Rhodium(I) complexes with κp coordinated ω- phosphinofunctionalized alkyl phenyl sulfide, sulfoxide and sulfone ligands and their reactions with sodium bis(trimethylsilyl)amide and Ag[BF4]

Article abstract of DOI:10.1016/j.jorganchem.2010.12.019

Reactions of ω-diphenylphosphinofunctionalized alkyl phenyl sulfides Ph₂P(CH₂)_nSPh (n = 1, 1a; 2, 2a; 3, 3a), sulfoxides Ph₂P(CH₂)_nS(O)Ph (n = 1, 1b; 2, 2b; 3, 3b) and sulfones Ph₂P(CH₂)_nS(O) ₂Ph (n = 1, 1c; 2, 2c; 3, 3c) with dinuclear chlorido bridged rhodium(I) complexes [(RhL₂)₂(μ-Cl)₂] (L₂ = cycloocta-1.5-diene, cod, 4; bis(diphenylphosphino)ethane, dppe, 5) afforded mononuclear Rh(I) complexes of the type [RhCl{Ph ₂P(CH₂)_nS(O)_xPh-κP}(cod)] ¹ (n/x = 1/0, 6a; 1/1, 6b; 1/2, 6c; 2/0, 8a; 2/1, 8b; 2/2, 8c; 3/0, 10a; 3/1, 10b; 3/2, 10c) and [RhCl{Ph₂P(CH₂) _nS(O)_xPh-κP}(dppe)] (n/x = 1/0, 7a; 1/1, 7b; 1/2, 7c; 2/0, 9a; 2/1, 9b; 2/2, 9c; 3/0, 11a; 3/1, 11b; 3/2, 11c) having the P^S(O)_x ligands κP coordinated. Addition of Ag[BF₄] to complexes 6-11 in CH₂Cl₂ led with precipitation of AgCl to cationic rhodium complexes of the type [Rh{Ph₂P(CH ₂)_nS(O)_xPh-κP,κS/O}L ₂][BF₄] having bound the P^S(O)_x ligands bidentately in a κP,κS (13a-18a, 15b-18b) or a κP,κO (13b, 14b, 13c-18c) coordination mode. Unexpectedly, the addition of Ag[BF ₄] to 6a in THF afforded the trinuclear cationic rhodium(I) complex [Rh₃(μ-Cl)(μ-Ph₂PCH₂SPh-κP: κS)₄][BF₄]₂·4THF (12·4THF) with a four-membered Rh₃Cl ring as basic framework. Addition of sodium bis(trimethylsilyl)amide to complexes 6-11 led to a selective deprotonation of the carbon atom neighbored to the S(O)_x group (α-C) yielding three different types of organorhodium complexes: a) Organorhodium intramolecular coordination compounds of the type [Rh{CH{S(O) _xPh}CH₂CH₂PPh₂-κC,κP} L₂] (22a-c, 23a-c), b) zwitterionic complexes [Rh{Ph ₂PCHS(O)_xPh-κP,κS/O}L₂] having κP,κS (21a, 21b) and κP,κO (20b/c, 21c) coordinated anionic [Ph₂PCHS(O)_xPh] ligands, and c) the dinuclear rhodium(I) complex [{Rh{μ-CH(SPh)PPh₂-κC:κP}(cod)} ₂] (19). All complexes were fully characterized spectroscopically and complexes 15b, 15c, 12·4THF and 19·THF additionally by X-ray diffraction analysis. DFT calculations of zwitterionic complexes gave insight into the coordination mode of the [Ph₂PCHS(O)Ph] ligand (κP,κS versus κP,κO).

Full text of DOI:10.1016/j.jorganchem.2010.12.019

Journal of Organometallic Chemistry 696 (2011) 1768e1781
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Rhodium(I) complexes with kP coordinated u-phosphinofunctionalized alkyl
phenyl sulfide, sulfoxide and sulfone ligands and their reactions with sodium
bis(trimethylsilyl)amide and Ag[BF4]
,
Michael Block a, Martin Bette a, Christoph Wagner a, Jürgen Schmidt b, Dirk Steinborn a
*
a Institute of Chemistry e Inorganic Chemistry, Martin Luther University Halle-Wittenberg, Kurt-Mothes-Straße 2, 06120 Halle, Germany
b Department of Bioorganic Chemistry, Leibniz Institute of Plant Biochemistry, Weinberg 3, 06120 Halle, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
Reactionsof
sulfoxides Ph2P(CH2)nS(O)Ph (n ¼ 1, 1b; 2, 2b; 3, 3b) and sulfones Ph2P(CH2)nS(O)2Ph (n ¼ 1, 1c; 2, 2c; 3, 3c)
with dinuclear chlorido bridged rhodium(I) complexes [(RhL2)2(
-Cl)2] (L2 ¼ cycloocta-1.5-diene, cod, 4; bis
u
-diphenylphosphinofunctionalized alkyl phenylsulfides Ph2P(CH2)nSPh(n ¼ 1, 1a; 2, 2a; 3, 3a),
Received 27 October 2010
Received in revised form
30 November 2010
m
(diphenylphosphino)ethane, dppe, 5) afforded mononuclear Rh(I) complexes of the type [RhCl{Ph2P(CH2)nS
Accepted 14 December 2010
(O)xPh-
k
P}(cod)]1 (n/x ¼ 1/0, 6a; 1/1, 6b; 1/2, 6c; 2/0, 8a; 2/1, 8b; 2/2, 8c; 3/0,10a; 3/1,10b; 3/2,10c) and [RhCl
{Ph2P(CH2)nS(O)xPh-
11c) having the P^S(O)x ligands
precipitation of AgCl to cationic rhodium complexes of the type [Rh{Ph2P(CH2)nS(O)xPh-
having bound the P^S(O)x ligands bidentately in a P, S (13ae18a, 15be18b) or a P, O (13b, 14b, 13ce18c)
coordination mode. Unexpectedly, the addition of Ag[BF4] to 6a in THF afforded the trinuclear cationic
rhodium(I) complex [Rh3( -Cl)( -Ph2PCH2SPh- P: S)4][BF4]2$4THF (12$4THF) with a four-membered Rh3Cl
ring as basic framework. Addition of sodium bis(trimethylsilyl)amide to complexes 6e11 led to a selective
deprotonation of the carbon atom neighbored to the S(O)x group ( -C) yielding three different types of
organorhodium complexes: a) Organorhodium intramolecular coordination compounds of the type [Rh{CH
{S(O)xPh}CH2CH2PPh2- C, P}L2] (22aec, 23aec), b) zwitterionic complexes [Rh{Ph2PCHS(O)xPh- P, S/O}L2]
having P, S (21a, 21b) and P, O (20b/c, 21c) coordinated anionic [Ph2PCHS(O)xPh] ligands, and c) the
dinuclear rhodium(I) complex [{Rh{ -CH(SPh)PPh2- C: P}(cod)}2] (19). All complexes were fully charac-
k
P}(dppe)] (n/x ¼ 1/0, 7a; 1/1, 7b; 1/2, 7c; 2/0, 9a; 2/1, 9b; 2/2, 9c; 3/0,11a; 3/1,11b; 3/2,
Keywords:
P,S ligands
P,O ligands
Organorhodium intramolecular
coordination compounds
Zwitterionic complexes
kP coordinated. Addition of Ag[BF4] to complexes 6e11 in CH2Cl2 led with
k
P, S/O}L2][BF4]
k
k
k
k k
m
m
k k
a
k
k
k k
k
k
k k
m
k k
terized spectroscopically and complexes 15b, 15c, 12$4THF and 19$THF additionally by X-ray diffraction
analysis. DFTcalculations of zwitterioniccomplexes gave insight into the coordination mode of the [Ph2PCHS
(O)Ph] ligand (kP,kS versus kP,kO).
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
an example, bidentate P^S and P^O type ligands are equipped with
a strong and a weak donor group; thus, they might offer a hemilabile
character which permits a temporary generation of a vacant coor-
dination site at the metal center [6]. Moreover, complexes bearing
ligands of that type can play an important role in various homoge-
neously catalyzed reactions [7e10] or as chemosensors [11].
Furthermore, deprotonation of such ligands may lead to the
formation of zwitterionic (betaine-like) complexes. They are charac-
terized bya formal charge separation between a cationic metal center
and a negatively charged ancillary ligand moiety within an overall
neutralmolecularframework[12]. Hence, theycombinethereactivity
of related cationic complexes with the solubility properties of neutral
species which makes them useful in some homogeneously catalyzed
reactions [13e15]. If the deprotonation of the P^S and P^O ligands
Sterical and electronical effects of bidentate ligands on the
structure and reactivity of metal complexes are a substantial subject
of research in organometallic chemistry as well as in homogeneous
catalysis. While many investigations were done with homobide-
ntate ligands such as diphosphanes [1e3], heterobidentate ligands
offer the possibility to introduce two completely different donor
centers having different electronic (e.g. trans influence, trans effect)
and sterical effects. In this way, stability and reactivity of interme-
diates in a reaction may be influenced in a targetted manner [4,5]. As
* Corresponding author. Tel.: þ49 345 55 25620; fax: þ49 345 55 27028.
E-mail address: dirk.steinborn@chemie.uni-halle.de (D. Steinborn).
1
leads to a
kC,kP coordination, organometallic intramolecular coordi-
Here and in the following the letters a, b, and c in the numbering schemes refer
nation compounds (also named “organometallic inner complexes”)
to a sulfanyl (x ¼ 0), sulfinyl (x ¼ 1) and sulfonyl (x ¼ 2) functionality, respectively.
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.12.019

M. Block et al. / Journal of Organometallic Chemistry 696 (2011) 1768e1781
1769
are formed. In general, they are characterized as metallacyclic
compounds with an MeC bond and a bond of the metal to a neutral
Lewis-basic heteroatom group like NR2, PR2, OR or SR being also part
ofthecycle.Overthe pastyears,theyweresubjectofalargenumberof
researches [16e19], thus, from almost all metals of the periodic table
organometallic intramolecular coordination compounds are known
and they are widely used in various ways in organic syntheses.
in dependence on the type of the sulfur functionalization (x ¼ 0e2)
and on the spacer length (n ¼ 1e3). Thus, it is reported on the
formation and characterization of organorhodium intramolecular
coordination compounds and zwitterionic complexes having the
deprotonated P^S(O)x ligands kC,kP, kP,kS and kP,kO coordinated as
well as of cationic complexes with non-deprotonated P^S(O)x-
kP,kS/O
ligands.
We are interested in
a,
u
-functionalized ligands of the type RmY
(CH2)nS(O)xR bearing
a Lewis-basic heteroatom group YRm
2. Results and discussion
(YRm ¼ PR2, NR2, OR; R ¼ alkyl, aryl) as well as, respectively, a sul-
fanyl (x ¼ 0), sulfinyl (x ¼ 1) and sulfonyl group (x ¼ 2). While the
2.1. Syntheses
functionalized sulfides and sulfones can act as
kS,kY and kO,kY
donors, respectively, in case of the analogous flexidentate sulfox-
ides both coordination modes are possible [20e22]. Structure and
reactivity of metal complexes with the requisite deprotonated
ligands depend on the nature of sulfur functionalization neigh-
Chlorido bridged Rh(I) complexes [(RhL2)2(
dppe, 5) were reacted with compounds of the type Ph2P(CH2)nS
(O)xPh that include -diphenylphosphinofunctionalized alkyl
phenyl sulfides (x ¼ 0), sulfoxides (x ¼ 1) and sulfones (x ¼ 2). As
spacers between the two donor sites the methylene (n ¼ 1),
dimethylene (n ¼ 2) and trimethylene (n ¼ 3) groups were used. As
shown in Scheme 1 (routes a/b/c) the reactions afforded neutral
rhodium(I) complexes (6a/b/ce11a/b/c) having bound the Ph2P
m
-Cl)2] (L2 ¼ cod, 4;
u
bored to the carbanionic atom (
sulfide group (x ¼ 0) next to the
C, Y coordinated in most cases, thereby organometallic intra-
a
-C). Ligands with a Lewis-basic
a-carbon atom are found to be
k
k
molecular coordination compounds are formed, irrespective of the
nature of the metal [23e26]. However, in the analogous complexes
with a functionalized sulfone ligand (x ¼ 2) the dipole stabilization
of the SO2 group gives rise to the formation of a less basic carbanion
[27]. While in solid state the majority of the respective lithiated
(CH2)nS(O)xPh ligands in a kP coordination mode as it was shown
for complexes 10a/11a [24] and 10c/11c [29] before. The reactions
were conducted in THF at room temperature. Using methylene
chloride as solvent, the reactions with the dppe complex 5 have to
be performed at ꢀ78 ꢁC to avoid the oxidative addition of methy-
lene chloride to 5 which results in the formation of a methylene-
bridged rhodium(III) complex [33]. Complexes 6e11 were obtained
as yellow to orange moderately air and moisture sensitive solids in
good to excellent yields (72e91%) and they were characterized
NMR spectroscopically (1H, 13C, 31P) as well as by high-resolution
mass spectrometric (HRMS-ESI) investigations. All complexes were
soluble in THF and CH2Cl2. Solutions were found to be stable at
room temperature, except for complexes 8a and 8b that showed
a decomposition within several hours. In chloroform all complexes
(except of 6, 8c and 10) decomposed within several minutes.
Addition of Ag[BF4] to complexes 6a/b/ce11a/b/c led with
precipitation of AgCl to cationic rhodium complexes of the type [Rh
compounds are higher aggregated having the sulfonyl group kO
coordinated to the Li atom resulting in a “free” carbanionic center
[28] the corresponding transition metal complexes were generally
found to be mononuclear organometallic intramolecular coordi-
nation compounds exhibiting a kC,kY coordination [29,30]. On the
other hand, the sulfinyl functionalization (x ¼ 1) can be regarded
both as a Lewis-basic and a dipole-stabilized heteroatom group. Yet
there have been only few studies on these ligands; even for non-
functionalized ligands of the type ӨCHReS(O)R only few structural
data are presented in the literature. They seem to resemble more
the sulfones: lithiated sulfoxides exhibit a
a “free” carbanionic center [31] whereas in transition metal
complexes a C coordination is observed [32].
Here we present a systematic study on reactions of rhodium(I)
complexes of the type [RhCl{Ph2P(CH2)nS(O)xPh-
P}L2] (L2 ¼ cod,
dppe) with sodium bis(trimethylsilyl)amideand Ag[BF4], respectively,
kO coordination with
k
{Ph2P(CH2)nS(O)xPh-
chelating P^S(O)x ligands with a
mode, respectively (Scheme 1, routes d/e/f). To simplify these
k
P,
kS/O}L2][BF4] (13a/b/ce18a/b/c) bearing
k
k
P, S and a P, O coordination
k
k k
Scheme 1. Synthesis of rhodium complexes bearing monodentately coordinated P^S(O)x-kP ligands (6e11) and chelating P^S(O)x-kP,kS/O ligands (13e18).

1770
M. Block et al. / Journal of Organometallic Chemistry 696 (2011) 1768e1781
2+
Reactions of the neutral rhodium complexes 6e11 with sodium
bis(trimethylsilyl)amide at ꢀ78 ꢁC led to a selective deprotonation
Ph
S
Ph2
P
Ph
Ph
S
S
of the
a-carbon atom yielding three different types of organo-
Rh
Cl
PPh2
Ph2P
rhodium complexes (Scheme 2, routes a/b/c):
Rh
Rh
Route a. Starting from the neutral complexes having a tri-
methylene spacer (n ¼ 3; 10, 11) organorhodium intramolecular
coordination compounds of the type [Rh{CH{S(O)xPh}CH2CH2PPh2-
Ph2P
SPh
Chart 1. Structural formula of the cation in [Rh3(
[BF4]2$4THF (12$4THF).
m
-Cl)(m-Ph2PCH2SPh-kP:kS)4]
kC,kP}L2] (22, 23) were obtained. The two complexes bearing the
deprotonated sulfinylfunctionalized ligand (x ¼ 1; 22b, 23b) were
isolated in yields of about 75% as yellow highly air and moisture
sensitive solids which were found to be soluble in THF and CH2Cl2
without decomposition. Moreover, they showed a moderate solu-
bility in n-pentane. Complexes 22a/c and 23a/c have been prepared
before by using lithium diisopropyl amide as base [24,29]. Hence, in
this work the formation of these complexes has been proved by 31P
NMR spectroscopic measurements of the reaction solutions only.
Route b. The second class are zwitterionic complexes of the type
syntheses, the neutral complexes 6e11 obtained via routes a/b/c do
not have to be isolated. In such a way complexes 13e18 were iso-
lated in yields of 78e92% as yellow moderate air and moisture
sensitive solids. While 16c showed only a limited stability in CH2Cl2
(ca 1 h at room temperature) all other complexes were soluble in
methylene chloride without decomposition.
Complexes 13e18 were characterized by 1H, 13C, 31P NMR
spectroscopy as well as by HRMS-ESI measurements. The phos-
[Rh{Ph2PCHS(O)xPh-
starting from the neutral complexes bearing a methylene spacer
(n ¼ 1; 6, 7). These complexes have P, S (21a, 21b) and P, O (20b/c,
kP,kS/O}L2] (20, 21) which were obtained by
phinofunctionalized sulfides (x ¼ 0) and sulfones (x ¼ 2) are
and P, O coordinated, respectively. The corresponding sulfoxides
exhibit both a P, P,
kP,kS
k
k
k k
k
k
21c) coordinated anionic [Ph2PCHS(O)xPh] ligands, thus the methine
C atom is not coordinated to Rh. The complexes were obtained as
brown highly air and moisture sensitive solids showing limited
thermal stability only. Due to that, they were isolated without
removing the NaCl formed in the course of the reaction. Furthermore,
they exhibited a pronounced solubility even in n-pentane which
made it difficult to remove residual amounts of HN(SiMe3)2. Complex
21a was characterized by 31P NMR spectroscopy from the reaction
mixture only. All attempts to isolate complex 21a in substance led to
decomposition. Complexes 20c and 21b were found to decompose in
THF within 1 h at room temperature and immediately in methylene
chloride. For complexes 20b and 21c the opposite was the case.
Complexes 20e23 (except of complex 21a) were characterized by
NMR spectroscopy (1H, 13C, 31P) and HRMS-ESI measurements.
Route c. In contrast, the reaction of the neutral complex [RhCl
k
k
S (n ¼ 2, 3) and a
k
k
O (n ¼ 1) coordination, thus
forming five- and six-membered rhodacycles. 31P NMR spectro-
scopic measurements of the reaction solutions showed that all
reactions were highly selective with the exception of complex 18c
where several by-products (>60%) were found which could not be
removed. Furthermore, attempts failed to obtain complex 18c
alternatively by ligand substitution (cod / dppe) from complex
17c: As shown NMR spectroscopically, adding 1 equivalent dppe to
complex 17c resulted with cleavage of cod in the formation of the
two homoleptic cationic complexes [Rh(dppe)2]þ and [Rh-
{Ph2PCH2CH2CH2S(O)2Ph-kP,k
O}2]þ.
While the addition of Ag[BF4] to complex 6a in CH2Cl2 afforded
selectively the cationic rhodium complex 13a (Scheme 1), the
analogous reaction performed in THF led to the immediate forma-
tion of a deep red solution which contains three different complexes
in a ratio of about 2:1:2 as revealed by 31P NMR spectroscopic
measurements. Within 24 h, one of these products precipitated as
redcrystals which wereisolated in ayield of 32%. NMR spectroscopic
and structural measurements exhibited that a trinuclear rhodium(I)
(Ph2PCH2SPh-
of the dinuclear rhodium complex [{Rh{
k
P)(cod)] (6a) with NaN(SiMe3)2 led to the formation
-CH(SPh)PPh2- C: P}
m
k k
(cod)}2] (19). As 31P NMR spectroscopic measurements from the
reaction mixture revealed, the reaction proceeded with a high
selectivity (>90%), too. Within 24 h, 19 crystallized from the reac-
tion mixture as THF adduct (19$THF) in a yield of 81% as orange
complex, [Rh3(m-Cl)(m-Ph2PCH2SPh-kP:kS)4][BF4]2$4THF (12$4THF;
Chart 1), has been formed.
Scheme 2. Synthesis of organorhodium intramolecular coordination compounds (22, 23), zwitterionic complexes (20, 21) and a dinuclear organorhodium complex (19).

M. Block et al. / Journal of Organometallic Chemistry 696 (2011) 1768e1781
1771
Table 1
Selected NMR spectroscopic data (
d
in ppm, J in Hz) of [RhCl{Ph2P(CH2)nS(O)xPh-kP}L2] (6e11).
L (x)
Ph2PCaH2S(O)xPh
da (1JP,C
Ph2PCbH2CaH2S(O)xPh
Ph2PCgH2CH2CaH2S(O)xPh
da (3JP,C
)
dP (1JRh,P
)
da-C (2JP,C
)
db (1JP,C
)
dP (1JRh,P
)
)
dg (1JP,C
)
dP (1JRh,P
)
-C
-C
-C
-C
cod (0)
cod (1)
cod (2)
dppe (0)
dppe (1)
dppe (2)
6a
6b
6c
7a
7b
7c
31.4 (17.8)
62.3 (18.3)
54.9 (6.8)
32.0 (13.7)
63.1 (13.8)
53.7 (6.9)
28.1 (150.1)
30.8 (151.2)
24.0 (154.1)
24.4 (132.2)
27.9 (142.3)
22.0 (135.0)
8a
8b
8c
9a
9b
9c
36.9 (7.2)
52.9 (s)
53.5 (2.7)
38.4 (9.0)
53.6 (6.3)
52.7 (5.1)
31.4 (15.9)
20.1 (22.9)
22.6 (23.6)
32.4 (22.8)
20.4 (21.6)
21.2 (19.6)
26.1 (150.7)
26.8 (151.2)
24.7 (153.2)
60.6 (134.9)
23.1 (133.2)
22.1 (133.8)
10aa
10b
35.4 (15.0)
58.0 (12.1)
57.1 (13.8)
35.4 (15.8)
58.7 (13.0)
57.6 (13.6)
26.9 (25.2)
26.9 (25.3)
26.6 (25.2)
28.4 (22.7)
27.1 (21.9)
26.9 (22.5)
26.2 (147.1)
26.8 (146.4)
27.8 (149.2)
23.8 (131.6)
24.2 (131.5)
23.7 (131.6)
10cb
11aa
11b
11cb
a
Values taken from Ref. [24].
Values taken from Ref. [29].
b
moderately air and moisture sensitive crystals being suitable for
a single-crystal X-ray diffraction analysis. Moreover, the isolated
product was found to be insoluble in all common solvents which
prevented further NMR spectroscopic characterization.
By analogy to the synthesis of the cationic rhodium complexes
13e18, for the synthesis of all these complexes (19e23) the inter-
mediate compounds 6e11 do not have to be isolated. Hence,
complexes 19e23 can be obtained in a one-pot procedure directly
from the dinuclear starting complexes 4 and 5. In no case we suc-
ceeded to obtain definite complexes starting from rhodium comp-
lexesbearingP^S(O)x ligandswiththedimethylenespacer(n¼ 2;8, 9)
sinceallreactionswithNaN(SiMe3)2 ledtodecomposition, as31PNMR
spectroscopic investigations revealed.
the Ph2PCH2S(O)Ph-kP ligand exhibited a doublet of doublet
pattern caused by 2JH,H (13.5/13.5 Hz, 6b; 13.3/13.3 Hz, 7b) and 2JP,H
couplings (9.1/8.0 Hz, 6b; 7.4/6.4 Hz, 7b). Due to signal overlapping
and/or additional H,H couplings only broad signals or non-resolved
multiplets were observed in the other complexes bearing ligands
with a sulfinyl functionalization.
2.2.2. Cationic rhodium complexes bearing P,S and P,O chelate
ligands and [Rh3(m-Cl)(m-Ph2PCH2SPh-kP:kS)4][BF4]2$4THF
Selected NMR spectroscopic parameters of complexes 13e18 are
given in Table 2. The 31P NMR spectra of the complexes bearing
a dppe ligand appeared as first order AEMX spin systems (14a, 14c,
16c, 18a, 18b, 18c) as well as higher order ABMX (14b, 16a) and ABCX
(16b) spin systems, respectively (A, B, C, E, M ¼ 31P; X ¼ 103Rh)
which were analyzed by using the PERCH NMR software package
[35]. The 31P NMR spectra of all cod complexes (13, 15, 17) were AX
spin systems.
2.2. Spectroscopic investigations
2.2.1. Rhodium complexes with Ph2P(CH2)nS(O)xPh-kP ligands
(n ¼ 1e3, x ¼ 0e2)
As expected, the 1JRh,P couplings (P is part of the P^S(O)x ligands)
were in a similar range as those of the analogous neutral complexes
6e11. Only in complexes 13a and 14a the formation of a four-
Selected NMR spectroscopic parameters of complexes 6e11 are
given in Table 1. The 31P NMR spectra were of first order where all
dppe complexes (7, 9, 11) exhibited an AEMX spin system and all
cod complexes (6, 8, 10) an AX spin system (A, E, M ¼ 31P;
1
membered RhPCS cycle led to a decrease of the JRh,P coupling
constants by 30.6 Hz (13a) and 21.1 Hz (14a), respectively. Moreover,
in complexes 13a and 14a the 31P resonances of the Ph2PCH2SPh
ligand exhibited a marked highfield shift by 59.2 ppm (13a) and
47.2 ppm (15a) compared tothe respective neutral complexes 6a and
7a (Table 1). These pronounced highfield shifts are also found in
structurallysimilar rhodium complexes having bound a dppm-k2P,P0
ligand (four-membered RhP2C ring) [29,36,37]. Furthermore, the
formation of the four-membered rhodacycles led to a, respectively,
strong (DdC 76.3 ppm, 13a) and a reasonable (DdC 28.3 ppm, 14a)
X ¼ 103Rh). The
kP coordination of the P^S(O)x ligands went along
with a strong lowfield shift of the 31P resonances (DdP > 30 ppm).
The 1JP,C couplings for ligands with the same spacer length (6/7, 8/9,
10/11) were in a narrow range, with the exception of 6c, 7c and 8c.
In all dppe complexes (7, 9, 11) the 1JRh,P couplings (P is part of the
P^S(O)x ligands) were about 20 Hz smaller than those of the cod
complexes (6, 8, 10) reflecting the higher trans influence of phos-
phanes compared to olefines [34]. Due to the chiral sulfur center in
the rhodium complexes bearing
u
-phosphinofunctionalized alkyl
lowfield shift of the
coordination of the P^S(O)x ligands in all other complexes had only
little effect on the 13C NMR shifts of the
-carbon atoms (Dd ꢂ 7 ppm)
compared to the neutral rhodium complexes 6e11.
a-C resonances whereas the kP,kO and kP,kS
phenyl sulfoxide ligands (6be11b) the aliphatic and olefinic (6b, 8b,
10b) hydrogen atoms are diastereotopic. The best it could be seen in
case of complexes 6b and 7b where each of the aliphatic protons of
a
Table 2
Selected NMR spectroscopic data (
d
in ppm, J in Hz) for complexes [Rh{Ph2P(CH2)nꢀ1CaH2S(O)xPh-
kP,
kS/O}L2][BF4] (13e18).
L2 ¼ cod
L2 ¼ dppe
n/x
da
-C
(
mJP,C
)
dP (1JRh,P
)
dC]
(1JRh,C
)
n/x
da (
mJP,C
-C
)
dP (1JRh,P
)
dP b (1JRh,P
)
a
0
0
C
13a
13b
13c
15a
15b
15c
17a
17b
17c
1/0
1/1
1/2
2/0
2/1
2/2
3/0
3/1
3/2
107.7 (7.3)c
57.4 (10.2)c
57.2 (10.0)c
37.5 (7.2)d
52.9 (s)
ꢀ31.1 (119.5)
53.6 (162.7)
25.3 (149.0)
59.0 (147.2)
52.7 (135.8)
18.9 (149.5)
12.4 (140.0)
11.0 (140.0)
24.2 (147.8)
86.5 (9.3)
69.4/74.1 (13.9/14.5)
72.4 (14.3)
87.7 (10.8)
78.0/78.3 (8.1/11.3)
71.1 (15.6)
86.0 (11.2)
94.5/99.0 (10.0/8.4)
71.6 (15.3)
14a
14b
14c
16a
16b
16c
18a
18b
18c
1/0
1/1
1/2
2/0
2/1
2/2
3/0
3/1
3/2
60.3 (19.3)c
56.6 (s)
56.4 (s)
ꢀ22.8 (111.1)
55.5 (146.3)
27.1 (129.7)
59.4 (135.3)
57.8 (136.4)
16.5 (136.6)
7.1 (131.1)
69.1 (166.6)
74.0 (182.4)
76.2 (184.7)
65.5 (151.2)
60.1 (145.1)
77.4 (204.5)
66.4 (160.0)
60.0 (148.2)
70.5 (182.5)
39.2 (10.9)d
60.3 (9.5)d
52.4 (6.4)d
35.9 (8.8)e
58.7 (7.6)e
e
51.9 (s)
39.3 (3.6)e
57.7 (4.8)e
57.0 (3.8)e
7.7 (132.2)
21.2 (127.0)
a
C]C is part of the cod ligand and trans to S and O, respectively.
b
c
P0 is part of the dppe ligand and trans to S and O, respectively.
m ¼ 1.
m ¼ 2.
m ¼ 3.
d
e

1772
M. Block et al. / Journal of Organometallic Chemistry 696 (2011) 1768e1781
1
1
JRh,C
JRh,P'
16
14
12
10
200
: n = 1 (13a−c)
: n = 1 (14a−c)
: n = 2 (16a−c)
: n = 3 (18a−c)
: n = 2 (15a−c)
: n = 3 (17a−c)
190
180
170
160
150
Ph2P(CH2) SPh Ph2P(CH2) S(O)Ph Ph2P(CH2) S(O)2Ph
Ph2P(CH2) S(O)2Ph
Ph2P(CH2) SPh Ph2P(CH2) S(O)Ph
n
n
n
n
n
n
(c)
(a)
(c)
(b)
(a)
(b)
Fig. 1. Graphical representation of 1JRh,C couplings in complexes 13, 15, 17 (left) and 1JRh,P couplings in complexes 14, 16, 18 (right). In complexes 13b, 15b and 17b the mean value of
0
1
the two JRh,C couplings are given.
The different trans influences of the R2S group (S donor) and the
R2SO2 group (O donor) allowed an assignment of the coordination
In the 31P NMR spectrum of the trinuclear complex 12$4THF the
resonances of two magnetically inequivalent phosphorus atoms
1
mode (kP,kS versus
kP,kO) of the
u-phosphinofunctionalized alkyl
appeared as ddd patterns from which the JRh,P (140.7/180.3 Hz),
2
phenyl sulfoxide ligands in complexes 13be18b. In Fig. 1, the
2JP,P (35.3/35.3 Hz) and JRh,P (2.5/3.5 Hz) couplings could be
magnitudes of the 1JRh,C (C is trans to S/O) and 1JRh,P (P0 is trans to S/
obtained. Apart from the THF signals and the resonances in the
aromatic region the 1H NMR spectrum showed one broad singlet at
2.78 ppm whereas in the 13C NMR spectrum two doublet patterns
0
O) couplings of the complexes bearing sulfinylfunctionalized ligands
(x ¼ 1) are compared to those of the analogous complexes having
bound functionalized sulfide (x ¼ 0) and sulfone (x ¼ 2) ligands
(
dC 31.6/42.5 ppm) appeared showing 1JP,C couplings (27.8/26.7 Hz).
where the
(Fig. 1).
kP,kS and
kP,kO coordination, respectively, is obvious
The solid-state structure of this complex (vide infra, Fig. 4) let
expect the AA0EE0 part of an AA0EE0MM0X spin system (A, E ¼ 31P; M,
X ¼ 103Rh) in the 31P NMR spectrum. An analysis with the PERCH
As it can be seen, the two rhodium complexes having bound the
Ph2PCH2S(O)Ph ligand (13b, 14b) most likely adopt a P, O coor-
3
4
k
k
software revealed that due to small JRh,P and JP,P long-range
couplings (<2 Hz) the NMR spectrum is simplified, hence two ddd
patterns are found only, which is in full accord with the experi-
mental findings.
dination thus avoiding a strained four-membered ring whereas the
other sulfoxide ligands in complexes 15b, 16b, 17b and 18b most
probably exhibit a kP,kS coordination mode. For 15b this is in full
accordance with the result of the single-crystal X-ray diffraction
analysis (vide infra, Fig. 2).
2.2.3. Organorhodium intramolecular coordination and
zwitterionic complexes, [{Rh{m-CH(SPh)PPh2-kC:kP}(cod)}2]
While the 31P NMR spectra of the intramolecular coordination
compounds bearing a dppe ligand 23 (Table 3) appeared as higher
order ABCX spin systems, those of the zwitterionic rhodium com-
plexes [Rh{Ph2PCHS(O)xPh-kP,kS/O}(dppe)] (21) were found to be
first order AEMX spin systems (A, B, C, E, M ¼ 31P; X ¼ 103Rh).
However, all cod complexes (20, 22) proved to be of first order with
an AX spin system.
As revealed NMR spectroscopically, the reaction of 10b and 11b
with NaN(SiMe3)2 to form the organometallic complexes [Rh{CH{S
(O)Ph}CH2CH2PPh2-
a deprotonated sulfinyl ligand and thereby having two centers of
chirality (sulfur and -C atom) proceeded diastereoselectively. This
kC,k
P}L2] (L2 ¼ cod, 22b; dppe, 23b) with
a
was confirmed by the presence of only one set of signals in the NMR
spectra (1H, 13C, 31P). Noteworthy, in the case of 22b initially two
diastereomers in an intensity ratio of about 1:1 were observed in
the 31P NMR spectrum of the reaction solution (dP 51.6/52.1 ppm;
1JRh,P ¼ 174.6/176.4 Hz). At room temperature within 2 h an isom-
erization took place yielding selectively only one diastereomer (dP
51.6 ppm). The a-carbon atoms in the cod complex 22b appeared as
dd pattern showing 1JRh,C and 2JP,C couplings. In contrast, the signal
of the Ca atom in the dppe complex (23b) proved to be of too high
multiplicity to be resolved.
In the zwitterionic complexes 20 and 21 the signals of the a-
Fig. 2. Molecular structure of the cation in crystals of [Rh{Ph2PCH2CH2S(O)Ph-kP,kS}
carbon nuclei appeared as doublet (1JP,C) and broad singlet patterns,
(cod)][BF4] (15b). The ellipsoides are shown with a probability of 30%. H atoms have
been omitted for clarity. Selected structural parameters (distances in Å, angles in ꢁ):
RheP 2.269(2), RheC21/22cg (cg ¼ center of gravity) 2.0868(5), RheC25/26cg 2.1425(5),
RheS 2.270(2), C21eC22 1.361(9), C25eC26 1.346(1), SeO 1.462(5), PeRheS 85.8(5),
PeRheC21/22cg 94.6(1), C21/22cgeRheC25/26cg 85.7(1), C25/26cgeRheS 94.1(1), C25/
26cgeRheP 179.1(1), C21/22cgeRheS 173.0(1).
respectively, which excluded a coordination of the Ca atom to the
1
rhodium atom due to the missing JRh,C couplings. Furthermore,
from the signal pattern in the 31P NMR spectra (d, 20; 3 ꢃ ddd, 21) it
could be seen that the complexes were mononuclear. On the basis

M. Block et al. / Journal of Organometallic Chemistry 696 (2011) 1768e1781
1773
Table 3
Selected NMR spectroscopic data (
d
in ppm, J in Hz) for complexes [Rh{Ph2PCHS(O)xPh-
k
P,
kS/O}L2] (20, 21) and [Rh{CH{S(O)xPh}CH2CH2PPh2-kC,kP}L2] (22, 23).
Ph2PCaHS(O)xPh
Ph2PCgH2CH2CaHS(O)xPh
da (1JP,C
)
dC]
(1JRh,C
)
dP (1JRh,P
0a
)
L
x
da (2JP,C
)
dg (1JP,C
)
dP (1JRh,P
)
a
0
L
x
-C
C
-C
-C
22ab
cod
cod
cod
dppe
dppe
dppe
0
1
2
0
1
2
35.5 (4.5)
63.0 (4.9)
63.0 (4.6)
41.9e42.8 (m)
57.9e59.8 (m)
61.1e63.0 (m)
31.9 (22.4)
34.0 (26.9)
33.0 (26.9)
33.6 (17.1)
29.3 (15.9)
35.0 (22.2)
58.6 (168.3)
51.6 (174.6)
52.0 (172.0)
58.6 (162.3)
58.0 (156.1)
55.5 (153.1)
20b
20c
21ad
21b
21c
cod
cod
dppe
dppe
dppe
1
2
0
1
2
70.1 (14.3)
69.0 (14.7)
e
87.0/87.3 (10.1/9.7)
85.5/87.9 (9.9/9.8)
e
e
e
e
e
22b
22cc
23ab
23b
23cc
69.4 (159.1)
67.1 (157.3)
74.1 (189.0)
66.6 (s)
37.4 (s)
a
trans to S or O, respectively.
Values taken from Ref. [24].
Values taken from Ref. [29].
b
c
d
Not isolated in substance; only characterized 31P NMR spectroscopically.
of these facts it was concluded that complexes 20 and 21 have the
anionic [Ph2PCHS(O)Ph] ligand P, S (21a/b) and P, O (20b/c, 21c)
in 15b (2.0868(5) Å, trans toS) is markedlylonger than the analogous
bond in 15c (1.9877(3) Å, trans to O). Furthermore, the olefinic CeC
bond trans to O in 15c is considerably longer than the other three
CeC double bonds trans to P and S in 15b/c (1.413(6) Å versus 1.346
(1)e1.361(9) Å), respectively. This might be traced back to the weak
k
k
k k
coordinated. Since the central methine carbon atom is not coordi-
nated to Rh, these are zwitterionic complexes as it is found in
numerous structurally similar dppmeH-
k2P,P0 complexes [36,38,39].
Till now, in literature zwitterionic complexes with P^S ligands are
described only in which the anionic carbon atom is part of a car-
boborane [40] or of a ring system [41]. The assignment of the
coordination mode of the flexidentate anionic [Ph2PCHS(O)Ph]
trans influence of the R2SO2-kO donor which goes along with the
above mentioned short RheC bond; similar observations were made
in other cod rhodium complexes [42e44].
ligand in 20b (
k
P,
k
O) and 21b (
k
P,
kS) was performed on the same
2.3.2. Structure of [Rh3(m-Cl)(m-Ph2PCH2SPh-kP:kS)4]
basis as it was done for the appropriate cationic rhodium
complexes 13b and 14b (see Section 2.2.2.).
[BF4]2$4THF (12$4THF)
Crystals of 12$4THF suitable foran X-ray diffraction analysis were
obtained from CH2Cl2 solution with a layer of n-pentane at room
The 31P NMR spectrum of the dinuclear complex 19 which was
obtained directly from the reaction solution exhibited a higher
order spectrum showing 6 lines. Considering the solid-state
temperature. The complex crystallized as discrete [Rh3(
m-Cl)(m-
Ph2PCH2SPh- P:
k
k
S)4]2þ cations and [BF4]ꢀ anions without unusual
structure of [{Rh(
m
-Ph2PCH(SPh)-
k
C:
k
P)(cod)}2]$THF (19$THF)
intermolecular interactions (shortest distance between non-
(vide infra, Fig. 5) the pattern can be interpreted as an AA0XX0 spin
hydrogenatoms:3.486(9) Å, C20/O10). The structure of the cation is
system (A ¼ 31P, X ¼ 103Rh) showing only 6 instead of the expected
3
10 lines caused by a too small (<1 Hz) JRh,Rh coupling constant.
Using the PERCH software 1JRh,P (169.6/167.3 Hz), 2JRh,P (4.0/1.0 Hz)
and 3JP,P (147.4 Hz) coupling constants could be identified. Complex
19$THF, which crystallized from the reaction mixture within 24 h,
could not be re-dissolved in any common solvent which prevented
further NMR spectroscopic investigations.
2.3. Structures
2.3.1. Structures of [Rh{Ph2PCH2CH2S(O)xPh}(cod)][BF4]
(x ¼ 1, 15b; x ¼ 2, 15c)
Crystals of 15b and 15c suitable for X-ray diffraction analyses
were obtained from THF solutions at room temperature. The two
complexes crystallized as discrete cations and anions without
unusual intermolecular interactions (shortest distance between
non-hydrogen atoms: 3.323(8) Å, C2/F30, 15b; 3.054(5) Å, C2/F30,
15c). The structures of the cations are shown in Figs. 2 and 3.
Selected structural parameters are given in the figure captions.
In the two complexes the rhodium atoms exhibit a slightly dis-
torted square-planar configuration where the primary donor sets
are built up by the bidentately bound cycloocta-1,5-diene ligand
and, respectively, a chelating
functionalized ethyl phenyl sulfoxide ligand (15b) and a chelating
P, O coordinated -phosphinofunctionalized ethyl phenyl sulfone
kP,kS coordinated b-phosphino-
k
k
b
ligand (15c). In the two complexes all angles between neighbored
ligands are close to 90ꢁ (85.7(1)e94.6(1)ꢁ, 15b; 87.0(1)e93.1(1)ꢁ,
15c) and those between trans standing ligands are close to 180ꢁ
(179.1(1)/173.0(1)ꢁ, 15b; 178.0(1)/172.9(1)ꢁ, 15c). The trans influ-
Fig. 3. Molecular structure of the cation in crystals of [Rh{Ph2PCH2CH2S(O)2Ph-kP,kO}
(cod)][BF4] (15c). The ellipsoides are shown with a probability of 30%. H atoms have
been omitted for clarity. Selected structural parameters (distances in Å, angles in ꢁ):
RheP 2.2859(8), RheC21/22cg 1.9877(3), RheC25/26cg 2.1433(3), RheO1 2.166(2),
C21eC22 1.413(6), C25eC26 1.358(6), PeRheO1 92.2(1), PeRheC21/22cg 93.1(1), C22/
23cgeRheC25/26cg 87.0(1), C25/26cgeRheO1 87.9(1), C25/26cgeRheP 178.0(1), C21/
22cgeRheO1 172.9(1).
ence order PR3 > R2SO-kS > R2SO2-kO is clearly reflected in different
RheColefin bond lengths. As expected, the RheC25/26cg (C25/26cg is
trans to P; cg ¼ center of gravity) bonds are of the same length
(2.1433(3) Å,15b; 2.1425(5) Å,15c). However, the RheC21/22cg bond

1774
M. Block et al. / Journal of Organometallic Chemistry 696 (2011) 1768e1781
square-planar configuration where the primary donor set is built up
by two cis standing sulfur atoms of two -Ph2PCH2SPh ligands and by
m
the other two rhodium atoms Rh2 and Rh3. In contrast, these two
rhodium atoms exhibit a square-pyramidal configuration having Rh1
in the apical position each. The equatorial positions are occupied by
the m-Cl ligand as well as by two cis standing phosphorus atoms and
one sulfur atom. The torsion angle Rh1eRh2/Rh3eCl is 173.38(4)ꢁ,
thus the four-membered ring is almost planar. Regarding the Rh3Cl
cycle, the CleRh2eRh1 (99.85(3)ꢁ) and the CleRh3eRh1 (98.92(3)ꢁ)
angles are of a similar size whereas the Rh2eRh1eRh3 (74.06(1)ꢁ)
and the Rh2eCleRh3 (86.72(3)ꢁ) angles are considerably smaller.
The two five-membered rhodacycles Rh1eS1eC1eP1eRh2 and
Rh1eS2AeC2AeP2eRh3/Rh1eS2BeC2BeP2eRh3 adopt
a half-
chair conformation twisted on P1 and C1 as well as on P2 and C2A/
C2B, respectively. Even though the Rh1eRh2 bond (2.7357(5) Å) is
shorter than the Rh1eRh3 bond (2.7606(5) Å), both are in the
expected range for RheRh bonds (median: 2.760 Å, lower/higher
quartile: 2.682/2.822 Å, n ¼ 4446; n ¼ number of observations) [45].
The distances between Rh2 and Rh3 (3.3100(5) Å) as well as between
Rh1 and Cl (3.940(1) Å) exclude any interactions between these
atoms.
Fig. 4. Molecular structure of the cation in crystals of [Rh3(m-Cl)(m-Ph2PCH2SPh-
kP:kS)4][BF4]2$4THF (12$4THF). The ellipsoides are shown with a probability of 30%.
For clarity, H atoms have been omitted and phenyl rings are displayed as wire model.
One CH2SPh group (C2A/S2A and C2B/S2B) was found to be disordered over two
positions with an occupancy of 58.8(4) and 41.2(4)%; only the major occupied position
is shown. Selected structural parameters (distances in Å, angles in ꢁ): Rh1eRh2 2.7357
(5), Rh1eRh3 2.7606(5), Rh2eCl 2.406(1), Rh3eCl 2.415(1), Rh1eS2A 2.637(2),
Rh1eS2B 2.458(3), Rh1eS1 2.553(1), Rh2eP1 2.266(1), Rh2eP3 2.276(1), Rh2eS4
2.401(1), Rh3eP2 2.249(1), Rh3eP4 2.288(1), Rh3eS3 2.371(1), Rh2eRh1eRh3 74.06
(1), Rh1eRh2eCl 99.85(3), Rh1eRh3eCl 98.92(3), Rh2eCleRh3 86.72(3),
Rh1eRh2eS1 101.63(3), Rh1eRh2eP1 84.02(3), P1eRh2eCl 176.13(4), S4eRh2eP3
170.65(5), P2eRh3eCl 175.62(4), P4eRh3eS3 172.85(4), Rh1eRh2$$$Rh3eCl 173.38
(4).
2.3.3. Structure of [{Rh{m-CH(SPh)PPh2-kC:kP}(cod)}2]$THF
(19$THF)
Crystals of 19$THF suitable for an X-ray diffraction analysis were
obtained from THF solution at room temperature. The complex
crystallized as discrete dinuclear entities and between them no
unusual intermolecular contacts were found (shortest intermolec-
ular distance between non-hydrogen atoms is 4.09(2) Å, C25/C1200).
The dinuclear complex exhibits crystallographically imposed C2
symmetry. The structure is shown in Fig. 5, selected structural
parameters are given in the figure caption. The rhodium atoms are in
a distorted square-planar geometry and surrounded by a bidentately
bound cycloocta-1,5-diene ligand as well as by a sulfur and a carbon
shown in Fig. 4. Selected structural parameters aregivenin the figure
caption.
The cation is built up by a four-membered Rh3Cl cycle and four
m-
atom of the m-CH(SPh)PPh2-kC:kP ligand. Due to the higher trans
Ph2PCH2SPh- P: S ligands. The overall disposition of the ligands is
k
k
influence of the anionic C ligand compared to the neutral P ligand the
RheC20/21cg bond (2.0979(3) Å, trans to C) is markedly longer than
the RheC24/25cg bond (2.0625(3) Å, trans to P). The six-membered
Rh2C2P2 ring adopts a twist-boat conformation having the SPh
groupsalmostperpendiculartoit.Notably, thereisaweakinteraction
between the rhodium and the sulfur atom (Rh/S ¼ 2.5449(8) Å)
giving rise to a pseudo-five-coordination [46] which results in
a severe distortion from the ideal square-planar geometry (C20/
21cgeRheC1, 169.05(6)ꢁ; C24/25cgeRheP, 150.93(2)ꢁ).
consistent with a C2 symmetry (axis through Rh1 and Cl) in rough
approximation. The central rhodium atom (Rh1) adopts a distorted
2.3.4. Structures of calculated zwitterionic complexes
To get insight into the coordination mode of the flexidentate
[Ph2PCHS(O)Ph] ligand (kP,kS versus kP,kO), quantum chemical
calculations on the DFT level of theory were performed. The
calculated structures of the two isomeric zwitterionic complexes
with a cod coligand [Rh{Ph2PCHS(O)Ph-
k
P,
k
S/O}(cod)] (20bcalc
,
20b0calc) are shown in Fig. 6. The complex with the
k
P,kO coordi-
nation (20bcalc) possessing a five-membered RhPCSO cycle was
found to be energetically more stable by 4.4 kcal/mol (Gibbs free
energy at 298 K) than the constitutional isomer [Rh{Ph2PCHS(O)
Ph-kP,k
S}(cod)] (20b0calc). This is in full accordance with the expe-
rimental findings.
In addition, for structural comparison, the protonated congeners
[Rh{Ph2PCH2S(O)Ph-
Ph- P,
S}(cod)]þ (13b0calc) have been calculated. Thus, complex
13bcalc represents the calculated cation of the isolated complex [Rh
{Ph2CH2S(O)Ph- P, O}(cod)][BF4] (13b). In both complexes the
deprotonation of the CH2 group goes along with a considerable
shortening of the PeC bonds (1.758/1.741 Å, 20bcalc/20b0calc) and
the SeC bonds (1.674/1.687 Å, 20bcalc/20b0calc) compared to their
kP,k
O}(cod)]þ (13bcalc) and [Rh{Ph2PCH2S(O)
k
k
Fig. 5. Molecular structure of [{Rh{m-CH(SPh)PPh2-kC:kP}(cod)}2] (19) in crystals of
19$THF. The ellipsoides are shown with a probability of 30%. For clarity, H atoms have
been omitted and phenyl rings are displayed as wire model. Selected structural
parameters (distances in Å, angles in ꢁ): RheP 2.3429(8), RheC1 2.077(2), RheC20/21cg
2.0979(3), RheC24/25cg 2.0625(3), C1eRheP 95.42(7), PeRheC20/21cg 93.24(2), C20/
21cgeRheC24/25cg 85.23(1), C24/25cgeRheC1 90.42(1), SeC1eRh 81.5(1), C20/
21cgeRheC1, 169.05(6); C24/25cgeRheP, 150.93(2).
k
k

M. Block et al. / Journal of Organometallic Chemistry 696 (2011) 1768e1781
1775
afford a
kP,kO coordination. In all cases thermodynamically
favored five- and six-membered rhodacycles are formed. Thus,
phosphinofunctionalized sulfoxides are flexidentate ligands
(kP,kS versus kP,kO). Here the coordination mode is dependent
on the ring size and not on the Lewis basicity of the coligand
(cod, dppe), as it is described for non-functionalized sulfoxides
[20] as well as for N-phosphino sulfinamide ligands (PNSO-
type ligands) [48].
2. Incontrast, typeIsulfide(x¼ 0)and sulfoneligands(x¼ 2)arenot
flexidentate. Thus, in the respective complexes [Rh{Ph2P(CH2)n
SPh-kP,kS}L2][BF4] (13ae18a) and [Rh{Ph2P(CH2)nS(O)2Ph-kP,kO}
L2][BF4] (13ce18c) also four- (n ¼ 1, 13a/14a) and seven-
membered (n ¼ 3, 17c/18c) rhodacycles are yielded. The O coor-
dination of the sulfonyl group was unambiguously proved by the
solid-state structure in case of 15c, being one of the few struc-
turally characterized complexes bearing sulfone ligands which is
attributed to their low donor capability [49].
Fig. 6. Calculated structures of [Rh{Ph2PCHS(O)Ph-
{Ph2PCHS(O)Ph- P,
S}(cod)] (20b0calc). For clarity, only the H atoms of the methine
carbon atoms are displayed. Gibbs free energy of 20b0calc is relative to that of 20bcalc
kP,kO}(cod)] (20bcalc) and [Rh
k
k
3. Theweakercoordination capabilityof the cod ligand comparedto
the dppe ligand is evident in the reaction of the rhodiumcomplex
.
bearing a
[BF4] leading, with cleavage of the cod ligand, to the formation of
the trinuclear Rh(I) complex [Rh3( -Cl)( -Ph2PCH2SPh- P: S)4]
[BF4]2$4THF (12$4THF). Noteworthy, 12$4THF contains the
structural motif of an A-frame complex (P1eRh2e -CleRheP2)
which is well known from complexes with dppm ligands [50,51].
The formal addition of Rh1 to that structural unit results in two
five-coordinated Rh centers (Rh2, Rh3). The four-membered
Rh3Cl cycle as structural unit in complex 12$4THF is only found in
one further complex, namely in an osmiumerhodium carbonyl
cluster [52].
4. Type II ligands with a C3 spacer (n ¼ 3) are found to form
organorhodium intramolecular coordination compounds (22,
23) irrespective of the nature of the sulfur functionalization
(x ¼ 0e2) [24,29]. In the case of the sulfinylfunctionalized
ligands (x ¼ 1) the deprotonation of the prochiral CH2 group
creates a second chiral center; noteworthy, the formation of the
respective organorhodium complexes (22b, 23b) proved to be
diastereoselective. The diastereoselective synthesis of metal-
lacycles [53e55] and their use as catalysts [56,57] have been
described in literature previously.
5. In contrast, the anionic type II ligands with a C1 spacer (n ¼ 1) are
found to form zwitterionic complexes containing both four- and
five-membered rhodacycles. Interestingly, the coordination of
the flexidentate sulfinyl group was found to be dependent on
the coligand: With the more strongly electron donating dppe
k
P coordinated type I ligand (x ¼ 0, n ¼ 1, 6a) with Ag
protonated congeners (PeC: 1.880/1.867 Å; SeC: 1.827/1.839 Å;
13bcalc/13b0calc). Such a shortening of the PeC bonds is also found in
m
m
k k
complexes bearing an anionic dppmeH-
k2P,P0 ligand which is
explained in terms of an ylidic bonding model with some charge
delocalization within the PCP moiety [47]. Moreover, the fact that
m
the calculated complex with the kP,kO coordinated ligand (13bcalc)
is the thermodynamically favored isomer (DDGӨ ¼ 10.7 kcal/mol;
see Supplemental Material, Figure S 3) is in full accordance with the
assignment of the coordination mode of the Ph2CH2S(O)Ph ligand
in complex [Rh{Ph2CH2S(O)Ph-kP,kO}(cod)][BF4] (13b) which was
done on the basis of the magnitudes of the 1JRh,C coupling constants
(see Section 2.2.2).
For the dppe complex 21b the two calculated constitutional
isomers [Rh{Ph2PCHS(O)Ph-
kP,kO}(dppe)] (21bcalc) and [Rh{Ph2PCHS
(O)Ph- P,
k
k
S}(dppe)] (21b0calc; see Supplemental Material, Figure S 1)
were found to be of the same energy within the margin of error
(
DDGӨ ¼ 0.1 kcal/mol), thus the proposed coordination mode based
on NMR spectroscopic investigations (kP,kS) could be neither vali-
dated nor invalidated. Additionally, the analogous dmpe complexes
([Rh{Ph2PCHS(O)Ph-kP,kO}(dmpe)], 24calc; [Rh{Ph2PCHS(O)Ph-kP,kS}
(dmpe)], 240calc) were calculated and found to be of the same energy,
too (DDGӨ ¼ 0.2 kcal/mol; see Supplemental Material, Figure S 2).
2.4. Conclusions
coligand a
k
P,
k
S coordination of the [Ph2PCHS(O)Ph] ligand was
P, O coordination.
From the experimental investigations and quantum chemical
calculations performed in this work the following conclusions on
found, whereas the cod coligand causes a
k
k
Such a coligand-dependency on the coordination mode of
sulfoxide ligands has been discussed on the basis of the HSAB
theory [58]. A marked influence of the coligand was also found
in the complexes bearing the anionic [Ph2PCHSPh] ligand: With
dppe a zwitterionic complex (21a) was formed as described
above, whereas with cod a dinuclear complex (19$THF) was
the coordination behavior of
u-diphenylphosphinofunctionalized
sulfide (x ¼ 0), sulfoxide (x ¼ 1) and sulfone (x ¼ 2) ligands (type I,
Chart 2) and their deprotonated congeners (type II) can be drawn:
1. Reactions of [(RhL2)2(m-Cl)2] with type I sulfoxide ligands
(x ¼ 1) followed by the addition of Ag[BF4] give rise to the
yielded having coordinated
only structurally similar dinuclear rhodium complex described
in literature is the Rh(III) complex [{Rh(Cp*)Me(
-PMe2CH2-
C: P)}2] [59].
m-Ph2PCHSPh-kC:kP ligands. Yet the
formation of cationic complexes of the type [Rh{Ph2P(CH2)nS
(O)Ph-kP,kS/O}L2][BF4] (13e18). While the ligands with the
m
dimethylene (n ¼ 2) and the trimethylene (n ¼ 3) spacer exhibit
k
k
a
k
P,
kS coordination, those with the methylene spacer (n ¼ 1)
These investigations show the versatile coordination behavior of
bidentate neutral P^S(O)x ligands of type I (Chart 2) and their
deprotonated congeners (type II) which can be understood in terms
of the type of the sulfur functionality (sulfanyl versus sulfinyl
versus sulfonyl) and the length of the spacer between the two
Chart 2.
u
-Diphenylphosphinofunctionalized sulfides (x ¼ 0), sulfoxides (x ¼ 1) and
coordination centers (kP,kS; kP,kO; kC,kP). Thus, these ligands offer
sulfones (x ¼ 2) I (n ¼ 1e3) and their deprotonated congeners II being used as ligands
an easy access to formation of novel cationic rhodium complexes,
in Rh(I) complexes.

1776
M. Block et al. / Journal of Organometallic Chemistry 696 (2011) 1768e1781
organorhodium intramolecular coordination compounds as well as
zwitterionic rhodium complexes.
551.0673. 1H NMR (400 MHz, CD2Cl2):
d 1.91e1.95/2.04e2.11/2.41
(m/m/m, 2H/2H/4H, 4ꢃ CH2, cod), 3.16/5.50 (s/s, br/br, 2H/2H, 4ꢃ
CH (cod)), 4.60 (d, 2J(31P,1H) ¼ 7.4 Hz, CH2SO2Ph), 7.41e8.00 (m,15H,
3. Experimental part
HPh). 13C NMR (100 MHz, CD2Cl2):
d
28.9/32.9 (s/s, br/br, 4ꢃ CH2,
cod), 54.9 (d, 1J(13C, 31P) ¼ 6.8 Hz, CH2SO2Ph), 71.3/105.1 (d/dd, 1J
3.1. General comments
(
103Rh,13C) ¼ 13.6/12.2 Hz, 2J(31Ptrans
,
13C) ¼ 7.4 Hz, 4ꢃ CH, cod),
127.7e142.1 (CPh). 31P NMR (81 MHz, CD2Cl2):
31P) ¼ 154.1 Hz, PPh2).
d
24.0 (d, 1J(103Rh,
All reactions and manipulations were carried out under argon
using standard Schlenk techniques. Diethyl ether, toluene, n-
pentane, THF were dried over Na/benzophenone, CH2Cl2 over CaH2
and freshly distilled prior to use. NMR spectra (1H, 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
L2 ¼ cod, n ¼ 2, x ¼ 0 (8a). Yield: 211 mg (72%). HRMS (ESI): m/z
Calcd. for [C28H31PRhS]þ: 533.4900; found for [MꢀCl]þ: 533.4907.
1H NMR (400 MHz, CD2Cl2):
d
1.61e1.82/2.35 (m, 8H, 4ꢃ CH2, cod),
2.53 (s, br, 2H, CH2PPh2), 2.74e2.81 (m, CH2SPh), 4.13 (s, br, 4H, 4ꢃ
CH, cod), 7.26e7.40 (m,15H, HPh). 13C NMR (100 MHz, CD2Cl2):
d 31.1
(s, 4ꢃ CH2, cod), 31.4 (d, 1J(31P, 13C) ¼ 15.9 Hz, CH2PPh2), 36.9 (d, 2J
128.0; THF-d8, dH 1.73/3.58, dC 25.4/67.6) as internal references;
(
d
(
31P, 13C) ¼ 7.2 Hz, CH2SPh), 76.6 (m, 4ꢃ CH, cod), 128.5e133.4 (CPh).
31P) is relative to external H3PO4 (85%). Multiplets in NMR spectra
31P NMR (202 MHz, CD2Cl2):
d
26.1 (d, 1J(103Rh, 31P) ¼ 150.7 Hz,
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 were obtained by using the PERCH NMR software
package. For couplings in ring systems only the shortest coupling
path is given. Microanalyses were performed in the Microanalytical
Laboratory of the University of Halle using a CHNS-932 (LECO)
elemental analyzer. The high-resolution ESI mass spectra were
obtained from a Bruker Apex III Fourier transform ion cyclotron
resonance (FT-ICR) mass spectrometer (Bruker Daltonics) equipped
with an Infinity cell, a 7.0 T superconducting magnet (Bruker), a rf-
only hexapole ion guide, and an external APOLLO electrospray ion
source (Agilent, off-axis spray). The sample solutions were intro-
duced continuously via a syringe pump with a flow rate of
PPh2).
L2 ¼ cod, n ¼ 2, x ¼ 1 (8b). Yield: 252 mg (89%). HRMS (ESI): m/z
Calcd. for [C28H31OPRhS]þ: 549.4894; found for [MꢀCl]þ: 549.4888.
1H NMR (400 MHz, CD2Cl2):
(cod)), 2.54 (m, 2H, CH2PPh2), 2.73e2.83 (m, 2H, CH2SOPh), 4.12 (s,
br, 4H, 4ꢃ CH (cod)), 7.24e7.40 (m, 15H, HPh). 13C NMR (125 MHz,
d
1.60/2.34 (m/m, 4H/4H, 4ꢃ CH2
CD2Cl2):
d
20.1 (d, 1J(31P, 13C) ¼ 22.9 Hz, CH2PPh2), 31.1/31.3 (s/s, br/
br, 4ꢃ CH2, cod), 52.9 (s, br, CH2SOPh), 71.2/106.4 (d/s, e/br, 1J
(
103Rh,13C) ¼ 14.2 Hz, 4ꢃ CH, cod), 106.4e140.5 (CPh). 31P NMR
(202 MHz, CH2Cl2):
d
26.8 (d, 1J(103Rh, 31P) ¼ 151.2 Hz, PPh2).
L2 ¼ cod, n ¼ 2, x ¼ 2 (8c). Yield: 252 mg (89%). HRMS (ESI): m/z
Calcd. for [C28H31O2PRhS]þ: 565.4888; found for [MꢀCl]þ: 565.4874.
1H NMR (400 MHz, CD2Cl2):
d
1.89/2.02/2.29 (m/m/m, 2H/2H/4H, 4ꢃ
CH2, cod), 2.75e2.82 (m, 2H, CH2PPh2), 3.73e3.79 (m, CH2SO2Ph),
2.95/5.43 (s/s, br/br, 2H/2H, 4ꢃ CH (cod)), 7.32e7.89 (m, 15H, HPh).
120
a complete set of their NMR spectroscopic data are given in the
Supplemental Material. [{Rh(cod)}2( -Cl)2] (4), [{Rh(dppe)}2(
m
L hꢀ1. Details of the preparation of starting compounds and
13C NMR (125 MHz, CD2Cl2):
d
22.6 (d, 1J(31P, 13C) ¼ 23.6 Hz,
m
m-
CH2PPh2), 29.5/33.7 (s/s, 4ꢃ CH2, cod), 53.5 (d, 2J(31P, 13C) ¼ 2.7 Hz
CH2SO2Ph), 71.2/106.4 (d/s, e/br, 1J(103Rh, 13C) ¼ 14.2 Hz, 4ꢃ CH,
Cl)2] (5), Ph2PCH2CH2CH2SPh (3a) and Ph2PCH2CH2CH2S(O)2Ph (3c)
were prepared according to literature procedures [24,29,60,61].
cod), 106.4e140.5 (CPh). 31P NMR (202 MHz, THF-d8): 24.7 (d, 1J
d
(
103Rh, 31P) ¼ 153.2 Hz, PPh2).
3.2. Preparation of [RhCl{Ph2P(CH2)nS(O)xPh-kP}L2] (6e11)
L2 ¼ cod, n ¼ 3, x ¼ 1 (10b). Yield: 270 mg (90%). HRMS (ESI): m/z
Calcd. for [C29H33OPRhS]þ: 563.5160; found for [MꢀCl]þ: 563.5169.
At ꢀ78 ꢁC to a stirred solution of [(RhL2)2(
m-Cl)2] (L2 ¼ cod, 4;
1H NMR (400 MHz, CD2Cl2):
d 1.92e1.99/2.27e2.40 (m/m, 4H/6H,
dppe, 5; 0.25 mmol) in CH2Cl2 (5 mL) Ph2P(CH2)nS(O)xPh
(0.50 mmol) dissolved in CH2Cl2 (2 mL) was added via a syringe and
the mixture was stirred for 1 h at room temperature. 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 ꢃ 5 mL) and dried in vacuo.
L2 ¼ cod, n ¼ 1, x ¼ 0 (6a). Yield: 228 mg (82%). HRMS (ESI): m/z
Calcd. for [C27H29PRhS]þ: 519.0778; found for [MꢀCl]þ: 519.0771. 1H
4ꢃ CH2 (cod), CH2CH2PPh2), 2.44e2.55/2.65e2.74 (m/m, 1H/1H,
CH2PPh2), 2.89e2.96/3.19e3.27 (m/m, 1H/1H, CH2SOPh), 4.14 (m,
4H, 4ꢃ CH, cod), 7.34e7.71 (m, 15H, HPh). 13C NMR (100 MHz,
CD2Cl2):
d
19.8 (d, 2J(31P, 13C) ¼ 2.9 Hz, CH2CH2PPh2), 26.9 (d, 1J(31P,
13C) ¼ 25.3 Hz, CH2PPh2), 31.1/31.3 (s/s, 4ꢃ CH2 (cod)), 58.0 (d, 3J
(
13C, 31P) ¼ 12.1 Hz, CH2SOPh), 87.7 (s, br, 4ꢃ CH, cod), 124.4e144.6
(CPh). 31P NMR (81 MHz, CD2Cl2):
PPh2).
d
26.8 (d, 1J(103Rh, 31P) ¼ 146.4 Hz,
NMR (400 MHz, CDCl3):
d
1.90e2.02/2.35 (m/s, e/br, 4H/4H, 4ꢃ CH2,
L2 ¼ dppe n ¼ 1, x ¼ 0 (7a). Yield: 384 mg (91%). HRMS (ESI): m/z
cod), 3.04/5.54 (s/s, br/br, 2H/2H, 4ꢃ CH, cod), 4.12 (d, 2J(31P,
1H) ¼ 5.6 Hz, 2H, CH2SPh), 7.08e7.79 (m,15H, HPh).13C NMR (100 MHz,
Calcd. for [C45H41P3RhS]þ: 809.1191; found for [MꢀCl]þ: 809.1191.1H
NMR (400 MHz, CD2Cl2):
d 1.81e1.93/2.02e2.15 (m/m, 2H/2H,
CDCl3):
d
28.8/33.0 (s/s, br/br, 4ꢃ CH2,cod), 31.4(d,1J(13C, 31P)¼ 17.8 Hz,
Ph2PCH2CH2PPh2), 3.81 (d, 2J(31P, 1H) ¼ 4.4 Hz, 2H, CH2SPh),
CH2SPh), 70.7/105.8 (s/s, br/br, 4ꢃ CH, cod),126.2e137.1 (CPh). 31P NMR
7.06e7.96 (m, 35H, HPh). 13C NMR (100 MHz, CD2Cl2):
d 25.8e26.3/
(81 MHz, CDCl3):
d
28.1 (d, 1J(103Rh, 31P) ¼ 150.1 Hz, PPh2).
34.7e35.2 (m/m, Ph2PCH2CH2PPh2), 32.0 (d, 1J(31P, 13C) ¼ 13.7 Hz,
L2 ¼ cod, n ¼ 1, x ¼ 1 (6b). Yield: 257 mg (90%). HRMS (ESI): m/z
CH2SPh), 125.5e138.1 (CPh). 31P NMR (81 MHz, THF-d8):
d 24.4 (ddd,
Calcd. for [C27H29OPRhS]þ: 535.0726; found for [MꢀCl]þ: 535.0723.
2J(31P, 31P) ¼ 355.0 Hz, 2J(31P, 31P) ¼ 35.8 Hz,1J(103Rh, 31P) ¼ 132.2 Hz,
1H NMR (400 MHz, CDCl3):
d
1.88e2.18/2.46 (m/s, e/br, 4H/4H, 4ꢃ
PPh2), 59.0 (ddd, 2J(31P, 31P) ¼ 355.0 Hz, 2J(31P, 31P) ¼ 33.4 Hz, 1J
31
CH2, cod), 3.20/3.29/5.61/5.65 (s/s/s/s, br/br/br/br, 1H/1H/1H/1H,
4ꢃ CH, cod), 3.86/4.08 (dd/dd, 2J(31P, 1H) ¼ 9.1/8.0 Hz, 2J(1H,
(
103Rh, P) ¼ 140.9 Hz, P of dppe trans to P), 73.9 (d0t0, 2J(31P,
31P) ¼ 35.8 Hz, 2J(31P, 31P) ¼ 33.4 Hz, 1J(103Rh, 31P) ¼ 183.8 Hz, P of
1H) ¼ 13.5/13.5 Hz, 1H/1H, CH2SOPh), 7.32e7.87 (m, 15H, HPh). 13
C
dppe trans to Cl).
NMR (100 MHz, CDCl3):
d
28.9/29.2/32.8/33.4 (s/s/s/s, br/br/br/br,
L2 ¼ dppe n ¼ 1, x ¼ 1 (7b). Yield: 379 mg (88%). HRMS (ESI): m/z
Calcd. for [C45H41OP3RhS]þ: 825.1141; found for [MꢀCl]þ: 825.1140.
4ꢃ CH2, cod), 62.3 (d, 1J(13C, 31P) ¼ 18.3 Hz, CH2SOPh), 70.4/72.6/
106.6/108.0 (m/m/s/s, e/e/br/br, 4ꢃ CH, cod), 123.9e146.7 (CPh).
1H NMR (400 MHz, CD2Cl2):
d 1.70e1.84/1.98e2.24 (m/m, 2H/2H,
31P NMR (81 MHz, CDCl3):
d
30.8 (d, 1J(103Rh, 31P) ¼ 151.2 Hz, PPh2).
Ph2PCH2CH2PPh2), 3.68/4.39 (dd/dd, 2J(31P, 1H) ¼ 7.4/6.4 Hz, 2J(1H,
L2 ¼ cod, n ¼ 1, x ¼ 2 (6c). Yield: 258 mg (88%). HRMS (ESI): m/z
1H) ¼ 13.3/13.3 Hz, 1H/1H, CH2SOPh), 6.75e8.11 (m, 35H, HPh).
Calcd. for [C27H29O2PRhS]þ: 551.0675; found for [MꢀCl]þ:
13C NMR (100 MHz, CD2Cl2):
d 26.4e26.8/35.3e35.8 (m/m,

M. Block et al. / Journal of Organometallic Chemistry 696 (2011) 1768e1781
1777
Ph2PCH2CH2PPh2), 63.1 (d, 1J(31P, 13C) ¼ 13.8 Hz, CH2SPh), 124.3e
(CPh). 31P NMR (81 MHz, CD2Cl2):
d
24.2 (ddd, 2J(31P, 31P) ¼ 351.2 Hz,
148.2 (CPh). 31P NMR (81 MHz, CD2Cl2):
d
27.9 (ddd, 2J(31P,
2J(31P, 31P) ¼ 35.7 Hz, 1J(103Rh, 31P) ¼ 131.5 Hz, PPh2), 58.9 (ddd, 2J
31P) ¼ 353.4 Hz, 2J(31P, 31P) ¼ 35.4 Hz, 1J(103Rh, 31P) ¼ 142.3 Hz,
(
31P, 31P) ¼ 351.2 Hz, 2J(31P, 31P) ¼ 33.4 Hz, 1J(103Rh, 31P) ¼ 140.2 Hz,
PPh2), 57.9 (ddd, 2J(31P, 31P) ¼ 353.4 Hz, 2J(31P, 31P) ¼ 33.6 Hz, 1J
P of dppe trans to P), 73.9 (d0t0, 2J(31P, 31P) ¼ 35.7 Hz, 2J(31P,
31
(
103Rh, P) ¼ 142.1 Hz, P of dppe trans to P), 75.3 (d0t0, 2J(31P,
31P) ¼ 33.4 Hz, 1J(103Rh, 31P) ¼ 184.9 Hz, P of dppe trans to Cl).
31P) ¼ 35.4 Hz, 2J(31P, 31P) ¼ 33.6 Hz, 1J(103Rh, 31P) ¼ 183.1 Hz, P of
dppe trans to Cl).
3.3. Preparation of [Rh3(m-Cl)(m-Ph2PCH2SPh-kP:kS)4]
L2 ¼ dppe n ¼ 1, x ¼ 2 (7c). Yield: 351 mg (80%). HRMS (ESI): m/z
Calcd. for [C45H41O2P3RhS]þ: 841.1088; found for [MꢀCl]þ:
[BF4]2$4THF (12$4THF)
841.1092. 1H NMR (400 MHz, CD2Cl2):
d
1.80e1.92/2.04e2.16 (m/m,
At room temperature to a stirred solution of [(Rh(cod))2(m-Cl)2]
2H/2H, Ph2PCH2CH2PPh2), 4.66 (d, 2J(31P, 1H) ¼ 4.6 Hz, 2H,
(123.3 mg, 0.25 mmol) in THF (5 mL) Ph2PCH2SPh (154.2 mg,
0.50 mmol) dissolved in THF (2 mL) was added and the mixture was
stirred for 1 h. Then, at ꢀ78 ꢁC Ag[BF4] (97.3 mg, 0.50 mmol) dis-
solved in THF (2 mL) was added. The reaction mixture was slowly
warmed to room temperature, stirred for 15 min and the precipi-
tated AgCl was filtered off. After 24 h the microcrystals precipitated
were filtered off, washed with THF (3 ꢃ 3 mL) and dried in vacuo.
Yield: 82 mg (32%). HRMS (ESI): m/z Calcd. for [C76H68
ClP4Rh2S4]þ: 1473.0947; found for [M ꢀ Rh]þ: 1473.0938. 1H NMR
CH2SO2Ph), 7.05e7.99 (m, 35H, HPh). 13C NMR (100 MHz, CD2Cl2):
d
25.8e26.2/34.9e35.4 (m/m, Ph2PCH2CH2PPh2), 53.7 (d, 1J(31P,
13C) ¼ 6.9 Hz, CH2SO2Ph), 125.5e138.1 (CPhr). 31P NMR (81 MHz,
CD2Cl2):
d
22.0 (ddd, 2J(31P, 31P) ¼ 361.8 Hz, 2J(31P, 31P) ¼ 35.3 Hz, 1J
(
(
103Rh, 31P) ¼ 135.0 Hz, PPh2), 60.5 (ddd, 2J(31P, 31P) ¼ 361.8 Hz, 2J
31P, 31P) ¼ 34.0 Hz, 1J(103Rh, 31P) ¼ 142.4 Hz, P of dppe trans to P),
73.5 (d0t0, 2J(31P, 31P) ¼ 35.3 Hz, 2J(31P, 31P) ¼ 34.0 Hz, 1J(103Rh,
31P) ¼ 183.7 Hz, P of dppe trans to Cl).
L2 ¼ dppe n ¼ 2, x ¼ 0 (9a). Yield: 352 mg (82%). HRMS (ESI): m/z
Calcd. for [C46H43P3RhS]þ: 823.1349; found for [MꢀCl]þ: 823.1364.
(400 MHz, CD2Cl2): d 1.82 (m, 16H, THF), 2.78 (s, br, 8H, CH2SPh),
3.67 (m, 16H, THF), 6.99e8.00 (m, 60H, HPh). 13C NMR (100 MHz,
1H NMR (400 MHz, CD2Cl2):
d
2.11e2.32 (m, 4H, Ph2PCH2CH2PPh2),
CD2Cl2):
d
25.9 (s, THF), 31.6/42.5 (d/d, 1J(31P, 13C) ¼ 27.8/26.7 Hz),
2.40e2.44 (m, 2H, CH2PPh2), 2.73e2.82 (m, 2H, CH2SPh), 7.03e7.49
68.0 (s, THF), 128.6e135.8 (CPh). 31P NMR (81 MHz, CD2Cl2):
d 28.4
(m, 35H, HPh). 13C NMR (100 MHz, CD2Cl2):
d
26.2e27.1/30.5e31.6
(ddd, 2J(31P, 31P) ¼ 35.3 Hz, 1J(103Rh, 31P) ¼ 140.7 Hz, 2J(103Rh,
(m/m, Ph2PCH2CH2PPh2), 32.4 (d, 1J(31P, 13C) ¼ 22.8 Hz, CH2PPh2),
31P) ¼ 2.5 Hz, PPh2 trans to S), 45.1 (ddd, 2J(31P, 31P) ¼ 35.3 Hz, 1J
38.4 (d, 2J(31P, 13C) ¼ 9.0 Hz, CH2SPh), 128.4e134.2 (CPh). 31P NMR
(
103Rh, 31P) ¼ 180.3 Hz, 2J(103Rh, 31P) ¼ 3.5 Hz, PPh2 trans to Cl).
(81 MHz, CD2Cl2):
d
58.2 (m, 2J(31P, 31P) ¼ 284.7 Hz, 2J(31P,
31P) ¼ 31.3 Hz, 1J(103Rh, 31P) ¼ 131.5 Hz, P of dppe trans to P), 60.6
(m, 2J(31P, 31P) ¼ 284.7 Hz, 2J(31P, 31P) ¼ 32.1 Hz, 1J(103Rh,
31P) ¼ 134.9 Hz, PPh2), 65.2 (d0t0, 2J(31P, 31P) ¼ 31.3 Hz, 2J(31P,
31P) ¼ 32.1 Hz, 1J(103Rh, 31P) ¼ 161.4 Hz, P of dppe trans to Cl).
L2 ¼ dppe n ¼ 2, x ¼ 1 (9b). Yield: 357 mg (85%). HRMS (ESI): m/z
Calcd. for [C46H43OP3RhS]þ: 839.1297; found for [M ꢀ Cl]þ:
3.4. Preparation of [Rh{Ph2P(CH2)nS(O)xPh-kP,kS/O}L2]
[BF4] (13e18)
At room temperature to [(RhL2)2(
m
-Cl)2] (L2 ¼ cod, 4; dppe, 5;
0.25 mmol) in THF (5 mL) Ph2P(CH2)nS(O)xPh (0.50 mmol) dis-
solved in THF (2 mL) was added with stirring. After 1 h Ag[BF4]
(97.3 mg, 0.50 mmol) dissolved in THF (2 mL) was added at ꢀ78 ꢁC.
The reaction mixture was allowed to warm to room temperature
and stirred for 15 min. Then, the precipitated AgCl was filtered off
and the filtrate 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 ꢃ 5 mL) and
dried in vacuo.
839.1305. 1H NMR (400 MHz, THF-d8):
d 1.82e2.12 (m, 4H,
Ph2PCH2CH2PPh2), 2.38e2.46/2.74e2.82 (m/m, 1H/1H, CH2PPh2),
2.90e2.98/3.51e3.58 (m/m, 1H/1H, CH2SOPh), 6.88e8.18 (m, 35H,
HPh). 13C NMR (125 MHz, THF-d8):
d
20.4 (d, 1J(31P, 13C) ¼ 21.6 Hz,
CH2PPh2), 25.2e26.8/33.5e34.6 (m/m, Ph2PCH2CH2PPh2), 53.6 (d,
2J(31P, 13C) ¼ 6.3 Hz, CH2SOPh), 133.9e145.5 (CPh). 31P NMR
(202 MHz, THF-d8):
d
23.1 (m, 2J(31P, 31P) ¼ 328.6 Hz, 2J(31P,
31P) ¼ 9.0 Hz, 1J(103Rh, 31P) ¼ 133.2 Hz, PPh2), 57.0 (m, 2J(31P,
31P) ¼ 328.6 Hz, 2J(31P, 31P) ¼ 48.8 Hz, 1J(103Rh, 31P) ¼ 140.9 Hz, P of
dppe trans to P), 74.0 (m, 2J(31P, 31P) ¼ 9.0 Hz, 2J(31P, 31P) ¼ 48.8 Hz,
1J(103Rh, 31P) ¼ 184.3 Hz, P of dppe trans to Cl).
L2 ¼ cod, n ¼ 1, x ¼ 0 (13a). Yield: 234 mg (90%). HRMS (ESI): m/z
Calcd. for [C27H29PRhS]þ: 519.0777; found for [M]þ: 519.0772. 1H
NMR (200 MHz, CD2Cl2):
d
2.26/2.53 (m/m, 3H/5H, 4ꢃ CH2, cod),
5.68/5.33 (s/s, br/br, 2H/2H, 4ꢃ CH, cod), 5.24 (d, 2J(31P, 1H) ¼ 5.8 Hz,
L2 ¼ dppe n ¼ 2, x ¼ 2 (9c). Yield: 387 mg (87%). HRMS (ESI): m/z
CH2SPh), 7.25e7.91 (m,15H, HPh). 13C NMR (50 MHz, CD2Cl2):
d 29.1/
Calcd. for [C46H43O2P3RhS]þ: 855.1246; found for [MꢀCl]þ:
31.7 (s/s, br/br, 4ꢃ CH2, cod), 86.5/106.0 (d/s, e/br, 1J(103Rh,
855.1263. 1H NMR (400 MHz, CD2Cl2):
d 1.80e1.90/2.00e2.10 (m/m,
13C) ¼ 9.3 Hz, 4ꢃ CH, cod), 107.7 (d, 1J(13C, 31P) ¼ 7.3 Hz, CH2SPh),
2H/2H, Ph2PCH2CH2PPh2), 2.48e2.53 (m, 2H, CH2PPh2), 3.41e3.46
127.5e134.3 (CPh). 31P NMR (81 MHz, CD2Cl2):
31P) ¼ 119.5 Hz, PPh2).
d
ꢀ31.1 (d, 1J(103Rh,
(m, 2H, CH2SO2Ph), 7.07e7.93 (m, 35H, HPh). 13C NMR (100 MHz,
CD2Cl2):
d
21.2 (d, 1J(31P, 13C) ¼ 19.6 Hz, CH2PPh2), 25.5e25.9/
L2 ¼ cod, n ¼ 1, x ¼ 1 (13b). Yield: 274 mg (88%). HRMS (ESI): m/z
34.6e35.1 (m/m, Ph2PCH2CH2PPh2), 52.7 (d, 2J(31P, 13C) ¼ 5.1 Hz,
Calcd. for [C27H29OPRhS]þ: 535.0722; found for [M]þ: 535.0718. 1H
CH2SO2Ph), 127.7e138.7 (CPh). 31P NMR (202 MHz, CD2Cl2):
d
22.1
NMR (400 MHz, CD2Cl2):
d
2.04e2.40/2.49e2.67 (m/m, 5H/3H, 4ꢃ
(ddd, 2J(31P, 31P) ¼ 357.6 Hz, 2J(31P, 31P) ¼ 35.7 Hz, 1J(103Rh,
31P) ¼ 133.8 Hz, PPh2), 58.9 (ddd, 2J(31P, 31P) ¼ 357.6 Hz, 2J(31P,
31P) ¼ 33.6 Hz, 1J(103Rh, 31P) ¼ 140.6 Hz, P of dppe trans to P), 74.0
(d0t0, 2J(31P, 31P) ¼ 35.7 Hz, 2J(31P, 31P) ¼ 33.6 Hz, 1J(103Rh,
31P) ¼ 183.1 Hz, P of dppe trans to Cl).
CH2, cod), 3.26/3.69/5.71/5.78 (s/s/s/s, br/br/br/br, 1H/1H/1H/1H,
4ꢃ CH, cod), 4.23/4.48 (dd/dd, 2J(31P, 1H) ¼ 9.0/2.8 Hz, 2J(1H,
1H) ¼ 14.9/14.9 Hz, 1H/1H, CH2SOPh), 7.23e7.60 (m, 15H, HPh). 13
C
NMR (100 MHz, CD2Cl2):
d
27.8/27.9/32.3/33.1 (s/s/s/s, 4ꢃ CH2, cod),
57.4 (d, 1J(13C, 31P) ¼ 10.2 Hz, CH2SOPh), 69.4/74.1/108.1/109.9 (d/d/
L2 ¼ dppe n ¼ 3, x ¼ 1 (11b). Yield: 351 mg (79%). HRMS (ESI): m/
dd/dd, br/br, 1J(103Rh, 13C) ¼ 13.9/14.5/10.5/9.9 Hz, 2J(31Ptrans
,
z
Calcd. for [C47H45OP3RhS]þ: 853.1454; found for [MꢀCl]þ:
13C) ¼ 7.1/7.2 Hz, 4ꢃ CH, cod), 124.1e136.1 (CPh). 31P NMR (81 MHz,
853.1474. 1H NMR (400 MHz, CD2Cl2):
d
1.81e2.36 (m, 8H,
CD2Cl2):
d
53.6 (d, 1J(103Rh, 31P) ¼ 162.7 Hz, PPh2).
CH2CH2CH2PPh2 þ Ph2PCH2CH2PPh2), 2.70e2.77/2.82e2.89 (m/m,
L2 ¼ cod, n ¼ 1, x ¼ 2 (13c). Yield: 268 mg (84%). HRMS (ESI): m/z
1H/1H, CH2SOPh), 7.07e7.95 (m, 35H, HPh). 13C NMR (100 MHz,
Calcd. for [C27H29O2PRhS]þ: 551.0675; found for [M]þ: 551.0675. 1H
CD2Cl2):
d
19.6 (d, 2J(31P, 13C) ¼ 4.5 Hz, CH2CH2CH2), 25.8e26.1/
NMR (400 MHz, CD2Cl2):
d
2.08e2.21/2.45e2.59 (m/m, 3H/5H, 4ꢃ
34.7e35.3 (m/m, Ph2PCH2CH2PPh2), 27.1 (d, 1J(31P, 13C) ¼ 21.9 Hz,
CH2PPh2), 58.7 (d, 3J(31P, 13C) ¼ 13.0 Hz, CH2SOPh), 123.9e144.7
CH2, cod), 3.74/5.71 (s/s, br/br, 2H/2H, 4ꢃ CH, cod), 4.36 (d, 2J(31P,
1H) ¼ 8.1 Hz, CH2SO2Ph), 7.51e8.31 (m, 15H, HPh). 13C NMR

1778
M. Block et al. / Journal of Organometallic Chemistry 696 (2011) 1768e1781
(100 MHz, CD2Cl2):
d
27.7/32.7 (s/s, br/br, 4ꢃ CH2, cod), 57.2 (d, 1J
L2 ¼ dppe, n ¼ 1, x ¼ 0 (14a). Yield: 394 mg (88%). HRMS (ESI): m/z
Calcd. for [C45H41P3RhS]þ: 809.1180; found for [M]þ: 809.1181. 1H
(
13C, 31P) ¼ 10.0 Hz, CH2SO2Ph), 72.4/109.6 (d/s, e/br 1J(103Rh,
13C) ¼ 14.3 Hz, 4ꢃ CH, cod), 126.0e137.0 (CPh). 31P NMR (81 MHz,
NMR (400 MHz, CD2Cl2): d 2.20e2.33/2.44e2.57 (m/m, 2H/2H,
CD2Cl2):
d
25.3 (d, 1J(103Rh, 31P) ¼ 149.0 Hz, PPh2).
Ph2PCH2CH2PPh2), 5.58 (d, 2J(31P, 1H) ¼ 5.7 Hz, 2H, CH2SPh),
L2 ¼ cod, n ¼ 2, x ¼ 0 (15a). Yield: 267 mg (86%). HRMS (ESI): m/z
6.94e7.93 (m, 35H, HPh). 13C NMR (100 MHz, CD2Cl2):
d 26.8e27.2/
Calcd. for [C28H31PRhS]þ: 533.4901; found for [M]þ: 533.4909. 1H
30.7e31.2 (m/m, Ph2PCH2CH2PPh2), 60.3 (d, 1J(31P, 13C) ¼ 19.3 Hz,
NMR (400 MHz, CD2Cl2):
d
2.30e2.48 (m, 8H, 4ꢃ CH2, cod),
CH2SPh), 128.7e135.2 (CPh). 31P NMR (81 MHz, CD2Cl2):
d
ꢀ22.8
2.60e2.65 (m, 2H, CH2PPh2), 2.90e2.99 (m, 2H, CH2SPh), 4.27/5.16
(ddd, 2J(31P, 31P) ¼ 305.2 Hz, 2J(31P, 31P) ¼ 22.8 Hz, 1J(103Rh,
31P) ¼ 111.1 Hz, PPh2), 61.6 (ddd, 2J(31P, 31P) ¼ 305.2 Hz, 2J(31P,
31P) ¼ 29.4 Hz, 1J(103Rh, 31P) ¼ 139.3 Hz, P of dppe trans to P), 69.1
(ddd, 2J(31P, 31P) ¼ 22.8 Hz, 2J(31P, 31P) ¼ 29.4 Hz, 1J(103Rh,
31P) ¼ 166.6 Hz, P of dppe trans to S).
(s/s, br/br, 2H/2H, 4ꢃ CH, cod), 7.53e7.72 (m, 15H, HPh). 13C NMR
(100 MHz, CD2Cl2):
d
29.1/32.0 (s/s, br/br, 4ꢃ CH2, cod), 30.2 (d,1J(31P,
13C) ¼ 30.2 Hz, CH2PPh2), 37.5 (d, 2J(31P, 13C) ¼ 7.2 Hz, CH2SPh), 87.7/
105.4 (d/dd, 1J(103Rh, 13C) ¼ 10.8/9.2 Hz, 2J(31Ptrans
,
13C) ¼ 6.7 Hz, 4ꢃ
CH, cod), 128.5e133.4 (CPh). 31P NMR (81 MHz, CD2Cl2):
d
59.0 (d, 1J
L2 ¼ dppe, n ¼ 1, x ¼ 1 (14b). Yield: 392 mg (86%). HRMS (ESI): m/z
(
103Rh, 31P) ¼ 147.2 Hz, PPh2).
Calcd. for [C45H41OP3RhS]þ: 825.1136; found for [M]þ: 825.1131. 1H
L2 ¼ cod, n ¼ 2, x ¼ 1 (15b). Yield: 280 mg (88%). HRMS (ESI): m/z
NMR (500 MHz, CD2Cl2):
4.39e4.47 (m, 2H, CH2SOPh), 6.76e8.14 (m, 35H, HPh). 13C NMR
(100 MHz, CD2Cl2): 22.6e23.0/32.4e32.9 (m/m, Ph2PCH2CH2PPh2),
d 1.93e2.78 (m, 4H, Ph2PCH2CH2PPh2),
Calcd. for [C28H31OPRhS]þ: 549.4890; found for [M]þ: 549.4887. 1H
NMR (400 MHz, CD2Cl2):
d
1.77e2.49 (m, 8H, 4ꢃ CH2 (cod)),
d
2.81e3.29 (m, 4H, CH2CH2SOPh), 4.09/4.212/4.24 (s/s/s, br, 1H/2H/
56.6 (s, br, CH2SOPh),124.4e137.5 (CPh). 31P NMR (202 MHz, CD2Cl2):
1H, 4ꢃ CH (cod)), 7.27e8.00 (m, 15H, HPh). 13C NMR (100 MHz,
d
55.5 (ddd, 2J(31P, 31P) ¼ 308.6 Hz, 2J(31P, 31P) ¼ 31.6 Hz, 1J(103Rh,
CD2Cl2):
d
29.1/32.0 (s/s, br/br, 4ꢃ CH2 (cod)), 30.2 (d, 1J(31P,
31P) ¼ 146.3 Hz, PPh2), 58.9 (ddd, 2J(31P, 31P) ¼ 308.6 Hz, 2J(31P,
31P)¼ 34.3 Hz,1J(103Rh, 31P)¼ 143.6 Hz, P of dppe transto P), 74.0 (d0t0,
2J(31P, 31P) ¼ 31.6 Hz, 2J(31P, 31P) ¼ 34.3 Hz, 1J(103Rh, 31P) ¼ 182.4 Hz, P
of dppe trans to O).
13C) ¼ 30.2 Hz, CH2PPh2), 52.9 (s, CH2SOPh), 78.0/78.3/79.0 (d/d/m,
1J(103Rh, 13C) ¼ 8.1/11.3 Hz, 4ꢃ CH, cod), 124.6e134.1 (CPh). 31P NMR
(81 MHz, CD2Cl2):
d
52.7 (d, 1J(103Rh, 31P) ¼ 135.8 Hz, PPh2).
L2 ¼ cod, n ¼ 2, x ¼ 2 (15c). Yield: 261 mg (80%). HRMS (ESI): m/z
L2 ¼ dppe, n ¼ 1, x ¼ 2 (14c). Yield: 367 mg (79%). HRMS (ESI): m/z
Calcd. for [C28H31O2PRhS]þ: 565.4881; found for [M]þ: 565.4875.
Calcd. for [C45H41O2P3RhS]þ: 841.1080; found for [M]þ: 841.1090. 1H
1H NMR (400 MHz, CD2Cl2):
d
2.01/2.12/2.46e2.62 (m/m/m, 2H/2H/
NMR (500 MHz, CD2Cl2): d 2.06e2.14/2.47e2.56 (m/m, 2H/2H,
4H, 4ꢃ CH2, cod), 3.10e3.15 (m, 2H, CH2PPh2), 3.39e3.46 (m,
Ph2PCH2CH2PPh2), 4.67 (d, 2J(31P, 1H) ¼ 6.9 Hz, 2H, CH2SO2Ph),
CH2SO2Ph), 3.25/5.38 (s/s, br/br, 2H/2H, 4ꢃ CH, cod), 7.54e7.89 (m,
7.16e8.03 (m, 35H, HPh). 13C NMR (100 MHz, CD2Cl2):
d 23.9e24.4/
15H, HPh). 13C NMR (125 MHz, CD2Cl2):
d
20.1 (d, 1J(31P,
33.5e34.2 (m/m, Ph2PCH2CH2PPh2), 56.4 (s, br, CH2SO2Ph),
13C) ¼ 23.3 Hz, CH2PPh2), 28.4/31.1/31.3 (s/s/s, e/e/br, 4ꢃ CH2, cod),
126.0e139.7 (CPh). 31P NMR (202 MHz, CD2Cl2): 27.1 (ddd, 2J(31P,
d
51.9 (s, CH2SO2Ph), 71.1/110.4 (d/dd, 1J(103Rh, 13C) ¼ 15.6/10.1 Hz, 2J
31P) ¼ 307.0 Hz, 2J(31P, 31P) 29.5 Hz, 1J(103Rh, 31P) ¼ 129.7 Hz, PPh2),
60.1 (ddd, 2J(31P, 31P) ¼ 307.0 Hz, 2J(31P, 31P) ¼ 34.4 Hz, 1J(103Rh,
31P) ¼ 145.6 Hz, P of dppe trans to P), 76.2 (d0t0, 2J(31P, 31P) ¼ 29.5 Hz, 2J
31
(
P
,
13C) ¼ 6.7 Hz, 4ꢃ CH, cod), 127.6e135.8 (CPh). 31P NMR
trans
(202 MHz, CD2Cl2):
d
18.9 (d, 1J(103Rh, 31P) ¼ 149.5 Hz, PPh2).
L ¼ cod, n ¼ 3, x ¼ 0 (17a). Yield: 285 mg (90%). HRMS (ESI): m/z
(
31P, 31P) ¼ 34.4 Hz, 1J(103Rh, 31P) ¼ 184.7 Hz, P of dppe trans to O).
L2 ¼ dppe, n ¼ 2, x ¼ 0 (16a). Yield: 414 mg (91%). HRMS (ESI): m/
Calcd. for [C29H33PRhS]þ: 547.5166; found for [M]þ: 547.5168. 1H
NMR (400 MHz, CD2Cl2):
d
2.02e2.21/2.34e2.42 (m/m, 6H/4H,
z Calcd. for [C46H43P3RhS]þ: 823.1348; found for [M]þ: 823.1354. 1H
CH2CH2CH2/4ꢃ CH2, cod), 2.78 (m, 2H, CH2PPh2), 3.52 (m, 2H,
NMR (500 MHz, CD2Cl2): d 2.18e2.28/2.37e2.44 (m/m, 2H/2H,
CH2SPh), 3.82/4.64 (s/s, br/br, 2H/2H, 4ꢃ CH, cod), 7.15e7.61 (m,
Ph2PCH2CH2PPh2), 2.54e2.58 (m, 2H, CH2PPh2), 2.78e2.83 (m, 2H,
15H, HAr). 13C NMR (125 MHz, CD2Cl2):
d 22.7 (s, br, CH2CH2CH2),
CH2SPh), 7.14e7.57 (m, 35H, HPh). 13C NMR (125 MHz, CD2Cl2):
25.6 (d, 1J(13C, 31P) ¼ 26.3 Hz, CH2PPh2), 29.26/29.27/32.16/32.19 (s/
s/s/s, 4ꢃ CH2, cod), 39.3 (d, 3J(13C, 31P) ¼ 3.6 Hz, CH2SPh), 86.0/104.8
(d/dd, 1J(13C, 103Rh) ¼ 11.2/10.0 Hz, 2J(13C, 31Ptrans) ¼ 7.1 Hz, 4ꢃ CH,
cod), 126.6e134.0 (CAr). 31P NMR (80 MHz, CD2Cl2): 12.4 (d, 1J(31P,
103Rh) ¼ 140.0 Hz, PPh2).
d
27.4e27.8/31.6e32.1 (m/m, Ph2PCH2CH2PPh2), 33.0 (d, 1J(31P,
13C) ¼ 23.6 Hz, CH2PPh2), 39.2 (d, 2J(31P, 13C) ¼ 10.9 Hz, CH2SPh),
129.3e134.9 (CPh). 31P NMR (202 MHz, CD2Cl2):
d
59.4 (m, 2J(31P,
31P) ¼ 285.2 Hz, 2J(31P, 31P) ¼ 31.6 Hz, 1J(103Rh, 31P) ¼ 135.3 Hz,
PPh2), 60.6 (m, 2J(31P, 31P) ¼ 285.2 Hz, 2J(31P, 31P) ¼ 31.7 Hz, 1J(103Rh,
31P) ¼ 132.1 Hz, P of dppe trans to P), 65.5 (d0t0, 2J(31P, 31P) ¼ 31.7 Hz,
2J(31P, 31P) ¼ 31.6 Hz, 1J(103Rh, 31P) ¼ 151.2 Hz, P of dppe trans to S).
L2 ¼ dppe, n ¼ 2, x ¼ 1 (16b). Yield: 361 mg (78%). HRMS (ESI):
m/z Calcd. for [C46H43OP3RhS]þ: 839.1290; found for [M]þ:
L2 ¼ cod, n ¼ 3, x ¼ 1 (17b). Yield: 288 mg (87%). HRMS (ESI): m/z
Calcd. for [C29H33OPRhS]þ: 563.5157; found for [M]þ: 563.5165. 1H
NMR (400 MHz, CD2Cl2):
d 2.02e2.44/2.50e2.61 (m/m, 8H/3H,
CH2CHHPPh2, 4ꢃ CH2, cod), 3.06 (m, 1H, CHHPPh2), 3.18/3.99 (m/m,
1H/1H, CH2SOPh), 4.15/4.37/4.54/5.17 (s/s/s/s, br/br/br/br, 4H, 4ꢃ
839.1284. 1H NMR (400 MHz, CD2Cl2):
d 1.89e3.39 (m, 8H,
CH, cod), 7.47e8.11 (m, 15H, HPh). 13C NMR (100 MHz, CD2Cl2):
d
17.3
Ph2PCH2CH2PPh2 þ CH2CH2SOPh), 6.99e8.23 (m, 35H, HPh). 13C
(s, br, CH2CH2PPh2), 24.2 (d, 1J(31P, 13C) ¼ 24.2 Hz, CH2PPh2), 28.7/
30.7/30.9/31.8 (s/s/s/s, 4ꢃ CH2 (cod)), 57.7 (d, 3J(31P, 13C) ¼ 4.8 Hz,
CH2SOPh), 94.5/99.0/104.3e104.7 (d/d/m, 1J(103Rh, 13C) ¼ 10.0/
8.4 Hz, 4ꢃ CH, cod), 125.5e141.3 (CPh). 31P NMR (81 MHz, CD2Cl2):
NMR (125 MHz, CD2Cl2):
d
21.6 (d, 1J(31P, 13C) ¼ 21.0 Hz, CH2PPh2),
26.4e27.6/35.1e35.8 (m/m, Ph2PCH2CH2PPh2), 60.3 (d, 2J(31P,
13C) ¼ 9.5 Hz, CH2SOPh), 124.4e143.4 (CPh). 31P NMR (202 MHz,
CD2Cl2):
(
d
57.8 (m, 2J(31P, 31P) ¼ 263.2 Hz, 2J(31P, 31P) ¼ 33.1 Hz, 1J
d
11.0 (d, 1J(103Rh, 31P) ¼ 140.0 Hz, PPh2).
103Rh, 31P) ¼ 136.4 Hz, PPh2), 59.0 (m, 2J(31P, 31P) ¼ 263.2 Hz, 2J(31P,
L2 ¼ cod, n ¼ 3, x ¼ 2 (17c). Yield: 277 mg (83%). HRMS (ESI): m/z
31P) ¼ 29.4 Hz, 1J(103Rh, 31P) ¼ 133.1 Hz, P of dppe trans to P), 60.1
Calcd. for [C29H33O2PRhS]þ: 579.5154; found for [M]þ: 579.5155. 1H
(m, 2J(31P, 31P)
¼
29.4 Hz, 2J(31P, 31P)
¼
33.1 Hz, 1J(103Rh,
NMR (400 MHz, CD2Cl2):
d
1.74e2.45 (m, 10H, CH2CH2CH2, 4ꢃ CH2,
31P) ¼ 145.1 Hz, P of dppe trans to S).
cod), 2.61 (m, 2H, CH2PPh2), 3.17/5.32 (s/s, br/br, 2H/2H, 4ꢃ CH (cod)),
L2 ¼ dppe, n ¼ 2, x ¼ 2 (16c). Yield: 361 mg (78%). HRMS (ESI): m/z
3.57 (m, 2H, CH2SO2Ph), 7.44e7.82 (m,15H, HPh). 13C NMR (100 MHz,
Calcd. for [C46H43O2P3RhS]þ: 855.1239; found for [M]þ: 855.1246.1H
CD2Cl2):
d
17.5 (s, br, CH2CH2CH2), 27.4 (d, 1J(13C, 31P) ¼ 17.3 Hz,
NMR (400 MHz, CD2Cl2): d 1.98e2.33 (m, 4H, Ph2PCH2CH2PPh2), 2.91
CH2PPh2), 28.3/33.2 (s/s, 4ꢃ CH2, cod), 57.0 (d, 3J(13C, 31P) ¼ 3.8 Hz,
CH2SO2Ph), 71.6/108.3 (d/s, e/br,1J(103Rh,13C) ¼ 15.3 Hz, 4ꢃ CH, cod),
(m, 2H, CH2PPh2), 3.31 (m, 2H, CH2SO2Ph), 7.05e7.89 (m, 35H, HPh).
13C NMR (50 MHz, CD2Cl2):
d
22.5 (d, 1J(31P, 13C) ¼ 1.9 Hz, CH2PPh2),
128.2e136.4 (CPh). 31P NMR (81 MHz, CD2Cl2):
31P) ¼ 147.8 Hz, PPh2).
d
24.2 (d, 1J(103Rh,
24.5e25.2/34.0e35.4 (m/m, Ph2PCH2CH2PPh2), 52.4 (d, 2J(31P,
13C) ¼ 6.4 Hz, CH2SO2Ph), 127.9e135.8 (CPh). 31P NMR (81 MHz,

M. Block et al. / Journal of Organometallic Chemistry 696 (2011) 1768e1781
1779
CD2Cl2):
(
d
16.5 (ddd, 2J(31P, 31P) ¼ 304.9 Hz, 2J(31P, 31P) ¼ 34.4 Hz, 1J
23b the reaction mixtures were allowed to warm to room
temperature. The precipitated NaCl was filtered off and n-pentane
(5 mL) was added to the filtrate. The precipitate obtained was
filtered off, washed with n-pentane (3 ꢃ 1 mL) and dried in vacuo.
L2 ¼ cod, n ¼ 1, x ¼ 1 (20b).2 HRMS (ESI): m/z Calcd. for
[C27H29OPRhS]þ: 535.0726; found for [M þ H]þ: 535.0733. 1H NMR
103Rh, 31P) ¼ 136.6 Hz, PPh2), 60.5 (ddd, 2J(31P, 31P) ¼ 304.9 Hz, 2J(31P,
31P) ¼ 33.1 Hz, 1J(103Rh, 31P) ¼ 139.0 Hz, P of dppe trans to P), 77.4
(d0t0, 2J(31P, 31P) ¼ 34.4 Hz, 2J(31P, 31P) ¼ 33.1 Hz, 1J(103Rh,
31P) ¼ 204.5 Hz, P of dppe trans to O).
L ¼ dppe, n ¼ 3, x ¼ 0 (18a). Yield: 425 mg (92%). HRMS (ESI): m/
z Calcd. for [C47H45P3RhS]þ: 837.1504; found for [M]þ: 837.1493. 1H
(500 MHz, THF-d8):
d
1.91e2.41 (m, 8H, 4ꢃ CH2, cod), 2.88 (d, 2J(31P,
NMR (500 MHz, CD2Cl2):
d
1.87e2.02/2.04e2.37 (m, 4H,
1H) ¼ 10.1 Hz, 1H, CHSOPh), 3.81/4.08/5.02/5.14 (s/s/s/s, br/br/br/br,
PH2PCH2CH2PPh2), 1.92e2.01 (m, 2H, CH2CH2CH2), 2.30 (m, 2H,
Ph2PCH2CH2CH2), 2.96 (m, 2H, PhSCH2), 6.80e7.74 (m, 35H, HAr).
1H/1H/1H/1H, 4ꢃ CH, cod), 6.98e8.35 (m, 15H, HPh). 13C NMR
(100 MHz, THF-d8):
d
27.7/30.0/31.9/32.4 (s/s/s/s, 4ꢃ CH2 (cod)), 70.1
13C NMR (125 MHz, CD2Cl2):
d
21.3 (s, CH2CH2CH2), 26.4 (dd, 1J(13C,
(d, 1J(13C, 31P) ¼ 14.3 Hz, CHSOPh), 87.0/87.3/99.4/101.4 (d/d/m/m, 1J
31P) ¼ 24.7 Hz, 3J(13C,
P
) ¼ 1.8 Hz, Ph2PCH2CH2), 27.7e27.9/
(
103Rh, 13C) ¼ 10.1/9.7 Hz, 4ꢃ CH, cod), 124.4e140.2 (CPh). 31P NMR
31
trans
32.5e33.1 (m/m, Ph2PCH2CH2PPh2), 35.9 (dd, 3J(13C, 31P)/3J(13C,
(81 MHz, THF-d8):
d
32.2 (d, 1J(103Rh, 31P) ¼ 149.6 Hz, PPh2).
31
P
trans
) ¼ 8.8 Hz/3.4 Hz, PhSCH2), 126.1e135.9 (CAr). 31P NMR
L2 ¼ cod, n ¼ 1, x ¼ 2 (20c).2 HRMS (ESI): m/z Calcd. for
[C27H29O2PRhS]þ: 551.0675; found for [M þ H]þ: 551.0669. 1H NMR
(81 MHz, CD2Cl2):
d
7.1 (ddd, 2J(31P, 31P) ¼ 33.2 Hz, 2J(31P,
31P) ¼ 287.8 Hz, 1J(31P, 103Rh) ¼ 131.1 Hz, PPh2), 59.6 (ddd, 2J(31P,
31P) ¼ 31.4 Hz, 2J(31P, 31P) ¼ 287.8 Hz, 1J(31P, 103Rh) ¼ 128.2 Hz, P
(dppe) trans to P), 66.4 (ddd, 2J(31P, 31P) ¼ 31.4 Hz, 2J(31P, 31P) ¼ 33.2,
1J(31P, 103Rh) ¼ 160.0 Hz, P (dppe) trans to S).
(500 MHz, CD2Cl2):
d
1.91e2.54 (m, 8H, 4ꢃ CH2, cod), 2.71 (d, 2J(31P,
1H) ¼ 12.8 Hz, 1H, CHSO2Ph), 3.39/4.79/4.84 (s/s/s, br/br/br, 2H/1H/
1H, 4ꢃ CH, cod), 6.86e8.44 (m, 15H, HPh). 13C NMR (100 MHz,
CD2Cl2):
d
27.6/28.3/31.2/31.7 (s/s/s/s, 4ꢃ CH2, cod), 69.0 (d, 1J(13C,
L2 ¼ dppe, n ¼ 3, x ¼ 1 (18b). Yield: 423 mg (90%). HRMS (ESI):
31P) ¼ 14.7 Hz, CHSO2Ph), 85.5/87.9/97.8/99.2 (d/d/m/m, 1J(103Rh,
m/z Calcd. for [C47H45P3ORhS]þ: 853.1448; found for [M]þ:
13C) ¼ 9.9/9.8 Hz, 4ꢃ CH, cod), 124.4e140.2 (CPh). 31P NMR (81 MHz,
853.1456. 1H NMR (400 MHz, CD2Cl2):
d
1.71e2.47 (m, 8H,
CD2Cl2):
d
26.6 (d, 1J(103Rh, 31P) ¼ 159.1 Hz, PPh2).
CH2CH2CH2PPh2 þ Ph2PCH2CH2PPh2), 3.16e3.20/3.24e3.29 (m/m,
L2 ¼ dppe, n ¼ 1, x ¼ 0 (21a).3 31P NMR (81 MHz, THF):
d 9.4 (ddd,
1H/1H, CH2SOPh), 6.95e8.14 (m, 35H, HPh). 13C NMR (100 MHz,
2J(31P, 31P) ¼ 8.2 Hz, 2J(31P, 31P) ¼ 248.7 Hz, 1J(31P, 103Rh) ¼ 112.3 Hz,
PPh2), 62.0 (ddd, 2J(31P, 31P) ¼ 10.0 Hz, 2J(31P, 31P) ¼ 248.7 Hz, 1J(31P,
103Rh) ¼ 148.9 Hz, P of dppe trans to P), 69.4 (ddd, 2J(31P,
31P) ¼ 8.2 Hz, 2J(31P, 31P) ¼ 10.0, 1J(31P, 103Rh) ¼ 159.1 Hz, P of dppe
trans to S).
CD2Cl2):
d 18.5 (s, CH2CH2CH2), 27.1e27.5/31.4e31.8 (m/m,
Ph2PCH2CH2PPh2), 27.3 (d, 1J(31P, 13C) ¼ 25.4 Hz CH2PPh2), 58.7 (dd,
3J(13C, 31P) ¼ 7.6 Hz, 3J(13C, 31Ptrans) ¼ 3.3 Hz, CH2SOPh),124.2e143.7
(CPh). 31P NMR (202 MHz, THF-d8):
d
7.7 (ddd, 2J(31P, 31P) ¼ 38.2 Hz,
2J(31P, 31P) ¼ 257.4 Hz, 1J(31P, 103Rh) ¼ 132.2 Hz, PPh2), 56.4 (ddd, 2J
L2 ¼ dppe, n ¼ 1, x ¼ 1 (21b).2 HRMS (ESI): m/z Calcd. for
(
31P, 31P) ¼ 29.3 Hz, 2J(31P, 31P) ¼ 257.4 Hz, 1J(31P, 103Rh) ¼ 134.2 Hz,
[C45H41OP3RhS]þ: 825.1147; found for [M þ H]þ: 825.1141. 1H NMR
P of dppe trans to P), 60.0 (ddd, 2J(31P, 31P) ¼ 38.2 Hz, 2J(31P,
(500 MHz, CD2Cl2): d 1.93e2.29 (m, 4H, Ph2PCH2CH2PPh2), 4.12 (s,
31P) ¼ 29.3, 1J(31P, 103Rh) ¼ 148.2 Hz, P of dppe trans to S).
br, 1H, CHSOPh), 6.97e8.05 (m, 35H, HPh). 13C NMR (125 MHz,
CD2Cl2): 27.5e28.0/30.0e30.4 (m/m, Ph2PCH2CH2PPh2), 66.6 (s,
L2 ¼ dppe, n ¼ 3, x ¼ 2 (18c). 31P NMR (81 MHz, THF-d8):
d
21.2
d
(ddd, 2J(31P, 31P) ¼ 30.6 Hz, 2J(31P, 31P)
¼
329.5 Hz, 1J(31P,
br, CHSOPh), 124.2e143.7 (CPh). 31P NMR (81 MHz, CD2Cl2):
d
ꢀ25.1
103Rh) ¼ 127.0 Hz, PPh2), 57.3 (ddd, 2J(31P, 31P) ¼ 28.4 Hz, 2J(31P,
31P)¼ 329.5Hz,1J(31P, 103Rh)¼ 121.6 Hz, Pofdppetransto P), 70.5(d0t0,
2J(31P, 31P) ¼ 30.6 Hz, 2J(31P, 31P) ¼ 28.4, 1J(31P, 103Rh) ¼ 182.5 Hz, P of
dppe trans to O).
(ddd, 2J(31P, 31P) ¼ 29.0 Hz, 2J(31P, 31P) ¼ 276.7 Hz, 1J(31P,
103Rh) ¼ 106.2 Hz, PPh2), 60.0 (ddd, 2J(31P, 31P) ¼ 30.4 Hz, 2J(31P,
31P) ¼ 276.7 Hz, 1J(31P, 103Rh) ¼ 145.7 Hz, P of dppe trans to P), 67.1
(ddd, 2J(31P, 31P)
¼
29.0 Hz, 2J(31P, 31P)
¼
30.4, 1J(31P,
103Rh) ¼ 157.3 Hz, P of dppe trans to S).
3.5. Preparation of [{Rh(
(19$THF)
m-Ph2PCH(SPh)-kC:kP)(cod)}2]$THF
L2 ¼ dppe, n ¼ 1, x ¼ 2 (21c).2 HRMS (ESI): m/z Calcd. for
[C45H41O2P3RhS]þ: 841.1090; found for [M þ H]þ: 841.1089. 1H NMR
(500 MHz, CD2Cl2):
d 1.93e2.51 (m, 4H, Ph2PCH2CH2PPh2), 2.78 (s,
At room temperature to a stirred solution of [(Rh(cod))2(
m-Cl)2]
1H, CHSOPh) 7.11e7.99 (m, 35H, HPh). 13C NMR (100 MHz, CD2Cl2):
25.3e25.8/31.5e31.8 (m/m, Ph2PCH2CH2PPh2), 37.4 (s, br,
CHSO2Ph),125.9e149.7 (CPh). 31P NMR (81 MHz, CD2Cl2):
8.7 (ddd,
(123.3 mg, 0.25 mmol) in THF (5 mL) Ph2PCH2SPh (154.2 mg,
0.50 mmol) dissolved in THF (2 mL) was added and the mixture was
stirred for 1 h. The solution was reduced to half of its volume and
sodium bis(trimethylsilyl)amide (0.50 mmol, 2 M in THF) was
added at ꢀ78 ꢁC. After 24 h the crystals formed were filtered off,
washed with THF (3 ꢃ 3 mL) and dried in vacuo.
d
d
2J(31P, 31P) ¼ 27.1 Hz, 2J(31P, 31P) ¼ 286.7 Hz, 1J(31P, 103Rh) ¼ 116.4 Hz,
PPh2), 60.4 (ddd, 2J(31P, 31P) ¼ 30.4 Hz, 2J(31P, 31P) ¼ 286.7 Hz, 1J(31P,
103Rh) ¼ 158.1 Hz, P of dppe trans to P), 74.1 (d0t0, 2J(31P, 31P) ¼ 27.1 Hz,
2J(31P, 31P) ¼ 30.4, 1J(31P, 103Rh) ¼ 189.0 Hz, P of dppe trans to O).
L2 ¼ cod, (22b). Yield: 209 mg (74%). HRMS (ESI): m/z Calcd. for
[C29H32NaOPRhS]: 585.0859; found for [M þ Na]þ: 585.0856. 1H
Yield: 210 mg (81%). Found: C, 62.48; H, 5.35; Calcd. for
C58H64OP2S2Rh2 (1109.02): C, 62.81;H, 5.82. 31PNMR (81MHz, THF):
d
20.8 (m, 1J(103Rh, 31P) ¼ 169.6 Hz, 2J(103Rh, 31P) ¼ 4.0 Hz, 3J(31P,
NMR (400 MHz, CD2Cl2):
d
1.28e3.03 (m, 12H, CH2CH2PPh2 þ 4ꢃ
31P) ¼ 147.4 Hz, PPh2), 20.9 (m, 1J(103Rh, 31P) ¼ 167.3 Hz, 2J(103Rh,
CH2, cod), 3.45 (s, br, 1H, CHSOPh), 3.94/4.05/5.56 (m/m/s, e/e/br,
31P) ¼ 1.0 Hz, 3J(31P, 31P) ¼ 147.4 Hz, PPh2).
1H/1H/2H, 4ꢃ CH, cod), 6.99e8.26 (m, 15H, HPh). 13C NMR
(100 MHz, CD2Cl2):
d
20.8 (d, 2J(31P, 13C) ¼ 13.9 Hz, CH2CH2PPh2),
3.6. Preparation of [Rh{Ph2PCHS(O)xPh-
{CH{S(O)Ph}CH2CH2PPh2- C, P}L2] (22b, 23b)
kP,
kS/O}L2] (20, 21) and [Rh
34.0 (d, 1J(31P, 13C) ¼ 26.9 Hz, CH2PPh2), 28.4/28.9/29.3/32.5 (s/s/s/s,
4ꢃ CH2, cod), 63.0 (dd, 2J(31P, 13C) ¼ 4.9 Hz, 1J(103Rh, 13C) ¼ 28.7 Hz,
CHSOPh), 81.1/82.7/93.6/100.4 (d/d/dd/dd, 1J(103Rh, 13C) ¼ 8.6/8.2/
k
k
To [(RhL2)2(
m-Cl)2] (L2 ¼ cod, 4; dppe, 5; 0.25 mmol) in THF
11.9/9.8 Hz, 2J(31Ptrans
,
13C) ¼ 7.2/7.8 Hz, 4ꢃ CH (cod)), 124.3e147.4
(5 mL) Ph2P(CH2)nS(O)xPh (0.50 mmol) dissolved in THF (2 mL) was
added with stirring. After 30 min the solution was reduced to half of
its volume, cooled to ꢀ78 ꢁC and sodium bis(trimethylsilyl)amide
(0.50 mmol, 2 M in THF) was added. In case of 20 and 21 n-pentane
(5 mL) was added, the precipitate filtered off, which was washed
with n-pentane (3 ꢃ 1 mL) and dried in vacuo. In case of 22b and
(CPh). 31P NMR (81 MHz, THF-d8):
PPh2).
d
51.6 (d, 1J(103Rh, 31P) ¼ 174.6 Hz,
2
Includes NaCl which was not separated.
Not isolated in substance; only characterized by 31P NMR spectroscopy.
3

1780
M. Block et al. / Journal of Organometallic Chemistry 696 (2011) 1768e1781
Table 4
Crystallographic data, data collection parameters and refinement parameters for 15b, 15c, 12$4THF and 19$THF.
15b
15c
12$4THF
19$THF
Empirical formula
Mr
Crystal System
Space group
a/Ǻ
C28H31BF4OPRhS
636.28
Orthorhombic
Pca21
16.738(1)
9.334(1)
17.413(1)
C28H31BF4O2PRhS
652.28
Orthorhombic
Pca21
17.432(3)
9.376(1)
16.759(2)
C92H100B2ClF8O4 P4Rh3S4
2039.64
Monoclinic
P21/n
20.6888(5)
19.4795(4)
23.0532(6)
107.593(2)
8856.1(4)
4
1.530
0.817
4168
2.09e25.00
45711
C58H64OP2Rh2S2
1108.97
Monoclinic
P2/n
13.103(2)
10.1480(9)
18.569(2)
94.67(1)
2460.8(5)
2
1.497
0.862
1144
1.98e25.00
11854
b/Ǻ
c/Ǻ
ꢁ
b
/
V/Ǻ3
2720.6(4)
4
1.553
0.811
1296
2.18e25.98
20426
3964
2739.0(6)
4
1.582
0.811
1328
2.34e26.00
9223
4682
Z
Dcalc/g cmꢀ1
m
(Mo-Ka)/mmꢀ1
F(000)
q
range/ꢁ
Rfln. collected
Refln. observed
11941
3227
[I > 2s(I)]
Rfln. independent
5307
4935
15572
4311
(Rint ¼ 0.0912)
(Rint ¼ 0.0199)
(Rint ¼ 0.0477)
(Rint ¼ 0.0384)
Data/restraints/
parameters
Goodness-of-fit
on F2
5307/1/334
4935/1/343
15572/28/1082
4311/5/316
0.928
1.052
1.043
0.836
R1, wR2 [I > 2
s
(I)]
0.0415, 0.0652
0.0705, 0.0712
0.624 and ꢀ0.351
0.0260, 0.0693
0.0277, 0.0700
0.380 and ꢀ0.497
0.0451, 0.0938
0.0678, 0.1018
0.987 and ꢀ0.479
0.0240, 0.0470
0.0404, 0.0489
0.380 and ꢀ0.299
R1, wR2 (all data)
Largest diff. peak and hole/e Ǻꢀ3
L2 ¼ dppe, (23b). Yield: 324 mg (76%). HRMS (ESI): m/z Calcd. for
[C47H45OP3RhS]: 853.7514; found for [M þ H]: 853.7511. 1H NMR
3.8. Computational details
(500 MHz, THF-d8):
d
1.12/1.78 (m/m, 1H/1H, CHCH2CH2PPh2), 1.93/
DFT calculations were carried out by the Gaussian 03 program
package [65] using the hybrid functional B3LYP [66]. 6-311þþG
(3df,3pd) (P, S) and 6-31þG* (O, C, H) basis sets were employed for
main group atoms [65,67]. The valence shell of rhodium has been
approximatedbyasplitvalencebasissettoo(Def2-TZVPP);foritscore
orbitals an effective core potential in combinationwith consideration
of relativistic effects has been used [68]. All systems were fully opti-
mized without any symmetry restrictions. The resulting geometries
were characterized as equilibrium structures by the analysis of the
force constants of normal vibrations. To limit the computational
2.13e2.27/2.58e2.66/3.09 (m/m/m/m, 2H/2H/2H/1H, CHCH2CH2
PPh þ Ph2PCH2CH2PPh2), 6.83e8.29 (m, 35H, HPh). 13C NMR
(50 MHz, THF-d8):
d 28.6 (s, CHCH2CH2), 28.8e29.0/37.0e37.4 (m/
m, Ph2PCH2CH2PPh2), 29.3 (dd, 1J(13C, 31P) ¼ 15.9 Hz, 3J(13C,
31
P
trans
) ¼ 5.3 Hz, CHCH2CH2), 57.9e59.8 (m, CHSOPh), 123.9e149.6
(CPh). 31P NMR (81 MHz, THF-d8):
d
58.0 (m, 2J(31P, 31P) ¼ 31.1 Hz, 2J
(
31P, 31P) ¼ 307.2 Hz, 1J(31P, 103Rh) ¼ 156.1 Hz, PPh2), 59.1 (m, 2J(31P,
31P) ¼ 27.2 Hz, 2J(31P, 31P) ¼ 31.1 Hz, 1J(31P, 103Rh) ¼ 128.0 Hz, P of
dppe trans to C), 65.2 (m, 2J(31P, 31P) ¼ 27.2 Hz, 2J(31P, 31P) ¼ 307.2, 1J
(
31P, 103Rh) ¼ 159.8 Hz, P of dppe trans to P).
expense, in the case of complexes with the dppe ligand (21bcalc,
21b0calc) 6-31G* basis sets for O, C and H were used only. Then, after
characterizing the structures asequilibrium structures by the analysis
of the force constants of normal vibrations, in a second step the
molecules were re-optimized with a small step-size (IOP(1/8¼3))
using the basis sets 6-31þG* for O, C and H as given above.
3.7. X-ray crystallography
Data for X-ray diffraction analyses of single crystals of 15c,
12$4THF and 19$THF were collected on a Stoe-IPDS 2T diffrac-
tometer at 200(2) K and of 15b on a Stoe-IPDS diffractometer at 223
(2) K using Mo-K
a
radiation (
l
¼ 0.7103 Å, graphite mono-
Appendix A. Supplementary material
chromator). A summary of the crystallographic data, the data col-
lection parameters and the refinement parameters is given in
Table 4. Absorption corrections were applied numerically with X-
RED32 [62] (Tmin/Tmax 0.86/0.96, 12$4THF; 0.86/0.92, 15b; 0.92/
0.96, 19$THF). The structures were solved with direct methods
using SHELXS-97 [63] and refined using full-matrix least-square
routines against F2 with SHELXL-97 [64]. All non-hydrogen atoms
were refined with anisotropic displacement parameters and
hydrogen atoms with isotropic ones. H atoms were placed in
calculated positions according to the riding model. In complex
12$4THF a part of one of the Ph2PCH2SPh ligands has been refined
disordered over two positions with a site occupancy of 58.8(4)%
(C2A, S2A, C23AeC28A) and 41.2(4)% (C2B, S2B, C23BeC28B). The
phenyl rings of these disordered units have been refined constraint.
In addition, for the refinement of the THF molecules as packing
solvents DFIX and DANG restraints have been used, explaining the
comparatively large number of restraints. In complex 19$THF the
THF molecule has been refined disordered over two positions with
equal occupancy using 5 DFIX restraints.
Crystallographic data (excluding structure factors) have been
deposited at the Cambridge Crystallographic Data Centre as supp-
lementary publication nos. CCDC 797346 (15b), CCDC 797347(15c),
CCDC 797348 (12$4THF), CCDC 797349 (19$THF). These data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/cgi-bin/
catreq.cgi or from the Business & Administration, Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ,
UK; fax: (þ44) 1223 336033; or email: admin@ccdc.cam.ac.uk.
Appendix. Supplementary material
Supplementary data related to this article can be found online at
doi:10.1016/j.jorganchem.2010.12.019.
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