in trans position.41–43
The coordination induced shifts of the aliphatic carbon atoms
of the PhSO2CH2CH2CH2PPh2 ligand proved to be small (up to
1.8 ppm) but considerably large for the respective proton shifts (up
to 0.68 ppm). The 1JRh,P couplings in complexes 13 (149.2 Hz) and
14 (186.1 Hz) are as expected for 31P atoms having an olefin ligand
in the trans position.44–47 The downfield shift of the 31P nucleus in 14
(d 48.7 ppm) is even larger than in 10a–d and 13 (d 23.3–27.8 ppm)
but still in the usual region.48,49 Compared to [{Rh(cod)}2(m-Cl)2]
=
(5; –CH CH–: dC 78.7 ppm, dH 4.18 ppm) and [{Rh(C2H4)2}2(m-
=
Cl)2] (6; CH2 CH2: dC 60.7 ppm, dH 3.10 ppm), in the olefin
complexes 13 and 14 the olefin carbon atoms and protons are no
longer chemically equivalent and were found at dC 70.6/105.3 ppm
d
H 2.96/5.40 ppm (13) and at dC 48.2 (br) ppm dH 2.05/2.90 ppm
Fig. 1 Simulated (above) and measured (81 MHz, below) 31P NMR spec-
trum of [Rh{CH(SO2Ph)CH2CH2PPh2-kC,kP}(dmpe)] (8a). The ABM
part of the ABMX spin system is shown (A, B, M = 31P; X = 103Rh).
(br/br) (14). The broadening of these signals in complex 14 and
of the aliphatic protons of the phosphino ligand may indicate
molecular dynamics possibly an exchange of the ethylene ligand
by solvent molecules (THF).
2.2.2. Organorhodium inner complexes. Selected NMR spec-
troscopic parameters of the organorhodium inner complexes (8a–
d, 9a–d, 11, 12) are given in Table 2. The 31P NMR spectra of
complexes 8b, 9a–d and 11 are of first order with AEMX (A,
E, M = 31P; X = 103Rh) (8b), AMX (9a–d) and AX spin systems
(11). The 31P nuclei in complexes 8a and 8d are part of ABMX
spin systems (A, B, M = 31P; X = 103Rh) (Fig. 1) and those of 8c
of an ABCX system (Fig. 2). In complexes 8a–d the signals of the
a-C atoms proved to be of too high multiplicity to be analyzed
whereas, as for 10a, the signals of the b- and g-C atoms in 8a
and 8d could be analyzed as first order spectra. For complex 8c
n
the JP,C coupling constants (n = 1, 2, Table 2) were obtained by
simulation the ABCMX spin systems (A, B, C = 31P; M = 13C;
X = 103Rh) using the PERCH software. Due to the less multiplicity
in complexes 9a–d all coupling constants were obtained directly
from the spectra, among them the 1JRh,C couplings (25.5–27.1 Hz).
In the organorhodium inner complexes 8a–d the differences
Fig. 2 Simulated (above) and measured (81 MHz, below) 31P NMR
spectrum of [Rh{CH(SO2Ph)CH2CH2PPh2-kC,kP}(dppe)] (8c). The ABC
part of the ABCX (A, B, C = 31P, X = 103Rh) spin system is shown.
and the C atom (1JRh,P = 113.5–133.0 Hz) of the P CHSO2Ph
ligand, respectively. In complexes 9a–d the differences between
the two 1JRh,P coupling constants (DJ = 27.7–46.5 Hz) are greater
due to the smaller trans influence of the NMe2 compared to the
between the two 1JRh,P coupling constants of the co-ligand P
P
from DJ = 16.0 Hz (8a) to DJ = 23.0 Hz (8d) allowed the
assignment of the P atoms trans to the P (1JRh,P = 133.7–155.5 Hz)
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PPh2 group.50,51 In the case of complexes 8 these assignments
were further confirmed by the magnitudes of the JP,P coupling
constants: the P atoms of the P P ligands trans to C have two cis-
couplings whereas the P¢ atoms (trans to P of the P CHSO2Ph
The O1–S–O2 (118.4(2)◦) and C29–S–C42 (103.9(2)◦) angles
were found to be as those in sulfones (median O–S–O: 118.6◦,
lower/higher quartile: 117.9/119.3◦ n = 2490; median C–S–C:
105.0◦, lower/higher quartile: 103.6/103.4◦ n = 2490; n–number
of observations60).
2
ligand) have one trans- and one cis-coupling. Both, the cis (2JP,Pcis
25.8–67.7 Hz) as well as the trans coupling constants (2JP,Ptrans
=
=
2.3.2. Structures of organorhodium inner complexes. Crys-
tals of [Rh{CH(SO2Ph)CH2CH2NMe2-kC,kN}(dppe)]·THF (9c·
THF), [Rh{CH(SO2Ph)CH2CH2PPh2-kC,kP}(cod)] (11) and
[Rh{CH(SO2Ph)CH2CH2NMe2-kC,kN}(cod)] (12) suitable for
X-ray diffraction analyses were obtained from THF/n-pentane
(9c·THF, 12) and THF (11), respectively, at room temperature.
All compounds crystallized in isolated molecules without un-
usual intermolecular interactions (shortest distance between non-
310.8–340.5 Hz) are in the expected range52,53 Deprotonation of
1/3 and the kC,kP/kC,kN coordination of the resulting anions
to Rh gives rise to lowfield shifts of the a-C atoms by 5–10 ppm
and of the P atoms (8a–d) by about 70 ppm. The greater trans
influence of the PPh2 group in complexes 8a–d compared to the
NMe2 group in complexes 9a–d is reflected in markedly smaller
(by 31–38 Hz) coupling constants between Rh and the P atom in
trans position. In the inner complex 11 having a cod co-ligand the
1JRh,P coupling constant was found to be greater by about 20 Hz
compared to 8a–d reflecting the order of the trans influence cod <
diphosphines.
˚
˚
hydrogen atoms: 3.722(7) A, C19 ◊ ◊ ◊ C4¢, 9c·THF; 3.183(6) A,
˚
O1 ◊ ◊ ◊ C12¢, 11; 3.285(5) A, C4 ◊ ◊ ◊ C4¢, 12). The molecular struc-
tures are shown in Fig. 4–6. Selected structural parameters are
given in the figure captions. In all three complexes the rhodium
atoms are located in the center of a distorted square planar
environment. The primary donor sets of the rhodium atoms are
built up by a bidentate neutral ligand (1,5-cyclooctadiene, 11, 12;
dppe, 9c·THF) and by a bidentate anionic a-phenylsulfonyl g-
phosphinopropyl (11) and g-aminopropyl ligand (12, 9c·THF)
with a kC,kP and a kC,kN coordination, respectively. In all
three complexes the five-membered rhodacycles RhYC3 reveal
quite small C1–Rh–Y angles (81.3(7)–82.1(1)◦) pointing to a
relatively small bite of the chelate ligand. While the two nitrogen
containing rhodacycles RhNC3 in 9c·THF and 12 adopt a half-
chair configuration twisted on C2 and C3 the metallacycle RhPC3
in 11 adopts an envelope configuration on C3.
2.3. Structural investigations
2.3.1. Structure of [RhCl(dppe)(Ph2PCH2CH2CH2SO2Ph-
jP)] (10c). Crystals of 10c suitable for X-ray diffraction analysis
were obtained from THF/n-pentane at room temperature. The
compound crystallized in isolated monomeric molecules without
unusual intermolecular interactions (shortest distance between
˚
non-hydrogen atoms: 3.240(5) A, O2 ◊ ◊ ◊ C46¢). The molecular
structure is shown in Fig. 3, selected structural parameters are
given in the figure caption. The rhodium atom is square-planar
coordinated by the two phosphorus atoms of the dppe ligand, by
the phosphorus atom of the phosphinofunctionalized sulfone as
well as by a chlorido ligand. Due to the bite of the dppe ligand
the P1–Rh–P2 angle (85.2(4)◦) is slightly diminished. The five-
membered rhodacycle (RhP2C2) adopts a half-chair conformation,
twisted on the two C atoms. The Rh–P3 and Rh–P2 bonds
˚
(2.320(1)/2.263(1) A) are in the expected range for P atoms having
another phosphorus atom in trans position.54–56 As expected, the
˚
Rh–P1 bond (2.179(1) A) is shorter than the other two Rh–P
bonds due to the smaller trans influence of the chlorido ligand.57–59
Fig. 4 Molecular structure of [Rh{CH(SO2Ph)CH2CH2NMe2-kC,kN}-
(dppe)] in crystals of 9c·THF. The ellipsoides are shown with a probability
of 50%. H atoms have been omitted for clarity. Selected structural
◦
˚
parameters (distances in A, angles in ): Rh–P1 2.258(1), Rh–P2 2.191(1),
Rh–C1 2.161(4), Rh–N 2.222(4), P1–Rh–P2 83.5(4), P1–Rh–N 99.8(9),
P2–Rh–C1 94.1(1), N–Rh–C1 82.1(1), P1–Rh–C1 175.1(1), P2–Rh–N
172.6(1).
Obviously due to the greater size of the P atom (compared to
˚
the N atom) the Rh–C1 bond in 11 is longer (2.181(3) A) than
Fig. 3 Molecular structure of [RhCl(dppe)(Ph2PCH2CH2CH2SO2Ph-
kP)] in crystals of 10c. The ellipsoides are shown with a probability
of 50%. H atoms have been omitted for clarity. Selected structural
˚
˚
in complexes 9c·THF (2.161(4) A) and 12 (2.149(3) A). On the
˚
other hand, the Rh–P bond in 11 (2.264(8) A) is slightly shorter
parameters (distances in A, angles in ◦): Rh–Cl 2.391(1), Rh–P1 2.179(1),
˚
than those in other rhodium(I) complexes with P ligands having
an olefin ligand in trans and a carbanion in cis position (median:
Rh–P2 2.263(1), Rh–P3 2.320(1), Cl–Rh–P2 89.0(3), Cl–Rh–P3 89.9(3),
P1–Rh–P2 85.2(4), P1–Rh–P3 95.8(3), Cl–Rh–P1 174.1(3), P2–Rh–P3
176.6(4), C29–S–C42 103.9(2), O1–S–O2 118.4(2).
60
˚
˚
2.298 A, lower/higher quartile: 2.278/2.325 A, n = 15 ). The
bidentate binding of the co-ligands L2 (dppe, 9c·THF; cod, 11, 12)
4640 | Dalton Trans., 2010, 39, 4636–4646
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gives rise to slightly diminished P1–Rh–P2 (83.5(4)◦, 9c·THF)
and C22/23cg–Rh–C26/27cg (85.4(9)◦, 11; 87.0(9)◦, 12; cg =
center of gravity) angles. The difference in the Rh–P bond lengths
˚
by 0.067 A in 9c·THF can be attributed to the difference in the
trans influence of a neutral N and an anionic C ligand and is in
the usual range.61–63
2.4 Conclusion
To summarize (Scheme 3), organorhodium inner complexes of the
type [Rh{CH(SO2Ph)CH2CH2YR2-kC,kY}L2] (III, IV; YR2 =
PPh2, NMe2; L2 = P P, cod) were prepared by reactions of
lithiated g-phosphino- and g-aminofunctionalized propyl phenyl
sulfones with the requisite dinuclear complexes [(RhL2)2(m-Cl)2]
(I → III, II → IV; Scheme 3). While in the case of the rhodaphos-
phacyclic complexes cod could be substituted by diphosphines
(III → IV), the respective reactions of the azarhodacyclic com-
plexes resulted with cleavage of both the organo ligands and the
cod co-ligand only in the formation of cationic bis(diphosphine)
complexes (III → V). Furthermore, chloridorhodium complexes
with neutral PhSO2CH2CH2CH2PPh2-kP ligands were obtained
in reactions of [(RhL2)2(m-Cl)2] (L2 = P P, cod, (C2H4)2) with
the phosphinofunctionalized sulfones (I/II → VI) whereas the
aminofunctionalized sulfones did not react at all. Syntheses of type
VI complexes opened up a way to prepare the inner complexes
III/IV by deprotonation the P coordinated sulfone with LDA
(VI → III/IV).
Fig. 5 Molecular structure of [Rh{CH(SO2Ph)CH2CH2PPh2-kC,kP}-
(cod)] in crystals of 11. The ellipsoides are shown with a prob-
ability of 50%.
H
atoms have been omitted for clarity. Selected
˚
structural parameters (distances in A, angles in ◦): Rh–P 2.264(8),
Rh–C22/23cg (cg
=
center of gravity) 2.142(4), Rh–C1 2.181(3),
Rh–C26/27cg 2.057(3), P–Rh–C26/27cg 95.3(2), C26/27cg–Rh–C22/23cg
85.4(9), P–Rh–C1 81.3(7), C22/23cg–Rh–C1 98.1(1), P–Rh–C22/23cg
177.8(2), C1–Rh–C26/27cg 175.4(7).
As shown here (I/II → VI) and as well known from numer-
ous reactions described in literature64 the cleavage of Rh–Cl–
Rh bridges by phosphines proceeds smoothly under formation
of phosphine rhodium complexes irrespective of the type of
the phosphine. Although analogous reactions of [{Rh(cod)}2(m-
Cl)2] with pyridines, secondary amines and diamines have been
described to proceed in most cases either with the formation
of type [RhCl(cod)L] or [Rh(cod)L2]+ complexes, the tertiary
aliphatic amine NEt3 was found not to react at all.65 Moreover,
in analogous reactions of iminophosphoranes with dinuclear
rhodium complexes [(RhL2)2(m-Cl)2] (L2 = cod, (CO)2) it was
shown that the reactivity of these ligands strongly depends on
the nucleophilicity of the N atom.66,67 Furthermore, the ease
Fig. 6 Molecular structure of [Rh{CH(SO2Ph)CH2CH2NMe2-kC,kN}-
(cod)] in crystals of 12. The ellipsoides are shown with a probability
of 50%. H atoms have been omitted for clarity. Selected structural
parameters (distances in A, angles in ◦): Rh–N 2.175(3), Rh–C22/23cg
˚
2.011(2), Rh–C1 2.149(3), Rh–C26/27cg 2.061(2), N–Rh–C26/27cg 94.6(7),
C26/27cg–Rh–C22/23cg 87.0(9), N–Rh–C1 81.6(1), C22/23cg–Rh–C1
97.1(8), N–Rh–C22/23cg 176.5(7), C1–Rh–C26/27cg 174.0(8).
Scheme 3 Different routes to organorhodium inner complexes.
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of cleaving Rh–N bonds as found in the reactions III → V
(Scheme 3) was demonstrated on similar complexes by reaction
of [RhCl(olefin)(i-PrPCH2CH2NMe2-kP,kN)] with CO, C2H4 and
H2.46 On the basis of all these findings the different reactivity of
g-phosphinopropyl and g-aminopropyl phenyl sulfones towards
dinuclear chloridobridged rhodium complexes can be understood.
Thus, an easy access to a series of new organorhodium inner
complexes bearing a-deprotonated sulfone ligands having an
additional P or N donor site was found.
mixture was stirred for 1 h at room temperature, cooled to -78 ◦C
again and LDA (0.55 ml, 0.50 mmol, 0.91 M in THF) was slowly
added. After warming to room temperature the mixture was stirred
for 30 min. The precipitated LiCl was filtered, the filtrate was
reduced to half of its volume and n-pentane (5 mL) was added.
The precipitated compound was filtered, washed with n-pentane
(3 ¥ 5 mL) and dried in vacuo.
Route C. At room temperature to a stirred suspension of
[{RhL2}2(m-Cl)2] (L2 = cod, 5; (C2H4)2, 6; 0.25 mmol) in toluene
(5 mL) PhSO2CH2CH2CH2PPh2 (1) (168.2 mg, 0.50 mmol)
dissolved in toluene (10 mL) was added slowly. After stirring for
3 h the respective diphosphine P P (0.50 mmol) dissolved in
toluene (5 mL) was added. The reaction mixture was stirred for
3. Experimental
3.1. General comments
◦
All reactions and manipulations were carried out under argon us-
ing standard Schlenk techniques. Diethyl ether, toluene, n-pentane,
and THF were dried over Na/benzophenone and freshly distilled
prior to use. NMR spectra (1H, 7Li, 13C, 31P) were recorded at 27 ◦C
on Varian Gemini 200, VXR 400, and Unity 500 spectrometers.
Chemical shifts are relative to solvent signals (CDCl3, dH 7.24, dC
77.0; CD2Cl2, dH 5.32, dC 53.8; C6D6, dH 7.15, dC 128.0; THF-
d8, dH 1.73/3.58, dC 25.4/67.6; CD3NO2, dH 4.33, dC 62.8) as
internal references; d(7Li) is relative to external LiCl (1 M in H2O);
d(31P) is relative to external H3PO4 (85%). Multiplets in NMR
spectra of higher order resulting in pseudo doublets and triplets
are denoted by “d” and “t”, respectively; the distance between the
outer lines is given as N. Coupling constants JP,P and JP,Rh from
higher order multiplets (“m”) were obtained by using the PERCH
NMR software package.40 For couplings in ring systems only the
shortest coupling path is given. Microanalyses (C, H, N) were
performed in the Microanalytical Laboratory of the University
of Halle using a CHNS-932 (LECO) as well as a VARIO EL
elemental analyzer. [{Rh(cod)}2(m-Cl)2] (5), [{Rh(C2H4)2}2(m-Cl)2]
(6) and [{Rh(P P)}2(m-Cl)2] (7a–d) were prepared according to
literature procedures.68,45,69 Details of the preparation of starting
compounds and a complete set of their NMR spectroscopic
data are given in the ESI.† Li[CH(SO2Ph)CH2CH2PPh2] (2) and
Li[CH(SO2Ph)CH2CH2NMe2] (4) were obtained by addition of
n-BuLi (0.31 ml, 0.50 mmol, 1.6 M in n-hexane) at -78 ◦C to
a solution of PhSO2CHCH2CH2YR2 (YR2 = PPh2, 1; NMe2, 3;
0.50 mmol) in toluene (5 mL). Compounds 2 and 4 were used
as obtained after stirring the reaction mixtures for 4 h at room
temperature.
3 h, at -78 C LDA (0.55 mL, 0.50 mmol, 0.91 M in THF) was
slowly added and stirred for further 30 min at room temperature.
The precipitated LiCl was filtered, the filtrate was reduced to half
of its volume and n-pentane (5 mL) was added. The precipitated
compound was filtered, washed with n-pentane (3 ¥ 5 mL) and
dried in vacuo.
P
P = dmpe (8a). Yield: 229 mg (74%, route A). Found:
C, 52.41; H, 5.73; Calcd. for C46H41P3SO2Rh (620.48): C, 52.27;
H, 5.85. H NMR (400 MHz, THF-d8): d 0.79/0.91/1.65/1.69
1
(d/d/d/d, 2J(1H,31P) = 7.5/7.5/8.3/8.3 Hz, 3H/3H/3H/3H,
P(CH3)2), 1.18–1.44 (m, 2H, CHCH2CH2), 1.35–1.39/1.57–1.82
(m/m, 2H/2H, Me2PCH2CH2PMe2), 3.55 (s, br, 1H, CHSO2Ph),
7.28–7.38 (m, 10H, m-, p-, o-H PPh2), 7.69–7.82 (m, 5H, m-, p-, o-
H SO2Ph). 13C NMR (100 MHz, THF-d8): d 15.4/15.7/17.8/18.1
(d/d/d/d, 1J(13C,31P) = 20.6/19.3/21.8/22.1 Hz, PCH3), 30.3
(d, 2J(13C,31P) = 19.5 Hz, CHCH2CH2), 31.5/31.7 (“d”/“d”,
1
N = 23.1/22.2 Hz Me2PCH2CH2PMe2), 36.5 (dd, J(13C,31P) =
22.9 Hz, 3J(13C,31Ptrans) = 7.1 Hz, CHCH2CH2), 61.0–61.8 (m,
CHSO2Ph), 128.3–146.9 (CAr). 31P NMR (81 MHz, THF-d8):
d 35.5 (m, 2J(31P,31P) = 34.9 Hz, 2J(31P,31P) = 332.9 Hz,
1J(31P,103Rh) = 144.8 Hz, P (dmpe) trans to P), 35.8 (m,
2J(31P,31P) = 34.9 Hz, 2J(31P,31P) = 29.9 Hz, 1J(31P,103Rh) =
128.8 Hz, P (dmpe) trans to C), 58.0 (ddd, 2J(31P,31P) = 29.9 Hz,
2J(31P,31P) = 332.9, 1J(31P,103Rh) = 144.3 Hz, CHCH2CH2PPh2).
P
P = dppm (8b). Yield: 377 mg (88%, route A). Found: C,
64.74; H, 5.09; Calcd for C46H42P3SO2Rh (854.73): C, 64.64; H,
4.95. 1H NMR (400 MHz, THF-d8): d 1.27–1.36/1.51–1.69 (m/m,
1H/1H, CHCH2CH2), 2.11/2.76 (m/m, 1H/1H, CHCH2CH2),
3.68 (m, 1H, CHSO2Ph), 3.91–3.99/4.29–4.37, (m/m, 1H/1H,
Ph2PCH2PPh2), 6.94–8.06 (m, 35H, HAr).
13C NMR (100 MHz, THF-d8): d 28.5 (d, 2J(13C,31P) =
3.2. Preparation of [Rh{CH(SO2Ph)CH2CH2PPh2-
jC,jP}(P P)] (8a–d)
17.3 Hz, CHCH2CH2), 34.2 (dd, 1J(13C,31P)
=
23.3 Hz,
3J(13C,31Ptrans) = 4.7 Hz, CHCH2CH2), 48.6 (“t”, N = 35.2 Hz,
Ph2PCH2PPh2), 61.6–62.6 (m, CHSO2Ph), 125.0–145.2 (m, CAr).
31P NMR (81 MHz, THF-d8): d–21.0 (ddd, 2J(31P,31P) = 67.7 Hz,
Route A. Li[CH(SO2Ph)CH2CH2PPh2] (2) (0.50 mmol) dis-
solved in toluene (5 mL) was added slowly via a syringe to a sus-
pension of the respective rhodium complex [{Rh (m-Cl)(P P)}2]
(7a–d) (0.25 mmol) in toluene (5 mL) at -78 ◦C. After warming to
room temperature the mixture was stirred overnight and filtered to
separate the precipitated LiCl. The filtrate was reduced to half of its
volume and n-pentane was added (5 mL). The resulted precipitate
was filtered, washed with n-pentane (3 ¥ 5 mL) and dried in vacuo.
2J(31P,31P) = 340.5 Hz, J(31P,103Rh) = 133.7 Hz, P(dppm) trans
1
to P), 13.7 (ddd, J(31P,31P) = 67.7 Hz, J(31P,31P) = 32.1 Hz,
1J(31P,103Rh) = 113.5 Hz, P(dppm) trans to C), 57.9 (ddd,
2J(31P,31P) = 32.1 Hz, 2J(31P,31P) = 340.58, 1J(31P,103Rh) = 154.8 Hz,
CHCH2CH2PPh2).
2
2
P
P = dppe (8c). Yield: 375 mg (86%, route A). Found:
Route B:. At -78 ◦C to a stirred suspension of the respective
rhodium complex [{Rh(P P)}2(m-Cl)2] (7a–d) (0.25 mmol) in
toluene (5 mL) PhSO2CH2CH2CH2PPh2 (1) (184.2 mg, 0.50 mmol)
in toluene (5 mL) was added via a syringe. Then the reaction
C, 64.32; H, 5.20; Calcd. for C47H44P3SO2Rh (868.76): C,
64.98; H, 5.10. 1H NMR (400 MHz, THF-d8): d 1.13–
1.25/1.70–1.84 (m/m, 1H/1H, CHCH2CH2), 1.95–2.20/2.36–
2.51 (m/m, 2H/2H, Ph2PCH2CH2PPh2), 2.21–2.30/2.99–3.09
4642 | Dalton Trans., 2010, 39, 4636–4646
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(m/m, 1H/1H, CHCH2CH2PPh2), 3.53 (s, br, 1H, CHSO2Ph),
6.89–7.88 (m, 35H, HAr). 13C NMR (100 MHz, THF-d8):
d 27.0/30.2 (m/m, CHCH2CH2/Ph2PCH2CH2PPh2), 29.5 (d,
2J(13C,31P) = 24.0 Hz, CHCH2CH2), 35.0 (dd, 1J(13C,31P) =
22.2 Hz, 3J(13C,31Ptrans) = 7.0 Hz, CHCH2CH2), 61.1–63.0 (m,
CHSO2Ph), 127.2–145.6 (CAr). 31P NMR (81 MHz, THF-d8):
d 55.5 (m, 2J(31P,31P) = 31.7 Hz, 2J(31P,31P) = 321.8 Hz,
1J(31P,103Rh) = 153.1 Hz, CHCH2CH2PPh2), 59.3 (m, 2J(31P,31P) =
28.7 Hz, 2J(31P,31P) = 31.7 Hz, 1J(31P,103Rh) = 133.0 Hz, P (dppe)
51.7–52.2 (m, Ph2PCH2PPh2/N(CH3)2), 57.1 (ddd, 2J(13C,31Pcis) =
7.0 Hz, 2J(13C,31Ptrans) = 68.8 Hz, 1J(13C,103Rh) = 27.1 Hz
CHSO2Ph), 65.8 (s, CH2NMe2), 127.3–146.4 (m, CAr). 31P
2
NMR (81 MHz, THF-d8): d -17.2 (dd, J(31P,31P) = 83.7 Hz,
2
1J(31P,103Rh) = 125.0 Hz, P trans to C),–1.7 (dd, J(31P,31P) =
83.7 Hz, 1J(31P,103Rh) = 165.5 Hz, P trans to N).
P
P = dppe (9c). Yield: 277 mg (76%). Found: C, 61.47;
H, 5.54; N, 1.79; Calcd. for C37H40NP2SO2Rh (727.66): C,
61.08; H, 5.50; N, 1.92. H NMR (500 MHz, THF-d8): d 1.11–
1
2
2
trans to C), 61.1 (m, J(31P,31P) = 28.7 Hz, J(31P,31P) = 321.8
1.20/1.25–1.34 (m/m, 1H/1H, CHCH2CH2), 1.45–1.52/1.83–
1J(31P,103Rh) = 155.5 Hz, P (dppe) trans to P).
1.89/2.13–2.22/2.23–2.30
(m/m/m/m,
1H/1H/1H/1H,
P
P = dppp (8d). Yield: 401 mg (91%, route A). Found:
Ph2PCH2CH2PPh2), 2.10/3.23 (m/m, 1H/1H, CHCH2CH2),
2.17/2.48 (s/s, 3H/3H, N(CH3)2), 2.66 (s, br, CHSO2Ph),
7.07–8.18 (m, 25H, HAr). 13C NMR (100 MHz, THF-d8): d 30.2–
30.6/34.2–34.8 (m/m, Ph2PCH2CH2PPh2), 30.4 (s, CHCH2CH2),
51.8/52.6 (s/s, N(CH3)2), 60.9 (ddd, 2J(13C,31Pcis) = 7.9 Hz,
C, 65.55; H, 5.01; Calcd. for C48H46P3SO2Rh (882.78): C,
65.31; H, 5.25. 1H NMR (400 MHz, THF-d8): d 0.74–
0.88/1.62–1.76 (m/m 1H/1H, CHCH2CH2), 1.21–1.42/2.01–
2.09 (m/m, 1H/1H, Ph2PCH2CH2CH2PPh2), 2.01–2.09/2.93
(m/m 1H/1H, CHCH2CH2), 2.13–2.25/2.70 (m/m 2H/2H,
Ph2PCH2CH2CH2PPh2), 2.81 (s, br, 1H, CHSO2Ph), 6.55–
1
2J(13C,31Ptrans) = 67.9 Hz, J(13C,103Rh) = 25.5 Hz, CHSO2Ph),
66.3 (s, CH2NMe2), 126.1–146.2 (m, CAr). 31P NMR (81 MHz,
THF-d8): d 58.2 (dd, 2J(31P,31P) = 30.1 Hz, 1J(31P,103Rh) =
150.5 Hz, P trans to C), 76.0 (dd, 2J(31P,31P) = 30.1 Hz,
1J(31P,103Rh) = 188.1 Hz, P trans to N).
8.08 (m, HAr). 13C NMR (125 MHz, THF-d8):
d 21.5
(s, Ph2PCH2CH2CH2PPh2), 29.5 (d, 2J(13C,31P) = 14.4 Hz,
CHCH2CH2), 30.0/30.9 (“d”/“d”,
N
=
23.6/18.5 Hz,
Ph2PCH2CH2CH2PPh2), 37.5 (dd, 1J(13C,31P)
=
23.8 Hz,
P
P = dppp (9d). Yield: 270 mg (73%). Found: C, 61.00; H,
3J(13C,31Ptrans) = 5.2 Hz, CHCH2CH2), 66.1–67.0 (m, CHSO2Ph),
126.4–147.1 (m, CAr). 31P NMR (81 MHz, THF-d8): d 16.3 (m,
2J(31P,31P) = 25.8 Hz , 2J(31P,31P) = 52.1 Hz, 1J(31P,103Rh) =
5.74; N, 1.91; Calcd. for C38H42NP2SO2Rh (741.69): C, 61.55; H,
5.71; N, 1.89. 1H NMR (500 MHz, benzene-d6): d 1.34–1.55 (m,
2H/2H, Ph2PCH2CH2CH2PPh2/CHCH2CH2), 1.79–1.83/1.92–
2.02/2.20–2.28 (m/m/m, 1H/2H/1H, Ph2PCH2CH2CH2PPh2),
2.15 (s, br, 6H, N(CH3)2), 2.31–2.40/2.60 (m/m, 1H/1H,
127.1 Hz, P (dppp) trans to C), 19.5 (m, J(31P,31P) = 52.1 Hz,
2
2J(31P,31P) = 310.8 Hz, 1J(31P,103Rh) = 150.1 Hz, P (dppp)
trans to P), 55.6 (m, J(31P,31P) = 25.8 Hz, J(31P,31P) = 310.8,
CHCH2CH2), 3.20 (s, br, CHSO2Ph), 6.86–8.49 (m, 25H, HAr). 13
NMR (100 MHz, benzene-d6): d 19.4 (s, Ph2PCH2CH2CH2PPh2),
C
2
2
1J(31P,103Rh) = 156.0 Hz, CHCH2CH2PPh2).
28.2/28.9 (dd/dd, 1J(13C,31P)
=
29.7 Hz, 2J(13C,103Rh)
=
10.4 Hz/1J(13C,31P) 26.3 Hz, 2J(13C,103Rh)
=
=
10.9 Hz
3.3. Preparation of [Rh{CH(SO2Ph)CH2CH2NMe2-
jC,jN}(P P)] (9a–d)
Ph2PCH2CH2CH2PPh2), 29.8 (s, CHCH2CH2), 53.85/53.89 (s/s,
N(CH3)2), 61.4 (ddd, 2J(13C,31Pcis) = 8.9 Hz, 2J(13C,31Ptrans) =
67.0 Hz, 1J(13C,103Rh) = 26.4 Hz CHSO2Ph), 66.4 (s, CH2NMe2),
127.0–145.8 (m, CAr). 31P NMR (81 MHz, benzene-d6): d 14.2
(dd, 2J(31P,31P) = 54.4 Hz, 1J(31P,103Rh) = 141.3 Hz, P trans to C),
Complexes 9a–d were obtained as described in 3.2 (route A) but
using Li[CH(SO2Ph)CH2CH2NMe2] (4) (0.50 mmol) instead of 2.
P
P
=
dmpe (9a). Yield: 114 mg (48%). Found:
2
1
C, 43.01; H, 6.51; N, 2.92; Calcd. for C17H32NP2SO2Rh
(479.38): C, 42.60; H, 6.73; N, 2.86. 1H NMR (400 MHz,
THF-d8):
6.2/6.3/9.3/9.6 Hz, 3H/3H/3H/3H, P(CH3)2), 1.50–1.66 (m,
4H, Me2PCH2CH2PMe2), 1.77–1.98 (m, 2H, CHCH2CH2), 2.14
(m, 2H, CH2NMe2), 2.61/2.71 (s/s, 3H/3H, N(CH3)2), 2.84–
2.91 (m, 1H, CHSO2Ph), 7.31–7.40 (m, 3H, m-, p-H, SO2Ph),
7.74–7.83 2H, o-H, SO2Ph). 13C NMR (100 MHz, THF-d8):
d 16.9–17.6 (m, ((CH3)2PCH2CH2P(CH3)2), 29.7–30.2/32.3–31.8
37.8 (dd, J(31P,31P) = 54.4 Hz, J(31P,103Rh) = 187.8 Hz, P trans
to N).
d
1.31/1.44/1.56/1.62 (d/d/d/d, 2J(1H,31P)
=
3.4. Preparation of [RhCl(P P)(Ph2PCH2CH2CH2SO2Ph-
jP)] (10a–d)
At room temperature to a stirred suspension of the respective
rhodium complex [{Rh(P P)}2(m-Cl)2] (7a–d; 0.25 mmol) in
toluene (5 mL) PhSO2CH2CH2CH2PPh2 (1) (184.0 mg, 0.50 mmol)
dissolved in toluene (3 mL) was added via a syringe and the mixture
was stirred for 1 h. The solution was concentrated under reduced
pressure to half of its volume before n-pentane (5 mL) was added.
The resulted precipitate was filtered off, washed with n-pentane
(3 ¥ 5 mL) and dried in vacuo.
(m/m, Me2PCH2CH2PMe2), 30.6 (s, CHCH2CH2), 51.8/52.5 (s/s,
31
N(CH3)2), 57.0 (ddd, 2J(13C,31Pcis) = 9.1 Hz, 2J(13C,
P
) =
trans
69.2 Hz, 1J(13C,103Rh) = 25.5 Hz, CHSO2Ph), 66.3 (s, CH2NMe2),
128.1 (s, m-C, SO2Ph), 128.5 (s, o-C, SO2Ph), 130.4 (s, p-C, SO2Ph),
146.9 (s, i-C, SO2Ph). 31P NMR (81 MHz, THF-d8): d 28.3 (dd,
2J(31P,31P) = 29.6 Hz, 1J(31P,103Rh) = 148.2 Hz, P trans to C), 47.1
(dd, 2J(31P,31P) = 29.6 Hz, 1J(31P,103Rh) = 175.9 Hz, P trans to N).
P
P = dmpe (10a). Yield: 212 mg (65%). Found: C
50.90, H, 5.76; Calcd. for C27H37ClP3SO2Rh (656.95): C, 49.37;
H, 5.68. 1H NMR (400 MHz, THF-d8): 0.83/1.47 (d/d,
2J(1H,31P) = 8.7/9.6 Hz, 6H/6H, P(CH3)2), 1.28–1.62 (m/m,
2H/2H, Me2PCH2CH2PMe2), 2.10–2.20 (m, 2H, CH2CH2CH2),
2.58 (m, 2H, CH2PPh2), 3.88 (“t”, N = 15.4 Hz, 2H, CH2SO2Ph),
7.06–7.92 (m, 15H, HAr). 13C NMR (100 MHz, THF-d8):
P
P = dppm (9b). Yield: 258 mg (72%). Found: C, 60.69; H,
5.11; N, 2.01; Calcd. for C36H38NP2SO2Rh (713.62): C, 60.59; H,
5.37; N, 1.96. 1H NMR (500 MHz, THF-d8): d 1.29–1.45 (m, 2H,
CHCH2CH2), 2.12–2.17/2.90–3.01(m/m, 1H/1H, CHCH2CH2),
2.23/2.78 (s/s, 3H/3H, N(CH3)2), 3.07 (m, CHSO2Ph), 3.55–
3.63/4.00–4.08 (m/m, 1H/1H, Ph2PCH2PPh2), 7.07–8.14 (m,
25H, HAr). 13C NMR (100 MHz, THF-d8): d 30.4 (s, CHCH2CH2),
14.5/17.1 (d/d, J(13C,31P) = 24.0/24.5 Hz, P(CH3)2), 20.7 (d,
1
2J(13C,31P) = 5.2 Hz, CH2CH2CH2), 26.0–26.5/34.5–35.2 (m/m,
Dalton Trans., 2010, 39, 4636–4646 | 4643
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1
Me2PCH2CH2PMe2), 27.6 (d, J(13C,31P) = 20.9 Hz, CH2PPh2),
3.5. Preparation of [Rh{CH(SO2Ph)CH2CH2PPh2-
58.2 (d, 3J(13C,31P) = 10.3 Hz, CH2SO2Ph), 125.9–141.6 (m, CAr).
jC,jP}(cod)]·LiCl (11·LiCl)
31P NMR (81 MHz, THF-d8): d 23.8 (m, J(31P,31P) = 6.5 Hz,
2
Complex 11·LiCl was obtained as described in 3.2 (route A) but
using [{Rh(cod)}2(m-Cl)2] (5) (123.3 mg, 0.25 mmol) instead of
7a–d. Yield: 245 mg (79%).
2J(31P,31P) = 355.1 Hz, 1J(31P,103Rh) = 118.0 Hz, PPh2), 43.4
(m, J(31P,31P) = 39.1 Hz, J(31P,31P) = 6.5 Hz, J(31P,103Rh) =
2
2
1
154.1 Hz, P (dmpe) trans to Cl), 45.8 (m, J(31P,31P) = 39.1 Hz,
2
Found: C, 56.72; H, 5.42; Calcd. for C29H32PLiClSO2Rh
(620.91): C, 56.10; H, 5.19. 1H NMR (400 MHz, THF-d8): d 1.87–
2.60 (m, 8H/2H/2H, 4 ¥ CH2 (cod)/CHCH2CH2/CH2PPh2),
3.08/4.00/5.93/6.24 (m/m/m/m, 1H/1H/1H/1H, 4 ¥ CH
(cod)), 3.51 (m, 1H, CHSO2Ph), 7.35–7.77 (m, 15H, HAr). 13C
NMR (100 MHz, THF-d8): d 29.4/29.9/32.6/33.4 (s/s/s/s, 4 ¥
CH2 (cod)), 29.7 (d, 2J(13C,31P) = 13.3 Hz, CHCH2CH2), 33.0 (d,
2J(31P,31P) = 355.1 Hz, J(31P,103Rh) = 141.4 Hz, P (dmpe) trans
1
to P).
P
P = dppm (10b). Yield: 336 mg (75%). Found: C, 61.55;
H, 4.83; Calcd. for C46H42ClO2P3SRh (890.19): C, 62.07; H, 4.76.
1H NMR (400 MHz, THF-d8): d 2.10 (m, 2H, CH2CH2CH2),
2.37 (m, 2H, CH2CH2CH2PPh2), 3.36 (“t”, N = 15.0 Hz, 2H,
CH2SO2Ph), 3.93 (“t”, N = 19.4 Hz, 2H, PPh2CH2PPh2), 6.99–
8.03 (m, 35H, HAr). 13C NMR (100 MHz, THF-d8): d 19.7 (d,
2J(13C,31P) = 5.2 Hz, CH2CH2CH2), 26.3 (d, 1J(13C,31P) = 22.3 Hz,
CH2CH2CH2PPh2), 49.4 (“t”, N = 42.6 Hz, PPh2CH2PPh2), 56.8
2
1J(13C,31P) = 26.9 Hz, CH2PPh2), 63.0 (dd, J(13C,31P) = 4.6 Hz,
1J(13C,103Rh) = 29.1 Hz, CHSO2Ph), 80.1/80.9/100.3/100.8
(d/d/“t”/dd, 1J(13C,103Rh) = 9.2 Hz/1J(13C,103Rh) = 8.3 Hz/N =
2
16.6 Hz/1J(13C,103Rh) = 12.0 Hz, J(13C,31P) = 6.7 Hz, 4 ¥ CH
(d, J(13C,31P) = 12.7 Hz, CH2SO2Ph), 127.9 (s, m-C, SO2Ph),
3
(cod)), 128.1–135.5 (CAr). 31P NMR (80 MHz, THF-d8): d 52.0 (d,
1J(31P, 103Rh) = 172.0 Hz, PPh2). 7Li NMR (194 MHz, THF-d8):
d 0.23 (s, LiCl).
128.0 (s, p-C, SO2Ph), 128.8 (s, o-C, SO2Ph), 140.5 (s, i-C, SO2Ph),
127.3–136.5 (CAr). 31P NMR (81 MHz, THF-d8): d -41.5 (ddd,
2J(31P,31P) = 98.4 Hz, 2J(31P,31P) = 386.0 Hz, 1J(31P,103Rh) =
118.5 Hz, P (dppm) trans to P), -15.5 (ddd, 2J(31P,31P) = 32.1 Hz,
3.6. Preparation of [Rh{CH(SO2Ph)CH2CH2NMe2-
jC,jN}(cod)]·LiCl (12·LiCl)
2J(31P,31P) = 98.4 Hz, J(31P,103Rh) = 156.0 Hz, P (dppm) trans
1
to Cl), 23.3 (ddd, J(31P,31P) = 32.1 Hz, J(31P,31P) = 386.0 Hz,
2
2
1J(31P,103Rh) = 134.2 Hz, CH2CH2CH2PPh2).
Complex 12·LiCl was obtained as described in 3.2 (route A)
but using Li[CH(SO2Ph)CH2CH2NMe2] (4) (0.50 mmol) and
[{Rh(cod)}2(m-Cl)2] (5) (123.3 mg, 0.25 mmol) instead of 2 and
7a–d, respectively. Yield: 159 mg (66%).
P
P = dppe (10c). Yield: 396 mg (88%). Found: C, 61.66; H,
5.11; Calcd. for C47H44ClO2P3SRh (904.21): C, 62.43; H, 4.90. 1H
NMR (400 MHz, CD2Cl2): d 1.77–1.89 (m, 2H, CH2CH2CH2),
1.97–2.13 (m/m, 2H/2H, PPh2CH2CH2PPh2), 2.16–2.22 (m, 2H,
CH2CH2CH2PPh2), 3.16 (“t”, N = 14.8 Hz, 2H, CH2SO2Ph),
6.88–8.01 (m, 35H, HAr)
Found: C, 47.83; H, 6.00; N, 2.96. Calcd. for
C19H28NSO2LiClRh (479.80): C, 47.56; H, 5.88; N, 2.92. 1H
NMR (400 MHz, THF-d8): d 1.01–1.09/1.39–1.50/1.98–2.63
(m/m/m, 1H/1H/6H/2H, 4¥CH2 (cod)/CH2PPh2), 1.55–1.65
13C NMR (100 MHz, CD2Cl2): d 20.1 (d, 2J(13C,31P) = 5.1 Hz,
CH2CH2CH2), 26.3/35.4 (m/m, Ph2PCH2CH2PPh2), 26.9 (d,
2
(m, 2H, CHCH2CH2), 2.74 (d“t”, J(1H,103Rh) = 2.5 Hz/N =
1J(13C,31P) = 22.5 Hz, CH2CH2CH2PPh2), 57.6 (d, J(13C,31P) =
3
5.4 Hz, 1H, CHSO2Ph), 3.81/3.90/4.64/5.21 (m/m/m/m,
1H/1H/1H/1H, 4 ¥ CH (cod)), 7.35–7.77 (m, 15H, HAr).
13.6 Hz, CH2SO2Ph), 128.2 (s, m-C, SO2Ph), 129.5 (s, p-C,
SO2Ph), 133.7 (s, o-C, SO2Ph), 139.9 (s, i-C, SO2Ph), 127.9–136.1
13C NMR (100 MHz, THF-d8):
d
28.74/29.7/31.6/34.1
(s/s/s/s, 4 ¥ CH2 (cod)), 30.6 (s, CHCH2CH2), 45.5/49.8 (s/s,
N(CH3)2), 54.9 (d, 1J(13C,103Rh)
30.4 Hz, CHSO2Ph),
66.5 (s, CH2NMe2), 76.5/76.6/85.3/86.4 (d/d/d/dd,
(CAr). 31P NMR (81 MHz, THF-d8): d 23.7 (ddd, J(31P,31P) =
2
35.6 Hz, 2J(31P,31P) = 351.5 Hz, 1J(31P,103Rh) = 131.6 Hz,
CH2CH2CH2PPh2), 58.9 (ddd, 2J(31P,31P) = 33.4 Hz, 2J(31P,31P) =
=
351.5 Hz, J(31P,103Rh) = 140.2 Hz, P (dppe) trans to P), 73.9
1
1J(13C,103Rh) = 7.9 Hz/1J(13C,103Rh) = 7.8 Hz/1J(13C,103Rh) =
10.1 Hz/1J(13C,103Rh) = 9.2 Hz, 4 ¥ CH (cod)), 128.1 (s, m-C,
SO2Ph), 128.7 (s, o-C, SO2Ph), 131.0 (s, p-C, SO2Ph), 146.0 (s,
i-C, SO2Ph). 7Li NMR (194 MHz, THF-d8): d 0.23 (s, LiCl).
(ddd, 2J(31P,31P) = 33.4 Hz, 2J(31P,31P) = 35.6 Hz, 1J(31P,103Rh) =
184.7 Hz, P (dppe) trans to Cl).
P
P = dppp (10d). Yield: 382 mg (83%). Found: C,
61.77; H, 5.15; Calcd. for C48H47ClO2P3SRh (919.25): C,
62.72; H, 5.15. 1H NMR (400 MHz, THF-d8): d 1.64–
1.79 (m, 2H, PhSO2CH2CH2CH2PPh2), 2.11 (s, br, 2H/2H,
PhSO2CH2CH2CH2PPh2/Ph2PCH2CH2CH2PPh2), 2.24 (s, br,
2H/2H, Ph2PCH2CH2CH2PPh2), 3.49 (“t”, N = 14.2 Hz,
2H, CH2SO2Ph), 6.82–7.94 (m, 35H, HAr). 13C NMR
(125 MHz, THF-d8): d 20.4 (s, Ph2PCH2CH2CH2PPh2), 21.3 (d,
2J(13C,31P) = 7.1 Hz, PhSO2CH2CH2CH2PPh2), 27.6–27.97/32.7
3.7. Preaparation of [RhCl(cod)(Ph2PCH2CH2CH2SO2Ph-
jP)] (13)
Complex 13 was obtained as described in 3.4 but using
[{Rh(cod)}2(m-Cl)2] (5) (246.5 mg, 0.50 mmol) instead of 7a–d.
Yield: 511 mg (83%).
Found: C, 56.41; H, 5.97; Calcd. for C29H33PClSO2Rh
(614.98): C, 56.65; H, 5.41. 1H NMR (400 MHz, CDCl3): d
1.86/2.01/2.23–2.44 (m/m/m, 2H/2H/6H, CH2CH2CH2 + 4 ¥
CH2 (cod)), 2.57 (m, 2H, CH2PPh2), 2.96/5.40 (s/s, br/br,
2H/2H, 4 ¥ CH (cod)), 3.33 (m, 2H, CH2SO2Ph), 7.33–
7.89 (m, 15H, HAr). 13C NMR (100 MHz, CDCl3): d 20.0
(d, 2J(13C,31P) = 2.7 Hz, CH2CH2CH2), 26.6 (d, 1J(13C,31P) =
25.2 Hz, CH2PPh2), 28.72/28.73/32.9/33.0 (s/s/s/s, 4 ¥ CH2
1
(m/m, Ph2PCH2CH2CH2PPh2), 27.98 (d, J(13C,31P) = 24.0 Hz,
PhSO2CH2CH2CH2PPh2), 58.2 (d, 3J(13C,31P)
=
13.0 Hz,
CH2SO2Ph), 127.8–141.7 (CAr). 31P NMR (81 MHz, THF-d8):
d 12.9 (ddd, 2J(31P,31P) = 56.4 Hz, 2J(31P,31P) = 349.0 Hz,
1J(31P,103Rh) = 132.5 Hz, P (dppp) trans to P), 25.6 (ddd,
2J(31P,31P) = 35.7 Hz, 2J(31P,31P) = 349.0 Hz, 1J(31P,103Rh) =
132.9 Hz, 1P, PhSO2CH2CH2CH2PPh2), 34.0 (ddd, J(31P,31P) =
2
56.4 Hz, 2J(31P,31P) = 35.7 Hz, 1J(31P,103Rh) = 174.9 Hz, P (dppp)
trans to Cl).
(cod)), 57.1 (d, J(13C,31P) = 13.8 Hz, CH2SO2Ph), 70.6/105.3
3
(d/dd, 1J(13C,103Rh)
=
13.8 Hz/1J(13C,103Rh)
=
12.2 Hz,
4644 | Dalton Trans., 2010, 39, 4636–4646
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View Article Online
Table 3 Crystallographic data, data collection parameters, and refinement parameters for 9c·THF, 10c, 11, and 12
9c·THF
10c
11
12
Empirical formula
Mr
C37H40NO2P2RhS·C4H8O
C47H45ClO2P3RhS
905.16
Monoclinic
C29H32O2PRhS
578.49
Triclinic
¯
P1
C19H28NO2RhS
437.39
Orthorhombic
799.71
Crystal System
Space group
Orthorhombic
Fdd2
30.109(3)
41.095(4)
12.580(3)
P21/c
Pbca
˚
a/A
21.349(5)
16.099(5)
12.008(5)
9.3705(9)
12.1565(11)
12.6514(13)
63.954(7)
78.562(8)
77.146(7)
1254.0(2)
2
1.532
0.853
596
2.61–29.17
17 184
12.2943(9)
17.1678(16)
17.2075(14)
˚
b/A
˚
c/A
a/◦
b/◦
g /◦
94.237(5)
3
˚
V/A
15565(4)
16
1.365
0.613
6656
1.5–30.0
33 320
7229
4116(2)
4
1.461
0.686
1864
2.71–25.19
65 301
3462
3631.9(5)
8
1.600
1.067
1808
2.36–27.50
32 256
3330
Z
Dc/g cm-1
m(Mo-Ka)/mm-1
F(000)
q range/◦
Rfln. collected
Refln. observed [I > 2s(I)]
Rfln. independent
6075
6724
7652
7399
4144
(Rint = 0.0665)
7652/1/444
1.126
0.0390
0.0837
0.0428
0.0854
0.597 and -0.431
(Rint = 0.1424)
7399/0/496
0.7
0.0325
0.0353
0.1089
0.0403
0.409 and -0.563
(Rint = 0.0322)
6724/0/436
1.110
0.0443
0.1188
0.0488
0.1215
0.825 and -1.112
(Rint = 0.0593)
4144/0/330
1.025
0.0392
0.0939
0.0524
0.1000
0.709 and -0.830
Data/restraints/parameters
Goodness-of-fit on F2
R1
wR2 [I > 2s(I)]
R1
wR2 (all data)
-3
˚
Largest diff. peak and hole/e A
2J(13C,31P) = 7.0 Hz, 4 ¥ CH (cod)), 127.9–137.2 (CAr). 31P NMR
(80 MHz, CDCl3): d 27.8 (d, 1J(31P, 103Rh) = 149.2 Hz, PPh2).
against F2 with SHELXL-97.73 All non-hydrogen atoms were
refined with anisotropic displacement parameters and hydrogen
atoms with isotropic ones. The positions of H atoms in 11 and
12 were found in the difference Fourier map and refined freely. H
atoms in 9c and 10c were placed in calculated positions according
to the riding model.
3.8. Preparation of [RhCl(C2H4)2(Ph2PCH2CH2CH2SO2Ph-
jP)] (14)
Complex 14 was obtained as described in 3.4 but using
[{Rh(C2H4)2}2(m-Cl)2] (6) (194.5 mg, 0.50 mmol) instead of 7a–
d and using thf instead of toluene as solvent. Yield: 405 mg (72%).
Found: C, 53.08; H, 5.25; Calcd. for C25H29PClSO2Rh (562.90):
References
1 C. Elschenbroich and A. Salzer, Organometallics, 2nd edn, Wiley-VCH,
Weinheim, 2003.
2 D. Steinborn, Grundlagen der metallorganischen Komplexkatalyse, 2nd
edn, Vieweg + Teubner, Wiesbaden 2010.
3 T. Satoh, K. Ueura and M. Miura, Pure Appl. Chem., 2008, 80, 1127.
4 K. V. L. Cre´py and T. Imamoto, Org. Synth., 2005, 82, 22.
5 L. Li, W. W. Brennessel and W. D. Jones, Organometallics, 2009, 28,
3492.
6 A. S. Tsai, R. M. Wilson, H. Harada, R. G. Bergman and J. A. Ellman,
Chem. Commun., 2009, 3910.
1
C, 53.34; H, 5.19. H NMR (400 MHz, THF-d8): d 2.05/2.90
=
(s/s, br/br 4H/4H, 4 ¥ CH2), 2.57 (m, 2H, CH2PPh2), 2.27 (s,
br, 2H, CH2CH2CH2), 2.42 (s, br, 2H, CH2PPh2), 3.27 (s, br, 2H,
CH2SO2Ph), 7.35–7.87 (m, 15H, HAr). 13C NMR (100 MHz, THF-
1
d8): d 20.9 (s, br, CH2CH2CH2), 28.2 (d, J(13C,31P) = 29.4 Hz,
3
13
31
=
CH2PPh2), 48.2 (s, br, 4 ¥ CH2), 57.3 (d, J( C, P) = 14.2 Hz,
CH2SO2Ph), 128.8–414.2 (CAr). 31P NMR (80 MHz, THF-d8): d
48.7 (d, br, 1J(31P, 103Rh) = 186.1 Hz, PPh2).
7 H. Harada, R. K. Thalji, R. G. Bergman and J. A. Ellman, J. Org.
Chem., 2008, 73, 6772.
8 S. S. Stahl, J. A. Labinger and J. E. Bercaw, Angew. Chem., Int. Ed.,
1998, 37, 2180.
9 R. R. Schrock, J. H. Freudenberger, M. L. Listemann and L. G.
McCullough, J. Mol. Catal., 1985, 28, 1.
10 A. H. Hoveyda and R. R. Schrock, Chem.–Eur. J., 2001, 7, 945.
11 G. Ba¨hr and G. E. Mu¨ller, Chem. Ber., 1955, 88, 251.
12 S. Matsuda, S. Kikkawa and I. Omae, Kogyo Kagaku Zasshi, 1966, 69,
646.
3.9. X-Ray crystallography
Data for X-ray diffraction analyses of single crystals of 9c·THF,
11 and 12 were collected on a Stoe-IPDS 2T diffractometer at
200(2) K and of 10c at 130(2) K on a CCD Oxford Xcalibur S
˚
diffractometer using Mo-Ka radiation (l = 0.7103 A, graphite
13 A. D. Ryabov, Chem. Rev., 1990, 90, 403.
monochromator). A summary of the crystallographic data, the
data collection parameters, and the refinement parameters is given
in Table 3. Absorption corrections were applied numerically with
X-RED3270 (Tmin/Tmax 0.90/0.93, 11; 0.84/0.95, 12) and multi-
scanning with SCALE3 ABSPACK71 (Tmin/Tmax 0.90/1.00, 10c),
respectively. The structures were solved with direct methods using
SHELXS-9772 and refined using full-matrix least-square routines
14 J. P. Kleiman and M. Dubeck, J. Am. Chem. Soc., 1963, 85, 1544.
15 I. Omae, J. Organomet. Chem., 2007, 692, 2608.
16 J. M. Thompson and R. F. Heck, J. Org. Chem., 1975, 40, 2667.
17 R. A. Holton, Tetrahedron Lett., 1977, 18, 355.
18 R. A. Holton and K. J. Natalie, Jr., Tetrahedron Lett., 1981, 22,
267.
19 W.-C. Yeo, J. J. Vittal, L. L. Koh, G.-K. Tan and P.-H. Leung,
Organometallics, 2004, 23, 3474.
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The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 4636–4646 | 4645
©

View Article Online
20 H.-F. Klein, M. Helwig, U. Koch, U. Flo¨rke and H.-J. Haupt,
Z. Naturforsch., 1993, 48b, 778.
21 F. Kakiuchi, M. Matsumoto, K. Tsuchiya, K. Igi, T. Hayamizu, N.
Chatani and S. Murai, J. Organomet. Chem., 2003, 686, 134.
22 R. F. Jordan and D. F. Taylor, J. Am. Chem. Soc., 1989, 111, 778.
23 K.-J. Chang, D. K. Rayabarapu and C.-H. Cheng, Org. Lett., 2003, 5,
3963.
24 J. K. Stille, Angew. Chem., Int. Ed. Engl., 1986, 25, 508.
25 N. Miyaura and A. Suzuki, Chem. Rev., 1995, 95, 2457.
26 W. A. Herrmann, V. P. W. Bo¨hm and C.-P. Reisinger, J. Organomet.
Chem., 1999, 576, 23.
27 T. K. Hollis and L. E. Overman, J. Organomet. Chem., 1999, 576, 290.
28 Q. Yao and Y. Zhang, Angew. Chem., Int. Ed., 2003, 42, 3395.
29 H. Clavier, N. Audic, J.-C. Guillemin and M. Mauduit, J. Organomet.
Chem., 2005, 690, 3585.
47 H.-C. Wu, S. Abd Hamid, J.-Q. Yu and J. B. Spencer, J. Am. Chem.
Soc., 2009, 131, 9604.
48 M. Aresta, A. Dibenedetto, I. Papai and G. Schubert, Inorg. Chim.
Acta, 2002, 334, 294.
49 G. Canepa, C. D. Brandt and H. Werner, Organometallics, 2001, 20,
604.
50 T. G. Appleton, H. C. Clark and L. E. Manzer, Coord. Chem. Rev.,
1973, 10, 335.
51 B. J. Coe and S. J. Glenwright, Coord. Chem. Rev., 2000, 203, 5.
52 J. G. Verkade, Coord. Chem. Rev., 1972, 9, 1.
53 A. R. Sanger, J. Chem. Soc., Dalton Trans., 1977, 120.
54 F. Dahan and R. Choukroun, Acta Crystallogr., Sect. C: Cryst. Struct.
Commun., 1985, 41, 704.
55 A. L. Balch, L. A. Fossett, R. R. Guimerans and M. M. Olmstead,
Organometallics, 1985, 4, 781.
30 M. Arisawa, Y. Terada, C. Theeraladanon, K. Takahashi, M. Naka-
gawa and A. Nishida, J. Organomet. Chem., 2005, 690, 5398.
31 W. Baratta, P. Da Ros, A. Del Zotto, A. Sechi, E. Zangrando and P.
Rigo, Angew. Chem., Int. Ed., 2004, 43, 3584.
32 M. Linnert, C. Bruhn, C. Wagner, M. Block, T. Ru¨ffer, H. Schmidt and
D. Steinborn, Advances in Coordination, Bioinorganic and Inorganic
Chemistry, ed. M. Melnik, J. Sima and M. Tatarko, STU Press,
Bratislava, 2005, 170.
56 T. E. Nappier, Jr., D. W. Meek, R. M. Kirchner and J. A. Ibers, J. Am.
Chem. Soc., 1973, 95, 4194.
57 D. P. Allen, C. M. Crudden, L. A. Calhoun, R. Wang and A. Decken,
J. Organomet. Chem., 2005, 690, 5736.
58 V. V. Grushin and W. J. Marshall, J. Am. Chem. Soc., 2004, 126, 3068.
59 S. S. Oster and W. D. Jones, Polyhedron, 2004, 23, 2959.
60 Cambridge Structural Database (ConQuest), Version 1.11, Crystal-
lographic Data Centre, University Chemical Laboratory, Cambridge,
UK, 2009.
61 C. Krug and J. F. Hartwig, J. Am. Chem. Soc., 2004, 126, 2694.
62 R. Cohen, M. E. van der Boom, L. J. W. Shimon, H. Rozenberg and
D. Milstein, J. Am. Chem. Soc., 2000, 122, 7723.
33 M. Block, M. Linnert, S. Go´mez-Ruiz and D. Steinborn, J. Organomet.
Chem., 2009, 694, 3353.
34 H. J. Gais, G. Hellmann, H. Gu¨nther, F. Lopez, H. J. Lindner and S.
Braun, Angew. Chem., Int. Ed. Engl., 1989, 28, 1025.
35 W. Hollstein, K. Harms, M. Marsch and G. Boche, Angew. Chem., Int.
Ed. Engl., 1988, 27, 846.
63 A. C. Chen, D. P. Allen, C. M. Crudden, R. Wang and A. Decken,
Can. J. Chem., 2005, 83, 943.
36 M. Linnert, C. Bruhn, C. Wagner and D. Steinborn, J. Organomet.
Chem., 2006, 691, 2358.
37 M. Linnert, C. Wagner, K. Merzweiler and D. Steinborn, Z. Anorg.
Allg. Chem., 2008, 634, 43.
38 B. R. James and D. Mahajan, Can. J. Chem., 1979, 57, 180.
39 D. A. Slack and M. C. Baird, J. Organomet. Chem., 1977, 142, C69.
40 PERCH NMR Software, Version 1/2000, University of Kuopio,
Finland, 2000.
64 R. P. Hughes, in Comprehensive Organometallic Chemistry, ed.
G. Wilkinson, F. G. A. Stone and E. W. Abel, Vol. 5, Pergamon, Oxford
1982, p. 277.
65 M. P. Li and R. S. Drago, J. Am. Chem. Soc., 1976, 98, 5129.
66 P. Imhoff, S. C. A. Nefkens, C. J. Elsevier, K. Goubitz and C. H. Stam,
Organometallics, 1991, 10, 1421.
67 P. Imhoff, C. J. Elsevier and C. H. Stam, Inorg. Chim. Acta, 1990, 175,
209.
41 M. L. Clarke, G. L. Holliday, A. M. Z. Slawin and J. D. Woollins,
J. Chem. Soc., Dalton Trans., 2002, 1093.
42 C. Pettinari, F. Marchetti, R. Pettinari, A. Pizzabiocca, A. Drozdov,
S. I. Troyanov and V. Vertlib, J. Organomet. Chem., 2003, 688, 216.
43 E. Arpac and L. Dahlenburg, J. Organomet. Chem., 1983, 241, 27.
44 D. A. Slack, I. Greveling and M. C. Baird, Inorg. Chem., 1979, 18,
3125.
45 D. P. Fairlie and B. Bosnich, Organometallics, 1988, 7, 936.
46 H. Werner, A. Hampp and B. Windmu¨ller, J. Organomet. Chem., 1992,
435, 169.
68 R. Cramer, Inorg. Synth., 1990, 28, 86.
69 P. Cao, B. Wang and X. Zhang, J. Am. Chem. Soc., 2000, 122, 6490.
70 X-RED32 (version 1.03): Stoe Data Reduction Program, Stoe & Cie
GmbH, Darmstadt 2002.
71 SCALE3 ABSPACK, Empirical Absorption Correction, CrysAlis–
Software package, Oxford Diffraction Ltd. 2006.
72 G. M. Sheldrick, SHELXS-97, Program for solution of crystal struc-
tures, University of Go¨ttingen, Germany, 1997.
73 G. M. Sheldrick, SHELXL-97, Program for refinement of crystal
structures, University of Go¨ttingen, Germany, 1997.
4646 | Dalton Trans., 2010, 39, 4636–4646
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