On the reactivity of rhodium(I) complexes with κp -coordinated γ-phosphino-functionalized propyl phenyl sulfide ligands: Routes to cyclic rhodium complexes with Κc,ΚP - And Κp,ΚS -coordinated ligands as well as bis(diphenylphosphino)methanide ligands

Article abstract of DOI:10.1021/om100878n

Reactions of dinuclear μ-chlorido rhodium(I) complexes [(RhL ₂)₂(μ-Cl)₂] (L₂ = cycloocta-1,5-diene, cod, 3; L₂ = PλP: Ph₂PCH ₂PPh₂, dppm, 4a; Ph₂P(CH_2<

Full text of DOI:10.1021/om100878n

Organometallics 2010, 29, 6749–6762 6749
DOI: 10.1021/om100878n
On the Reactivity of Rhodium(I) Complexes with KP-Coordinated
γ-Phosphino-Functionalized Propyl Phenyl Sulfide Ligands: Routes to
Cyclic Rhodium Complexes with KC,KP- and KP,KS-Coordinated
Ligands as Well as Bis(diphenylphosphino)methanide Ligands
†
Michael Block, Tim Kluge, Martin Bette, Jurgen Schmidt, and Dirk Steinborn*
†
†
‡
,†
€
†Institute of Chemistry, Martin Luther University Halle-Wittenberg, Kurt-Mothes-Strasse 2,
D-06120 Halle, Germany, and ‡Department of Bioorganic Chemistry, Leibniz Institute of Plant
Biochemistry, Weinberg 3, D-06120 Halle, Germany
Received September 10, 2010
Reactions of dinuclear μ-chlorido rhodium(I) complexes [(RhL2)2(μ-Cl)2] (L2=cycloocta-1,5-diene,
∧
cod, 3; L2=P P: Ph2PCH2PPh2, dppm, 4a; Ph2P(CH2)2PPh2, dppe, 4b; Ph2P(CH2)3PPh2, dppp, 4c;
Me2P(CH2)2PMe2, dmpe, 4d) with γ-phosphino-functionalized propyl phenyl sulfides PhSCH2CH2-
CH2PR2 (R=Ph, 1; Cy, 2) afforded mononuclear rhodium(I) complexes of the type [RhCl(R2PCH2-
∧
∧
CH2CH2SPh-κP)L2] ] (R=Ph/L2=P P, 5a-c;R=Ph/L2=cod, 6;R=Cy/L2=P P, 7a-d;R=Cy/L2 =
cod, 8). Single-crystal X-ray diffraction analysis of 7b C6H6 exhibited the expected square-planar
3
coordination of the rhodium atom having coordinated dppe-κ2P,P0, Cy2PCH2CH2CH2SPh-κP, and a
chlorido ligand. Deprotonation of complexes 5b/c, 6, 7b/c, and 8 with lithium diisopropyl amide (LDA)
yielded, with a selective deprotonation of the CH2 group next to the sulfur atom (R-CH2 group), com-
plexes of the type [Rh{CH(SPh)CH2CH2PR2-κC,κP}L2] (13b/c, 14, 15b/c, 16), thus being organorho-
dium intramolecular coordination compounds. Unexpectedly, reactions of the dppm complexes 5a and
7a with LDA led to deprotonation of the CH2 group of the dppm ligand, resulting in formation of
mononuclear rhodium complexes with a bis(diphenylphosphino)methanide-κ2P,P0 ligand and a
R2P SPh-κP,κS ligand, as well (17, 18). Single-crystal X-ray diffraction analysis of [Rh(dppm-H-κ P,P0)
2
∧
(Cy2PCH2CH2CH2SPh-κP,κS)] THF (18 THF) shows the rhodium atom located in the center of a
3
3
distorted square-planar environment having bound the P S-κP,κS ligand and the anionic dppm-H-κ2P,
P0 ligand with a very small P2-Rh-P3 angle (68.8(2)°) reflecting the small bite of that ligand. Addition
of Tl[PF6] to complexes 5-8 afforded cationic rhodium(I) complexes of the type [Rh(R2PCH2CH2CH2-
∧
∧
SPh-κP,κS)L2][PF6] (9-12) bearing bidentately coordinated neutral co-ligands (P P: 9, 11; cod, 10, 12)
and κP,κS-coordinated γ-phosphino-functionalized propyl phenyl sulfide ligands, as well. Single-crystal
X-ray diffraction analysis of 10 reveals that the rhodium atom adopts a slightly distorted square-planar
conformation. Complexes 9a-c and 11a-d were found to react with carbon monoxiþde, yielding cationic
2
0
∧
rhodium carbonyl complexes [Rh(CO)(R2PCH2CH2CH2SPh-κP,κS)(P P-κ P,P )] (19, 20), being in a
dynamic equilibrium between two diastereomers each at room temperature, which was additionally
verified by DFT calculations.
1. Introduction
Hence, from almost all metals of the periodic table organo-
metallic intramolecular coordination compounds are known,
and they are widely used in organic syntheses. Applications
are carbonylations9 and Diels-Alder reactions;10 see II and
III (Chart 1) as examples. Furthermore, they are used in
Since the synthesis and characterization of the organo-
aluminum compounds Ia/Ib (Chart 1), in which an alkyl ligand
is additionally coordinated to aluminum through a Lewis-
1
€
€
basic group (κO/κN), by Bahr and Muller in 1955 and the
report on the cyclometalation of azobenzene resulting in an
o-(phenylazo)phenyl nickel complex in 1963 by Kleimann
and Dubeck,2 the syntheses of organometallic intramolecu-
lar coordination compounds (also named “organometallic inner
complexes”1) were the subject of a large number of studies.3-8
(3) Nolte, M.; Singleton, E.; van der Stok, E. J. Organomet. Chem.
1977, 142, 387.
(4) Klei, E.; Teuben, J. H. J. Organomet. Chem. 1981, 214, 53.
(5) Al-Allaf, T. A. K. Asian J. Chem. 2000, 12, 869.
(6) Omae, I. J. Organomet. Chem. 2007, 692, 2608.
(7) Beck, R.; Frey, M.; Camadanli, S.; Klein, H.-F. Dalton Trans.
2008, 4981.
(8) Campos, J.; Esqueda, A. C.; Carmona, E. Chem. Eur. J. 2010, 16,
419.
(9) Thompson, J. M.; Heck, R. F. J. Org. Chem. 1975, 40, 2667.
(10) Leung, P.-H.; He, G.; Lang, H.; Liu, A.; Loh, S.-K.; Selvaratnam,
S.; Mok, K. F.; White, A. J. P.; Williams, D. J. Tetrahedron 2000, 56, 7.
*To whom correspondence should be addressed. E-mail: steinborn@
chemie.uni-halle.de.
€
€
(1) Bahr, G.; Muller, G. E. Chem. Ber. 1955, 88, 251.
(2) Kleiman, J. P.; Dubeck, M. J. Am. Chem. Soc. 1963, 85, 1544.
r
2010 American Chemical Society
Published on Web 12/01/2010
pubs.acs.org/Organometallics

6750 Organometallics, Vol. 29, No. 24, 2010
Block et al.
Chart 1
alkenylations11 and metal-catalyzed reactions such as me-
tathesis12,13 or cross-coupling reactions.14,15 In general, in
cyclometalations a precoordination of the ligand via a Lewis
basic heteroatom YRn (YRn=OR, SR, NR2,PR2,...) wasfound
followed by a deprotonation of a C-H bond in a chelating-
favorable position to the metal center under formation of an
M-C σ-bond. Among organometallic intramolecular coor-
dination compounds those complexes having five-membered
ring structures are of particular stability compared to four-
and six-membered metallacycles.16
Apart from complexes of the type described above, com-
plexes having bidentately coordinated ligands with different
donor sites, among those of the type R2P-(CH2)n-SR0
(R, R0 =alkyl, aryl), are also of interest for various reasons.17
For example, they may act as hemilabile ligands permitting
temporary generation of a vacant coordination site at the
metal center; thus reactions such as oxidative additions18,19
and substitutions20,21 may proceed more easily. Moreover,
they may facilitate the activation of small molecules such as
CO or O2, thus playing an important role in homogeneously
catalyzed reactions.22-24
We are interested in metal complexes with R-sulfur-func-
tionalized alkyl ligands of the type -CH{PhS(O)x}CH2CH2-
YRn (x=0-2) bearing in the γ-position an additional donor
site YRn=NR2, PR2, OR (R=alkyl, aryl). R-Lithiated thio-
ethers (x=0) without this donor functionality YRn tend to
yield oligonuclear compounds in the solid state,25,26 whereas
those having a donor functionality YRn (NR2, OR) were found
to be mononuclear organolithium intramolecular coordination
compounds in the solid state.27,28 Moreover, the corresponding
R-sulfonyl-functionlized ligands (x=2) were also found to yield
organorhodium intramolecular coordination compounds, thus
forming a Rh-C σ-bond.29 This is in contrast to the majority
of the lithiated compounds, which are mostly higher aggre-
gated and have the sulfone ligand κO-coordinated to the Li
atom, thus bearing a “free” carbanionic center.30,31
Here we report on the synthesis, characterization, and reac-
tivity of rhodium(I) complexes of the type [RhCl(R2PCH2-
CH2CH2SPh-κP)L2] (R=Ph, Cy; L=diphosphanes, cyclo-
octa-1,5-diene), which were found to yield organorhodium
intramolecular coordination compounds having anionic
∧
C P-κC,κP ligands upon deprotonation and cationic
∧
rhodium(I) complexes bearing hemilabile P S-κP,κS ligands
upon Cl- abstraction, and their reactions with carbon monoxide.
2. Results and Discussion
2.1. Syntheses. The reactions of dinuclear chlorido-bridged
rhodium complexes bearing cycloocta-1,5-diene and dipho-
sphanes as ligands (3, 4a-d) with γ-phosphino-functionalized
propyl phenyl sulfides 1 and 2 led to the formation of mono-
nuclear rhodium complexes of the type [RhCl(R2PCH2CH2-
CH2SPh-κP)L2] (5-8) (Scheme 1, routes a/c). Only the reac-
tion of the diphenylphosphino-functionalized thioether ligand
1 with the dmpe complex 4d resulted in decomposition. The
reactions were performed in either THF or CH2Cl2. Using
methylene chloride as solvent, the reactions with complexes 4
have to be performed at -78 °C to avoid the oxidative addition
of dichloromethane to 4, which results in the formation of
μ-methylene rhodium(III) complexes.32 The yellow to orange
air-sensitive complexes 5-8 were obtained in yields between
48% and 90% and were characterized NMR spectroscopically
(1H, 13C, 31P), by elemental analysis, and by a single-crystal
X-ray measurement (7b C6H6). All compounds were soluble
(11) Cravotto, G.; Demartin, F.; Palmisano, G.; Penoni, A.; Radice,
T.; Tollari, S. J. Organomet. Chem. 2005, 690, 2017.
(12) Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H.
3
in THF and dichloromethane but showed decomposition in
chloroform within a few hours at room temperature. The com-
plexes with the dicyclohexylphosphino-functionalized ligand
(7, 8) were even slightly soluble in n-pentane, explaining the
lower yields compared to complexes 5 and 6. Furthermore, it
has been shown that the reaction of the cylooctadiene rhodium
complexes [RhCl(R2PCH2CH2CH2SPh-κP)(cod)] (6, 8) with
J. Am. Chem. Soc. 2000, 122, 8168.
(13) Yao, Q.; Zhang, Y. Angew. Chem., Int. Ed. 2003, 42, 3395.
(14) Herrmann, W. A.; Brossmer, C.; Reisinger, C.-P.; Riermeier,
€
T. H.; Ofele, K.; Beller, M. Chem. Eur. J. 1997, 3, 1357.
(15) Ogo, S.; Takebe, Y.; Uehara, K.; Yamazaki, T.; Nakai, H.;
Watanabe, Y.; Fukuzumi, S. Organometallics 2006, 25, 331.
(16) (a) Omae, I. Coord. Chem. Rev. 1979, 28, 97. (b) Omae, I. Coord.
Chem. Rev. 1980, 32, 235. (c) Omae, I. Coord. Chem. Rev. 1982, 42, 245.
(d) Omae, I. Coord. Chem. Rev. 1988, 83, 137.
∧
diphosphanes (P P) resulted in a ligand substitution reaction
∧
(cod f P P) forming the respective diphosphane complexes 5
and 7 (Scheme 1, route a f e).
(17) Sanger, A. R. Can. J. Chem. 1983, 61, 2214.
(18) Bassetti, M.; Capone, A.; Salamone, M. Organometallics 2004,
23, 247.
(19) Gonsalvi, L.; Adams, H.; Sunley, G. J.; Ditzel, E.; Haynes, A.
Addition of Tl[PF6] to complexes 5-8 in THF or CH2Cl2
afforded, with precipitation of TlCl, cationic rhodium
J. Am. Chem. Soc. 2002, 124, 13597.
(20) Ulmann, P. A.; Mirkin, C. A.; DiPasquale, A. G.; Liable-Sands,
L. M.; Rheingold, A. L. Organometallics 2009, 28, 1068.
(21) Pamies, O.; Dieguez, M.; Net, G.; Ruiz, A.; Claver, C. Organo-
€
(27) Linnert, M.; Bruhn, C.; Wagner, C.; Block, M.; Ruffer, T.;
ꢀ
ꢁ
Schmidt, H.; Steinborn, D. In Advances in Coordination, Bioinorganic
and Inorganic Chemistry; Melnik, M.; Sima, J.; Tatarko, M., Eds.; STU
Press: Bratislava, 2005; p 170.
(28) Block, M.; Linnert, M.; Gomez-Ruiz, S.; Steinborn, D. J. Organ-
omet. Chem. 2009, 694, 3353.
(29) Block, M.; Wagner, C.; Gomez-Ruiz, S.; Steinborn, D. Dalton
metallics 2000, 19, 1488.
(22) Bressan, M.; Morandini, F.; Rigo, P. J. Organomet. Chem. 1983,
247, C8.
(23) Bressan, M.; Morandini, F.; Morvillo, A.; Rigo, P. J. Organo-
ꢁ
ꢁ
met. Chem. 1985, 280, 139.
(24) Dilworth, J. R.; Miller, J. R.; Wheatley, N.; Baker, M. J.; Sunley,
J. G. J. Chem. Soc., Chem. Commun. 1995, 1579.
(25) Amstutz, R.; Laube, T.; Schweizer, W. B.; Seebach, D.; Dunitz,
J. D. Helv. Chim. Acta 1984, 67, 224.
(26) Becke, F.; Heinemann, F. W.; Steinborn, D. Organometallics
1997, 16, 2736.
Trans. 2010, 39, 4636.
(30) Gais, H.-J.; Hellmann, G.; Gunther, H.; Lopez, F.; Lindner,
H. J.; Braun, S. Angew. Chem., Int. Ed. Engl. 1989, 28, 1025.
(31) Boche, G. Angew. Chem., Int. Ed. Engl. 1989, 28, 277.
(32) Ball, G. E.; Cullen, W. R.; Fryzuk, M. D; James, B. R.; Rettig,
S. J. Organometallics 1991, 10, 3767.
€

Article
Organometallics, Vol. 29, No. 24, 2010 6751
Scheme 1. Routes to Rhodium Complexes Bearing KP (5-8) and κP,κS (9-12) Coordinated R2PCH2CH2CH2SPh Ligands
Scheme 2. Routes to Organorhodium Intramolecular Coordina-
tion Compounds
complexes with κP,κS-coordinated phosphino-functionalized
propyl phenyl suldfides (9-12) (Scheme 1, routes b/d). The
complexes formed were found to be air-sensitive, yellow micro-
crystalline solids, which were islolated in yields between 71%
and 88%, and they were characterized by 1H, 13C, and 31
P
NMR spectroscopy, high-resolution mass spectrometric
(HRMS-ESI) investigations, and a single-crystal X-ray dif-
fraction (10). To simplify the syntheses, it has been shown
that complexes 9-12 can also be obtained according to route
a f b or c f d without isolation of the neutral rhodium com-
plexes 5-8. Furthermore, the cationic complexes bearing a
∧
P P ligand (9, 11) were easily accessible via route a f e f d
starting from the commerically available cod complex 3
without isolation of any intermediate complex (Scheme 1).
Reactions of complexes [RhCl(R2PCH2CH2CH2SPh-κP)L2]
(L2=dppe, 5b/7b; dppp, 5c/7c; L2=cod, 6/8) with lithium
diisopropylamide (LDA) in toluene at -78 °C led selectively
to deprotonation of the carbon atom neighboring the sulfur
center (R-C) and its coordination to rhodium, thus forming
organorhodium intramolecular coordination compounds of
the type [Rh{CH(SPh)CH2CH2PPh2-κC,κP}L2] (13b/c, 14,
15b/c, 16; Scheme 2). In contrast, the reaction of the dmpe
complex [RhCl(R2PCH2CH2CH2SPh-κP)(dmpe)] (7d) with
LDA did not lead to a type 15 complex but to decomposition
Unexpectedly, the reactions of the dppm complexes [RhCl-
(R2PCH2CH2CH2SPh-κP)(dppm)] (5a, 7a) with LDA led to
a deprotonation of the CH2 group of the dppm ligand, result-
ing in the formation of mononuclear rhodium complexes
having bound an anionic bis(diphenylphosphino)meth-
2
0
∧
∧
with cleavage of the P S ligand. In general, attempts to use
anide-κ P,P ligand and a R2P SPh-κP,κS ligand (17, 18)
(Scheme 3). Complexes 17 and 18 were obtained in yields of
about 72% as orange to brown air- and moisture-sensitive
solids, which were characterized by NMR spectroscopy
(1H, 13C, 31P), HRMS-ESI investigations, and a single-crystal
MeLi or n-BuLi as deprotonating agent led to decomposi-
tion, which might be attributed to the stronger nucleophili-
city of these bases. Complexes 13-16 were soluble in toluene,
benzene, and THF but showed decomposition in chloroform.
Moreover, the complexes with the dicyclohexylphosphino-
functionalized ligand (15b/c, 16) exhibited a pronounced
solubility in n-pentane, even at -78 °C, which made it impos-
sible to remove residual amounts of diisopropylamine. Thus,
the yields for the dark orange to brown air-sensitive com-
plexes were low for 15b/c and 16 (31-35%) but good for
complexes 13b/c and 14 (ca. 85%). The organorhodium com-
X-ray diffraction analysis (18 THF).
2.2. Structures. 2.2.1. Structure of [RhCl(Cy2PCH2CH2-
3
CH2SPh-KP)(dppe)] (7b). Crystals of 7b C6H6 suitable for
3
X-ray diffraction analysis were obtained from benzene solution
at room temperature. The compound crystallized in isolated
molecules without unusual intermolecular interactions (shortest
distance between non-hydrogen atoms: 3.410(3) A,C23 C370).
3 3 3
1
plexes were characterized by H, 13C, and 31P NMR spec-
The molecular structure is shown in Figure 1, and selected
structural parameters are given in the figure caption. The
rhodium atom adopts a square-planar geometry and is co-
ordinated by a chlorido ligand, a κ2P,P0-bound dppe ligand,
and a γ-phosphino-functionalized propyl phenyl sulfide with
a κP-coordination mode. The angles between neighboring
troscopy as well as by elemental analysis (13b/c, 14). By
analogy to the synthesis of the cationic rhodium complexes
9-12 the intermediate compounds 5-8 do not need to be
isolated; thus 13-16 can be obtained in a one-pot reaction
directly from the dinuclear starting complexes 3 and 4.

6752 Organometallics, Vol. 29, No. 24, 2010
Block et al.
Figure 2. Molecular structure of the cation in crystals of [Rh-
(Ph2PCH2CH2CH2SPh-κP,κS)(cod)][PF6] (10). The ellipsoids
are shown with a probability of 30%. H atoms of phenyl rings
have been omitted for clarity. Selected structural parameters
(distances in A, angles in deg): Rh-P 2.299(2), Rh-C22/23cg
(cg=center of gravity) 2.0602(2), Rh-C26/27cg 2.1388(5), Rh-S
2.353(2), C22-C23 1.378(9), C26-C27 1.362(9), P1-Rh-S
86.96(5), P-Rh-C22/23cg 92.25(4), C22/23cg-Rh-C26/27cg
85.32(2), C26/27cg-Rh-S 95.32(4), C26/27cg-Rh-P 177.23(4),
C22/23cg-Rh-S 173.70(4).
Figure 1. Molecular structure of [RhCl(Cy2PCH2CH2CH2SPh-
κP)(dppe)] in crystals of 7b C6H6. The ellipsoids are shown with
3
a probability of 30%. H atoms of phenyl and cyclohexyl rings
have been omitted for clarity. Selected structural parameters
(distances in A, angles in deg): Rh-P1 2.3476(7), Rh-P2
2.2024(7), Rh-P3 2.2987(7), Rh-Cl 2.4114(8), Cl-Rh-P1
88.35(2), P1-Rh-P2 97.06(2), P2-Rh-P3 83.77(3), P3-Rh-
Cl 90.69(2), Cl-Rh-P2 174.02(2), P1-Rh-P3 176.84(2).
Scheme 3. Synthesis of Zwitterionic Rhodium Complexes
ligands are all close to 90° (83.77(3)-97.06(2)°). The five-
membered RhP2C2 rhodacycle has a half-chair conformation
twisted on C22 and C23. Noteworthy, the Rh-P1 bond
(2.3476(7) A) is significantly longer than the Rh-P3 bond
(2.2987(7) A), which is in accordance with other rhodium(I)
complexes having a PPh2R and a PCy2R (R=alkyl) group
in mutual trans position.33,34 Both the Rh-P2 (2.2024(7) A)
and the Rh-Cl (2.4114(8) A) bond lengths are quite
standard for square-planar rhodium complexes bearing a
phosphane and a chlorido ligand trans to each other.35-38
2.2.2. Rhodium Complexes Bearing Bidentately Coordi-
nated P,S Ligands. Crystals of [Rh(Ph2PCH2CH2CH2SPh-
κP,κS)(cod)][PF6] (10) and [Rh(dppm-H-κ2P,P0)(Cy2PCH2-
CH2CH2SPh-κP,κS)] THF (18 THF) suitable for X-ray
Figure 3. Molecular structure of [Rh(dppm-H-κ2P,P0)(Cy2-
PCH2CH2CH2SPh-κP,κS)] in crystals of 18 THF. The ellip-
3
soids are shown with a probability of 30%. H atoms of phenyl
and cyclohexyl rings have been omitted for clarity. Selected
structural parameters (distances in A, angles in deg): Rh-P1
2.2965(5), Rh-P2 2.2963(4), Rh-P3 2.3130(4), Rh-S 2.3123(4),
P2-C34 1.725(2), P3-C34 1.728(2), P2-Rh-P3 68.82(2), P3-
Rh-S 91.41(2), S-Rh-P1 96.37(2), P1-Rh-P2 104.31(2), P2-
C34-P3 97.92(9), P2-Rh-S 159.31(2), P1-Rh-P3 163.55(2).
In both complexes the rhodium atom exhibits a distorted
square-planar conformation where the primary donor sets
are built up by the bidentately κP,κS-coordinated phosphi-
no-functionalized sulfides as well as by a bidentately bound
cycloocta-1,5-diene ligand (10) and a bis(diphenylphos-
3
3
diffraction analyses were obtained from THF solutions at
room temperature. Complex 10 crystallized as discrete cat-
ions and anions without unusual intermolecular interactions
(shortest distance between non-hydrogen atoms: 3.082(8) A,
C2 F40). Complex 18 THF crystallized in isolated mole-
phino)methanide-κ2P,P0 (dppm-H) ligand (18 THF), re-
3
3 3 3
3
spectively. The six-membered RhPC3S metallacycles adopt a
chair form (10) and a screw-boat form (18 THF), respec-
cules (shortest distance between non-hydrogen atoms: 3.510(3) A,
C8 C430). The molecular structures are shown in Figures 2
3
3 3 3
tively. In complex 10 all angles between neighboring ligands
are close to 90° (85.32(5)-95.32(5)°), and those between trans-
standing ligands are 173.70(4)° and 177.23(4)°, close to 180°.
Contrary to this, due to the small bite of the chelating dppm-H
and 3. Selected structural parameters are given in the figure
captions.
ꢂ
ꢂ ꢁ ꢃ ꢂ
(33) Lamac, M.; Cısarova, I.; Stepnicka, P. J. Organomet. Chem.
´
ligand (P2-Rh-P3 68.82(2)°) in complex 18 THF, greater
3
2005, 690, 4285.
ꢂ
(34) Lamac, M.; Cı
deviations were found. Thus, the angles between trans-stand-
ing ligands amount to 159.31(2)° (S-Rh-P2) and 163.55(2)°
(P1-Rh-P3).
ꢂ ꢁ ꢃ ꢂ
´
sarova, I.; Stepnicka, P. Eur. J. Inorg. Chem. 2007,
2274.
(35) Brown, A. M.; Ovchinnikov, M. V.; Stern, C. L.; Mirkin, C. A.
J. Am. Chem. Soc. 2004, 126, 14316.
(36) Rios-Moreno, G.; Toscano, R. A.; Redon, R.; Nakano, H.;
The Rh-P bond length in 10 (2.299(2) A) is in the expected
range for Rh(I) complexes containing a phosphane and a cod
ligand in mutual trans position (median: 2.307 A, lower/higher
quartile: 2.285/2.327 A, n=189).39 However, the Rh-P1 bond
ꢁ
Okuyama, Y.; Morales-Morales, D. Inorg. Chim. Acta 2005, 358, 303.
€
(37) Le Gall, I.; Laurent, P.; Soulier, E.; Salaun, J.-Y.; des Abbayes,
H. J. Organomet. Chem. 1998, 567, 13.
(38) Andrieu, J.; Richard, P.; Camus, J.-M.; Poli, R. Inorg. Chem.
2002, 41, 3876.
in 18 THF (2.2965(5) A) was found to be relatively short
3

Article
Organometallics, Vol. 29, No. 24, 2010 6753
compared to four-coordinated rhodium complexes bearing
two trans-standing phosphane ligands (median: 2.318 A, lower/
higher quartile: 2.298/2.333 A, n=432).39 The higher trans
influence of phosphanes compared to thioethers40 is reflected
in the longer bond of Rh-P3 (2.3130(4) A, P3 is trans to P1)
compared to Rh-P2 (2.2963(4) A, P2 is trans to S). Note-
worthy, the Rh-S bond in 10 (2.353(2) A) is considerably
the computational expense, the calculations were performed
by replacing the PCy2 groups in 18 THF by PPh2 groups,
3
thus representing complex 17. Two isomers were calculated,
namely, a complex bearing an anionic dppm-H ligand (17calc)
and a type 13 complex with an anionic -CH(SPh)CH2-
CH2PPh2-κC,κP ligand (13acalc), which are shown in Figure 4.
As found in the structure of 18 THF, the deprotonation of the
3
longer than that in 18 THF (2.3123(4) A).
dppm ligand gives rise to a marked shortening of the P2-
C34/P3-C34 bonds (1.786/1.784 A in 17calc versus 1.921/
1.913 A in 13acalc) and a concomitant lengthening of the
Rh-P3 bond (2.419 A in 17calc versus 2.392 A in 13acalc).
Noteworthy, the intramolecular coordination compound
13acalc was found to be more stable by 21.6 kcal/mol (Gibbs
free energy at 298 K). This clearly demonstrates that the
experimentally observed formation of complex 17 and also;
in analogy;of complex 18 is under kinetic control.
3
The structure of the deprotonated dppm ligand is of par-
ticular interest. The four-membered RhP2C cycle is slightly
more hinged (torsion angle Rh-P2 P3-C34 166.0(1)°)
3 3 3
than in other metal complexes bearing a dppm-H-κ2P,P0
ligand (median: 176.0°, lower/higher quartile: 170.6/177.9°,
n=18; absolute values of the torsion angles are given).39 The
Rh-P3 bond in 18 THF (2.3130(4) A, P3 is trans to P1) is of
3
a similar length as the Rh-P bonds of the dppm-H-κ2P,P0
ligand (2.342(3)/2.324(3) A) in complex [Rh(dppm-H-κ2P,P0)-
(dppm-κ2P,P0)];41 thus the deprotonation of the dppm ligand
is accompanied by a Rh-P bond elongation (dppm: Rh-P
2.293(3)/2.237(4) A).41 On the other hand, the P-C bond
2.3. Spectroscopic Investigations. 2.3.1. Rhodium Complexes
with PhSCH2CH2CH2PR2-KP Ligands. Selected NMRspectro-
scopic parameters of complexes 5-8are given in Table 1. All 31P
NMR spectra are of first order, exhibiting an AEMX spin
system (A, E, M=31P; X = 103Rh; 5, 7) and an AX spin system
(6, 8), respectively. Due to the smaller trans influence of olefin
lengths in 18 THF (1.725(2)/1.728(2) A) are clearly short-
3
ened compared to those of (nondeprotonated) dppm ligands
(1.839(2)-1.853(4) A),41-43 which can be explained in terms
of an ylidic bonding model with some charge delocaliza-
tion within the PCP moiety.44 Additionally, the transan-
1
ligands compared to phosphane ligands, the JRh,P coupling
∧
constants of the P atoms of the P S ligands in 6(147.1Hz) and8
(144.5 Hz) are larger than those in 5 and 7 (127.5-133.3 Hz).
The twoPatomsofthe P P ligands (P is trans to P; P is trans
0
00
0
00
∧
to Cl) in complexes 5and 7could be unambiguously assigned on
nular Rh C34 distance of 3.014(2) A clearly dem-
3 3 3
onstrates that there is no bond between these two atoms.
To get insight into the unexpected deprotonation of the
dppm ligand, quantum chemical calculations on the DFT
level of theory were performed. With the intention to limit
1
1
0
00
the basis of the difference in the JRh,P / JRh,P coupling con-
stants (ΔJ = 37.3-57.3 Hz), which reflects the trans influence
order PR3 > Cl, being also found in numerous structurally
similar complexes.45-48 Furthermore, the assignement was
2
confirmed by the magnitudes of the two JP,P coupling con-
stants: While P00 exhibits two cis couplings (31.5-98.8 Hz), P0
has one cis (32.6-98.8 Hz) and one trans coupling (338.6-
388.5 Hz). The coordination-induced shifts (CISs) of the ali-
∧
phatic carbon atoms of the propanediyl chains of the P S ligands
were found to be up to 4.2 ppm; those of the H atoms, up to 0.70
ppm. The absolute values of the 2JP,C couplings in complexes 5
were found to be decreased by about 13 Hz upon coordination
(in complexes 6, 7, and 8 the signals of the β-carbon atoms
appeared as broader singlets; thus the 2JP,C coupling constants
1
were estimated to be <2 Hz). However, the JP,C couplings
were found to be increased by about 10 Hz in 5 and 6
but decreased (ca. 5 Hz) in 7 and 8 compared to the “free”
ligands 1 and 2.
2.3.2. Cationic Rhodium Complexes Containing P,S Che-
late Ligands. Selected NMR spectroscopic data of the cationic
Figure 4. Calculated structures of [Rh(dppm-H-κ2P,P0)(Ph2-
PCH2CH2CH2SPh-κP,κS)] (17calc, left) and [Rh{CH(SPh)CH2-
CH2PPh2-κC,κP}(dppm-κ2P,P0)] (13acalc, right). H atoms of the
phenyl rings have been omitted for clarity.
Table 1. Selected NMR Sepctroscopic Data (δ in ppm, J in Hz) of [RhCl(PhSCH2CH2CH2PR2-KP)L2] (5-8)
PhS-CRH2-CβH2-CγH2-PR2
co-ligand L2
a
a
δR-C (3JP,C
)
δβ-C (2JP,C
)
δγ-C (1JP,C
)
δ
P (1JRh,P
)
δP (1JRh,P
)
δP (1JRh,P
)
00
0
0
00
R
L2
5a
5b
5c
6
Ph
Ph
Ph
Ph
Cy
Cy
Cy
Cy
Cy
Ph
Cy
dppm
dppe
dppp
cod
dppm
dppe
dppp
dmpe
cod
35.3 (15.0)
35.4 (15.8)
35.4 (16.1)
35.4 (15.0)
35.5 (11.9)
34.4 (17.7)
34.9 (13.9)
35.7 (12.4)
35.0 (11.3)
34.7 (14.0)
35.3 (13.7)
26.6 (3.9)
27.2 (4.8)
27.6 (5.5)
25.9 (s)
26.4 (s)
25.8 (s)
25.9 (s)
27.0 (s)
24.9 (s)
28.0 (21.5)
28.4 (22.7)
29.0 (24.2)
26.9 (25.2)
22.7 (13.9)
21.0 (15.2)
20.2 (15.7)
22.4 (14.6)
17.2 (17.0)
27.2 (13.2)
21.4 (19.4)
23.1 (133.3)
23.8 (131.6)
25.5 (133.3)
26.2 (147.1)
25.6 (131.4)
24.0 (127.5)
24.6 (128.4)
27.2 (128.1)
23.7 (144.5)
-16.2
-42.1 (118.9)
56.8 (141.6)
12.3 (133.3)
-15.8 (156.2)
73.9 (183.2)
34.5 (176.4)
7a
7b
7c
7d
8
-42.0 (115.5)
58.9 (135.4)
12.4 (129.1)
46.8 (131.7)
-14.7 (161.1)
71.2 (192.7)
32.3 (184.4)
40.5 (182.4)
1b
2b
25.7 (17.6)
28.9 (21.6)
-5.6
a P0 and P00 are trans to P of the PhSCH2CH2CH2PR2 ligand and Cl, respectively. b The values for PhSCH2CH2CH2PR2 (R = Ph, 1; Cy, 2) are given
for comparison.

6754 Organometallics, Vol. 29, No. 24, 2010
Block et al.
Table 2. Selected NMR Spectroscopic Data (δ in ppm, J in Hz) of [Rh(R2PCH2CH2CH2SPh-KP,KS)L2][PF6] (9-12)
PhS-CRH2-CβH2-CγH2-PR2
co-ligand L2
a
b
c
c
δR-C (3JP,C/3JP
)
,C
δβ-C
δγ-C (1JP,C
)
δ
P (1JRh,P
)
δP (1JRh,P
)
δP (1JRh,P
)
00
00
0
0
00
R
L2
9a
9b
9c
10
11a
11b
11c
11d
12
Ph
Ph
Ph
Ph
Cy
Cy
Cy
Cy
Cy
dppm
dppe
dppp
cod
dppm
dppe
dppp
dmpe
cod
40.3 (4.8/2.0)
36.3 (8.7/3.7)
35.2 (8.2/3.6)
39.4 (3.5/-)
40.0 (5.5/4.1)
39.0 (6.4/5.1)
35.4 (7.9/3.9)
36.7 (6.7/-)
39.3 (2.5/-)
22.8
21.5
21.0
22.7
25.1
23.1
22.2
23.1
24.8
27.2 (21.9)
26.0 (24.1)
27.0 (23.1)
25.7 (26.3)
17.3 (17.6)
15.5 (17.6)
12.7 (18.3)
16.0 (17.3)
16.6 (22.2)
10.3 (131.4)
7.2 (130.0)
8.9 (130.7)
12.3 (140.0)
17.9 (127.3)
13.1 (124.5)
16.3 (125.4)
18.2 (125.1)
14.4 (134.4)
-30.8 (113.8)
59.9 (128.7)
11.2 (134.1)
-18.3 (140.8)
66.8 (167.2)
21.3 (160.4)
-28.3 (111.2)
56.3 (126.4)
6.5 (120.8)
-14.1 (144.7)
71.2 (170.2)
19.0 (161.7)
36.9 (159.9)
37.4 (124.1)
2
c
a May be reversed. b The JP,C coupling constants were estimated to be <2 Hz. P0 and P00 are trans to P and S, respectively, of the
PhSCH2CH2CH2PR2 ligand.
rhodium complexes [Rh(PhSCH2CH2CH2PR2-κP,κS)L2][PF6]
(9-12) are given in Table 2. The 31P NMR spectra were
found to be of first-order AEMX (A, E, M=31P; X=103Rh;
9, 11) and AX spin systems (10, 12), respectively. The forma-
compounds (Table 3) appeared as higher order ABCX spin
systems in the case of the dppe derivatives 13b/15b and
ABMX spin systems in the case of the dppp deriv-
atives 13c/15c (A, B, C, M = 31P; X = 103Rh), which were
analyzed by using the PERCH NMR software package;50 see
Figure 5 for an example. In the complexes 13-16, hav-
ing κC,κP-coordianted P,S-functionalized organyl ligands,
lowfield shifts of the 31P resonances (up to 43.5 ppm) and
larger 1JRh,P coupling constants by up to 31.3 Hz were found
compared to the respective complexes 5b/c, 6, 7b/c, and 8
with the corresponding κP-coordinated neutral ligands (see
Tables 3 and 1). In the case of the diphosphane com-
plexes 13 and 15 the considerably higher trans influence of
tion of the RhPC3S rhodacycles go along with a decrease of
1
the JRh,P coupling constants (P00 is trans to S) by up to
00
about 20 Hz in 9 and 11 (Table 2) compared to the analogous
neutral complexes 5 and 7 (Table 1), in accord with the trans
influence order R2S > Cl.49 A comparison of the 13C NMR
data of the propanediyl group in complexes 9-12 to those in
complexes 5-8 reveals that the Cβ and Cγ resonances are
highfield shifted up to 7.5 ppm. Unexpectedly, the shift
differences of the R-C atoms were noticeable (ΔδC = 4-5
ppm) only for the dppm (9a, 11a), the cod complexes (10, 12),
and the dppe complex 11b. Noteworthy, in complexes 9 and
alkyl ligands compared to the chlorido ligand is attested by a
1
marked decrease of the JRh,P coupling constants (P00 is
00
∧
11 the additional κS coordination of the P S ligands gives
rise to a further splitting of the doublet patterns of the CR
trans to C or Cl, respectively) by up to 68.1 Hz. Furthermore,
the formation of the organorhodium intramolecular coordi-
nation compounds gives rise to lowfield shifts of the γ-C
atoms (about 6 ppm) as well as of the R-carbon atoms by ca.
10 ppm. The latter appeared as dd patterns in the cod
resonances into a doublet of doublets (3JP,C/3JP ,C). Both
00
coupling constants were found to be in a similar range; thus
they cannot clearly be assigned. Since the doublet pattern of
the R-C atoms in the cod complexes remains unchanged (10/
12 versus 6/8), it can be excluded that the additional coupling
1
2
complexes (14, 16) showing JRh,C and JP,C couplings,
whereas the signals of the CR atoms in the complexes hav-
ing coordinated diphosphanes (13, 15) proved to be of too
high multiplicity to be resolved. In the 1H NMR spectra the
most pronounced differences of 13-16 compared to 5-8
were found for the R-H signals, which were lowfield shifted
by up to 0.7 ppm.
2
is a JRh,C coupling constant. Surprisingly, in complexes
9a-c and 11a-c the signals of the γ-carbon atoms appeared
as dd patterns, too, exhibiting 1JP,C (17.6-24.1 Hz) and 3JP ,C
0
(2.1-3.2 Hz; P0 is trans to P) couplings, whereas the Cγ
resonances in the analogous neutral complexes 5 and 7 were
found to be doublets due to too small 3JP ,C constants.
0
A comparison of the NMR spectra of the zwitterionic com-
plexes 17 and 18, bearing a dppm-H ligand, to those of the
corresponding cationic complexes 9a and 11a, bearing a
dppm ligand, exhibits marked highfield shifts of the P-C-P
carbon atoms by 19.2 (17) and 16.8 ppm (18) as well as of the
2.3.3. Organorhodium Intramolecular Coordination Compounds
and Bis(diphenylphosphino)methanide Rhodium Complexes.
The 31P NMR spectra of the intramolecular coordination
(39) Cambridge Structural Database (ConQuest). Version 5.31; Crys-
tallographic Data Centre, University Chemical Laboratory, Cambridge
(UK), 2009.
(40) Appleton, T. G.; Clark, H. C.; Manzer, L. E. Coord. Chem. Rev.
1973, 10, 335.
(41) Chebi, D. E.; Fanwick, P. E.; Rothwell, I. P. Organometallics
1990, 9, 2948.
(42) Ohta, K.; Hashimoto, M.; Takahashi, Y.; Hikichi, S.; Akita, M.;
1
corresponding proton by 1.7 ppm in complex 17. The H
resonance of the CH- group in 18 could not be unambigu-
ously located due to signal overlapping.
Both the 1JRh,P coupling constants (P00 is trans to S) and
00
the 1JRh,P couplings (P is trans to P) were found to be dimin-
0
0
ished by, respectively, about 16 and 20 Hz compared to those
of the dppm ligands in complexes 9a/11a (Table 2). The only
Moro-oka, Y. Organometallics 1999, 18, 3234.
(43) Dai, C.; Robins, E. G.; Scott, A. J.; Clegg, W.; Yufit, D. S.;
Howard, J. A. K.; Marder, T. B. Chem. Commun. 1998, 1983.
(44) Karsch, H. H.; Reisky, M. Eur. J. Inorg. Chem. 1998, 905.
∧
differences in the NMR parameters of the P S ligands worth
mentioning are the larger 1JRh,P couplings (ca. 8 Hz) in com-
plexes 17 and 18 compared to 9a and 11a.
ꢁ
(45) Mezailles, N.; Avarvari, N.; Ricard, L.; Mathey, F.; Le Floch, P.
Inorg. Chem. 1998, 37, 5313.
(46) Hofmann, P.; Meier, C.; Englert, U.; Schmidt, M. U. Chem. Ber.
1992, 125, 353.
2.4. Reactions with Carbon Monoxide. Reaction of the cat-
ionic rhodium complexes [Rh(R2PCH2CH2CH2SPh-κP,κS)-
(47) Westcott, S. A.; Stringer, G.; Anderson, S.; Taylor, N. J.; Marder,
T. B. Inorg. Chem. 1994, 33, 4589.
(48) Brunner, H.; Zettler, C.; Zabel, M. Z. Anorg. Allg. Chem. 2003,
629, 1131.
(49) Graham, D. E.; Lamprecht, G. J.; Potgieter, I. M.; Roodt, A.;
∧
(P P)][PF6] (9, 11) with carbon monoxide in CH2Cl2 at -78 °C
led to the immediate formation of cationic monocarbonyl
(50) PERCH NMR Software, Version 1/2000; University of Kuopio,
Leipoldt, J. G. Transition Met. Chem. 1991, 16, 193.
Finland, 2000.

Article
Organometallics, Vol. 29, No. 24, 2010 6755
Table 3. Selected NMR Spectroscopic Data (δ in ppm, J in Hz) of [Rh{CH(SPh)CH2CH2PPh2-KC,KP}L2] (13-16) and [Rh(dppm-H
κ2P,P0)(R2PCH2CH2CH2SPh-κP,κS)] (R = Ph, 17; R = Cy, 18)
-
PhS-CRHn-CβH2-CγH2-PR2
co-ligand L2
δγ-C (1JP,C
)
δ
P (1JRh,P
)
δP (1JRh,P
)
δP (1JRh,P
)
00
a
b
c
0
0
00
R
L2
dppe
dppp
cod
dppe
dppp
cod
dppm-H
dppm-H
δR-C
δβ-C
13bd
13cd
14d
Ph
Ph
Ph
Cy
Cy
Cy
Ph
Cy
41.9-42.8
28.1
30.3
28.8
27.1
26.3
24.0
22.3
26.3
33.6 (17.1)
34.8 (24.4)
31.9 (22.4)
22.3 (18.9)
22.2 (19.6)
22.5 (15.9)
28.7 (18.6)
19.2 (13.0)
58.6 (162.3)
57.7 (164.6)
58.6 (168.3)
67.5 (155.2)
66.3 (156.5)
63.5 (170.2)
12.8 (144.1)
19.4 (137.7)
63.1 (165.9)
21.0 (162.1)
60.2 (123.6)
18.2 (119.1)
45.9-46.7
35.5 (16.4/4.5)f
41.2-43.3
15bd
15cd
16d
61.9 (159.5)
17.2 (154.5)
61.2 (124.6)
18.3 (120.9)
44.5-46.1
38.4 (20.6/4.0)f
38.6 (7.5/3.3)g
38.2 (8.1/5.3)g
17e
-35.0 (93.6)
-33.1 (93.0)
-24.2 (124.2)
-21.9 (129.0)
18e
2
b
c
a The JP,C coupling constants were estimated to be <2 Hz. P0 is trans to P of the PhSCHnCH2CH2PR2 ligand. P00 is trans to C and S of the
PhSCHnCH2CH2PR2 ligand, respectively. d CRHn with n = 1. e CRHn with n = 2. f 1JRh,C/2JP,C
.
J
P,C
/3JP ,C; may be reversed.
g 3
00
Table 4. Selected NMR (δ in ppm) and IR (ν in cm-1) Spectroþ-
∧
scopic Data of Cations [Rh(CO)(R2PCH2CH2CH2SPh)(P P)]
(19, 20)
a
a
∧
∧
∧
R
P P
δ
P (P P)
δ
P (P S)
δC (CO)
ν (CO)
19a Ph dppm
19b Ph dppe
19c Ph dppp
20a Cy dppm
20b Cy dppe
20c Cy dppp
20d Cy dmpe
-25.3
55.9
6.4
-20.6
55.3
6.8
29.9
27.3
24.8
37.6
34.5
39.9
42.1
190.7
190.1
190.7
190.0
189.8
192.8
192.2
1989, 2024
1988, 2022
1994, 2024
1994, 2025
1994, 2019
1994, 2022
1994, 2024
28.4
a Broad signals in an intensity ratio of 2:1.
for the major component three ddd coupling patterns were
found, and for the minor component only one ddd reso-
nance, whereas the other two resonances remained broad as
nonresolved signals. The coordination of CO was exhibited
13C NMR spectroscopically by broad signals in the typical
range for a carbonyl ligands (δC 189.8-192.8 ppm, Table 4).
Furthermore, IR spectra of reaction solutions showed two
ν(CO) bands in the region of terminally bound carbonyl
ligands at about 1990 and 2022 cm-1, in the typical range for
cationic pentacoordianted rhodium(I) phosphane carbonyl
complexes.53-55 HRMS-ESI measurements in the cationic
mode did not show the molecular peaks [M]þ but only the
mass peaks of the decarbonylated cations [M - CO]þ as the
most intensive peaks (base peaks) in all cases with the excep-
tion of 20a and 20c. Only in the case of 20c was the CO-
containing molecular peak detected being even the base
peak. In almost all spectraþpeaks of the bis(diphosphane)-
Figure 5. Simulated (above) and measured (81 MHz, below)
31P NMR spectra of [Rh{CH(SPh)CH2CH2PPh2-κC,κP}-
(dppe)] (13a). The ABC part of the ABCX spin system is shown
(A, B, C = 31P; X = 103Rh).
rhodium complexes 19 and 20, as revealed by NMR spectro-
scopic investigations (Table 4). In contrast, the analogous
cod complexes 10 and 12 did not react with CO, even at room
temperature. 13C and 31P NMR spectroscopic measurements
of the reaction solutions of 19 and 20 indicated theþformation
of complexes of the type [Rh(CO)(P S)(P P)] . The 31P
NMR spectra at room temperature showed broad signals
indicating molecular dynamics in solution (Table 4). All of
these reactions proceed quantitatively; no other signals were
∧
∧
∧
∧
found, especially none of the “free” P P andP S ligands. Only
in the case of the dppm complexes do additional doublets
at -21.1/-21.2 ppm (19a/20a) in the 31P NMR spectra point
to the formation of [Rh(dppm-κ2P,P0)2]þ51 as a side product.
Furthermore, in the case of 19a a doublet at 18.3 ppm is likely
caused by the formation of the dinuclear rhodium(I) carbonyl
complex [Rh2(μ-Cl)(μ-CO)(dppm-1κP:2κP0)2(CO)2]þ as side
product. This was further confirmed by a single-crystal
X-ray diffraction measurement of colorless crystals obtained
from the respective reaction solution, which proved to be of
the same molecular structure as described in ref 52.
∧
rhodium cations [Rh(P P)2] were found; in the case of 20a it
is even the base peak. The NMR investigations showed these
species are not present in the original solutions (with the
exception of 19a/20a), thus being formed during the ioniza-
tion process of the HRMS-ESI experiments. All attempts to
isolate complexes of type 19 and 20 failed. Evaporation of the
solvent (CH2Cl2) in vacuo or precipitation of the complexes
with nonpolar solvents such as n-pentane followed by filtra-
tion and drying led to decomposition with a partial re-
formation of the starting complexes 9 and 11.
In order to get insight into the formation of such rhodium
carbonyl complexes, quantum chemical calculations at the DFT
level of theory were performed. To reduce the computational
For 19b it was shown that at -80 °C the above-mentioned
equilibrium is frozen, showing two rhodium complexes at an
intensity ratio of 3:1. Each of these complexes has coordinated
three chemically inequivalent phosphorus atoms, in accord
with an AEMX spin system (A, E, M=31P, X=103Rh). Thus,
(53) Pignolet, L. H.; Doughty, D. H.; Nowicki, S. C.; Anderson,
M. P.; Casalnuovo, A. L. J. Organomet. Chem. 1980, 202, 211.
(54) Turculet, L.; Feldman, J. D.; Tilley, T. D. Organometallics 2004,
23, 2488.
(51) Ernsting, J. M.; Elsevier, C. J.; de Lange, W. G. J.; Timmer, K.
Magn. Reson. Chem. 1991, 29, S118.
(55) Tejel, C.; Shi, Y.-M.; Ciriano, M. A.; Edwards, A. J.; Lahoz,
(52) Cowie, M. Inorg. Chem. 1979, 18, 286.
F. J.; Modrego, J.; Oro, L. A. J. Am. Chem. Soc. 1997, 119, 6678.

6756 Organometallics, Vol. 29, No. 24, 2010
Block et al.
Scheme 4. Synthesis of Cationic Rhodium Carbonyl Complexes
Figure 6. Calculated structures of [Rh(CO)(Me2PCH2CH2CH2-
SMe)(dmpe)]þ having the Me2PCH2CH2CH2SMe ligand bound
κP (21acalc) and κP,κS (21bcalc, 21ccalc). H atoms have been omit-
ted for clarity. Energies are relative to the most stable isomer
(21acalc).
Furthermore, the corresponding calculations for the cod
complex were performed. Here, five equilibrium structures
of 22calc were found (Figure S1, Supporting Information).
The thermodynamically most stable isomer 22acalc showed a
square-planar geometry where the primary donor set of the
rhodium atom is built up by the Me2PCH2CH2CH2SMe-
κP,κS ligand, the carbonyl ligand (CO is trans to S), and the
cod ligand, which is coordinated in a monodentate fashion
expense, the calculations were done by substituting the
phenyl and cyclohexyl groups by methyl groups, thus calcu-
lating complexes of the type [Rh(CO)(Me2PCH2CH2-
CH2SMe)(dmpe)]þ (21calc). Three isomeric equilibrium struc-
tures could be located (Figure 6); using other starting geom-
etries resulted in the formation of one of these equilibrium
structures. In the thermodynamically most stable isomer,
21acalc, the rhodium atom is located in the center of a slightly
distorted square-planar environment, coordinated by the
dmpe-κ2P,P0, the Me2PCH2CH2CH2SMe-κP, and the car-
bonyl ligand. On the basis of the structural index τ56 the other
two isomers, 21bcalc and 21ccalc, can be described as, respec-
tively, strongly distorted trigonal-bipyramidal and square-
pyramidal complexes. In these two complexes the rhodium
atom has the carbonyl ligand coordinated equatorially, whereas
only. Slightly less stable (1.4 kcal/mol) is the isomer 22bcalc
,
where the cod ligand is coordinated in a bidentate fashion;
thus the rhodium atom exhibits a distorted square-pyramidal
geometry having the sulfur atom in the apical position. The
carbonyl complex formation of 22acalc according to the
equation
½RhðMe2PCH2CH2CH2SMe-KP, KSÞðcodÞꢀþ ð10calc
Þ
þ COf½RhðCOÞðMe2PCH2CH2CH2SMe-KP, KSÞðcodÞꢀþð22acalc
Þ
∧
the P S ligand adopts an equatorial-apical (e-a) coordina-
tion, with the posphorus atoms in the apical position. While
in 21bcalc the dmpe ligand is coordinated e-a, too, in 21ccalc
the dmpe ligand occupies the remaining equatorial positions.
Complex 21bcalc was found to be of a similar energy (3.0 kcal/
mol) to 21acalc. However, complex 21ccalc is the thermody-
namically least favorable (8.8 kcal/mol) isomer.
was calculated to be exothermic (ΔE=-10.4 kcal/mol, 0 K)
but only slightly exergonic (ΔGQ = -1.4 kcal/mol) under
standard conditions considering solvent effects (CH2Cl2).
This value lies within the margin of error of DFT calcula-
tions and must not be exaggerated; experimentally the cod
∧
complexes 10 and 12, which differ from 10calc in that the P S
The carbonyl complex formation
ligand has Ph2P/Cy2P and SPh substituents, were not found
to react with CO.
½RhðMe2PCH2CH2CH2SMeÞðdmpeÞꢀþ ð11dcalc
Þ
2.5. Conclusions. Reactions of dinuclear chlorido-bridged
rhodium(I) complexes [(RhL2)2(μ-Cl)2] with phosphino-func-
tionalized sulfides PhSCH2CH2CH2PR2 afford mononuc-
lear complexes of type I (Scheme 5) bearing κP-coordinated
þ CO f ½RhðCOÞðMe2PCH2CH2CH2SMeÞðdmpeÞꢀþ ð21calc
Þ
was found to be exothermic (ΔE = -16.1 kcal/mol, 0 K).
Calculation of the standard Gibbs free energy considering
solvent effects (CH2Cl2) using the polarized continuum
model57 was performed and revealed that the reaction is
exergonic (ΔGQ = -7.7 kcal/mol). If the results of the DFT
calculations are conveyed to the experimental findings, the
dynamic equilibrium found in complexes 19 and 20 is based
on an equilibrium between a four- and a five-coordinated
∧
P S ligands. These reactions go along with a cleavage of the
Rh-Cl-Rh bridges and formation of Rh-P bonds, as dem-
onstrated in numerous reactions described in the literature.58
Reactions of these complexes with LDA (I f II) lead to a
regioselective deprotonation of the R-carbon atom under for-
mation of organorhodium intramolecular coordination com-
pounds. This is noteworthy since the deprotonation of the
“free” ligands proceeds nonregioselectively (R- versus ortho-
metalation).28,59 The intramolecular coordination compounds
II are much more stable than rhodium complexes bearing
nonfunctionalized alkyl ligands60,61 because decomposition
reactions such as hydride eliminations are hampered for ste-
reoelectronic reasons. Reactions of LDA with I bearing
dppm as a ligand result in formation of type III complexes
∧
Rh(I) complex having the P S ligands, respectively, κP and
κP,κS coordinated (Scheme 4). Thus, the ligand is hemila-
bile, which might be an explanation for the;at least par-
tial;re-formation of the starting complexes 9 and 11 when
complexes 19 and 20 were attempted to be isolated.
(56) Addison, A. W.; Rao, T. N.; Reedijk, J.; van Rijn, J.; Verschoor,
G. C. J. Chem. Soc., Dalton Trans. 1984, 1349.
(57) (a) Cances, E.; Mennucci, B.; Tomasi, J. J. Chem. Phys. 1997,
107, 3032. (b) Cossi, M.; Barone, V.; Mennucci, B.; Tomasi, J. Chem. Phys.
Lett. 1998, 286, 253. (c) Mennucci, B.; Tomasi, J. J. Chem. Phys. 1997, 106,
5151.
(58) Hughes, R. P. In Comprehensive Organometallic Chemistry;
Wilkinson, G.; Stone, F. G. A.; Abel, E. W., Eds.; Pergamon: Oxford,
1982; Vol. 5, p 277.
ꢀ
€
(59) Linnert, M.; Bruhn, C.; Ruffer, T.; Schmidt, H.; Steinborn, D.
Organometallics 2004, 23, 3668.

Article
Organometallics, Vol. 29, No. 24, 2010 6757
∧
Scheme 5. Reactivity of Rhodium Complexes with P S Ligands toward Bases, Chloride Acceptors, and Carbon Monoxide
having bound an anionic dppm-H-κ2P,P0 ligand and a γ-
phosphino-functionalized thioether ligand (κP,κS coor-
dinated), as well. These neutral complexes have a formal
charge separation between a cationic metal center and a
negatively charged ligand; thus they are zwitterionic (betaine-
like) complexes,62 which might make them attractive in
homogeneous catalysis.63-65 The formation of these dppm-H
complexes (type III) proceeds under kinetic control because
the respective (calculated) organorhodium intramolecular
coordination compound bearing a (nondeprotonated) dppm
ligand of type II was found to be more stable by more than 20
kcal/mol. Apart from [Rh(dppm-H-κ2P,P0)(dppm-κ2P,P0)],41
complexes bearing hemilabile κP,κS-coordinated ligands
was found.
3. Experimental Part
3.1. General Comments. All reactions and manipulations
were carried out under argon using standard Schlenk techniques.
Diethyl ether, toluene, n-pentane, and THF were dried over
Na/benzophenone 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, δH 7.24, δC 77.0;
CD2Cl2, δH 5.32, δC 53.8; C6D6, δH 7.15, δC 128.0; THF-d8,
δH 1.73/3.58, δC 25.4/67.6) as internal references; δ(19F) is
relative to external CCl3F; δ(31P) is relative to external H3PO4
(85%). Multiplets in NMR spectra of higher order resulting in
pseudodoublets and pseudotriplets 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.50 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) 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 introduced
complex 18 THF is the only one structurally characterized
3
rhodium type III complex. Reactions of the neutral rhodium-
(I) complexes with Tl[PF6] (I f IV) afford cationic Rh(I)
complexes having the phoshino-functionalized propyl phenyl
sulfide ligands bound in κP,κS mode.
∧
Rhodium complexes bearing P S ligands were often found
to react with CO under formation of rhodium carbonyl com-
plexes.66 Here, the complexes with a cod ligand show no reac-
∧
tion, and those having diphosphanes as ligands (P P) are
found to react with CO (IV f V), yielding monocarbonyl
complexes that are in a dynamic equilibrium at room tem-
perature. DFT calculations indicated that this equilibrium is
∧
between two constitutional isomers having the P S ligand
bound monodentately κP and bidentately κP,κS, respec-
∧
tively. This reflects a hemilabile behavior of such P S ligand,
as also found in other transition metal complexes.67,68 On
the basis of all these findings, the reactivity of rhodium(I)
complexes bearing κP-coordinated phosphino-functionalized
propyl phenyl sulfide ligands toward deprotonation and
reaction with Tl[PF6] can be understood. Moreover, an
easy access to organorhodium intramolecular coordination
compounds, zwitterionic rhodium complexes, and rhodium
continuously via a syringe pump with a flow rate of 120 μL h-1
.
∧
[{Rh(cod)}2(μ-Cl)2] (3) and [{Rh(P P)}2(μ-Cl)2] (4a-d) were
prepared according to literature procedures.29,69-71 Details of
the preparation of starting compounds 1 and 2 and a complete
set of their NMR spectroscopic data are given in the Support-
ing Information.
3.2. Preparation of [RhCl(R2PCH2CH2CH2SPh-KP)L2]
(5-8). Route A. To a stirred suspension of the respective
rhodium complex [(RhL2)(μ-Cl)2)] (3, 4; 0.25 mmol) in THF
(3 mL) was added a solution of R2PCH2CH2CH2SPh (1, 2;
0.50 mmol) in THF (2 mL), and the mixture was stirred for
1 h. The solution was concentrated under reduced pressure
almost to dryness before n-pentane (5 mL) was added. The
resulting precipitate was filtered off, washed with n-pen-
tane (3 ꢁ 2 mL), and dried in vacuo.
(60) Cundy, C. S.; Lappert, M. F.; Pearce, R. J. Organomet. Chem.
1973, 59, 161.
(61) Keim, W. J. Organomet. Chem. 1968, 14, 179.
(62) Stradiotto, M.; Hesp, K. D.; Lundgren, R. J. Angew. Chem., Int.
Ed. 2010, 49, 494.
(63) Stradiotto, M.; Cipot, J.; McDonald, R. J. Am. Chem. Soc. 2003,
125, 5618.
(64) Cipot, J.; McDonald, R.; Stradiotto, M. Chem. Commun. 2005,
4932.
(65) Cipot, J.;Vogels,C. M.;McDonald, R.;Westcott, S. A.;Stradiotto,
Route B. To a stirred solution of [{Rh(cod)}2(μ-Cl)2] (123.3 mg,
0.25 mmol) in THF (3 mL) was added a solution of R2PCH2-
CH2CH2SPh (1, 2; 0.50 mmol) in THF (2 mL), and the mixture
was stirred for 1 h. The respective diphosphane (0.50 mmol) in
M. Organometallics 2006, 25, 5965.
(66) Yoo, H.; Mirkin, C. A.; DiPasquale, A. G.; Rheingold, A. L.;
Stern, C. L. Inorg. Chem. 2008, 47, 9727.
(67) Ulmann, P. A.; Mirkin, C. A.; DiPasquale, A. G.; Liable-Sands,
L. M.; Rheingold, A. L. Organometallics 2009, 28, 1068.
(68) Brown, A. M.; Ovchinnikov, M. V.; Mirkin, C. A. Angew.
Chem., Int. Ed. 2005, 44, 4207.
(69) Cramer, R. Inorg. Synth. 1990, 28, 86.
(70) Cao, P.; Wang, B.; Zhang, X. J. Am. Chem. Soc. 2000, 122, 6490.
(71) Fairlie, D. P.; Bosnich, B. Organometallics 1988, 7, 936.

6758 Organometallics, Vol. 29, No. 24, 2010
Block et al.
THF (3 mL) was added, and the reaction mixture was stirred for
5 h. The solution was concentrated under reduced pressure almost
to dryness before n-pentane (5 mL) was added. The resulting
precipitatewas filteredoff, washedwithn-pentane (5ꢁ 1 mL), and
dried in vacuo.
30.1/30.8 (s/d, J(13C, 31P) = 3.4 Hz, C2/C3, PCy2), 34.5
(d, J(13C, 31P) = 17.5 Hz, C1, PCy2), 35.5 (d, J(13C, 31P) =
11.9 Hz, CH2SPh), 51.3 (“t”, Ph2PCH2PPh2), 126.0-137.9
(CPh). 31P NMR (81 MHz, THF-d8): δ -42.0 (ddd, 2J(31P,
31P) = 98.1 Hz, 2J(31P, 31P)=374.6 Hz, 1J(31P, 103Rh) =
115.5 Hz, P (dppm) trans to P), -14.7 (ddd, 2J(31P, 31P) =
1
3
∧
R=Ph, L2=P P=dppm (5a). Yield: 213 mg (50%, route A).
2
1
32.7 Hz, J(31P, 31P)=98.1 Hz, J(31P, 103Rh) = 161.1 Hz, P
Anal. Found: C, 64.68; H, 5.04. Calcd for C46H42ClP3SRh
(858.19): C, 64.39; H, 4.93. 1H NMR (400 MHz, THF-d8):
δ 2.03 (m, 2H, CH2CH2CH2), 2.41 (m, 2H, CH2CH2CH2PPh2),
2.98 (“t”, N=14.3 Hz, 2H, CH2SPh), 3.93 (“t”, N=19.2 Hz, 2H,
PPh2CH2PPh2), 7.00-7.48 (m, 35H, HPh). 13C NMR (100 MHz,
THF-d8): δ 26.6 (d, 2J(13C, 31P) = 3.9 Hz, CH2CH2-
CH2), 28.0 (d, 1J(13C, 31P)=21.5 Hz, CH2CH2CH2PPh2), 35.3
(dppm) trans to Cl), 25.6 (ddd, J(31P, 31P)=32.7 Hz, J(31P,
2
2
31P)=374.6 Hz, 1J(31P, 103Rh) = 131.4 Hz, PCy2).
∧
R=Cy, L2=P P=dppe (7b). Yield: 213 mg (48%, route B).
Anal. Found: C, 63.34 H, 6.55. Calcd for C47H57ClP3SRh
(885.33): C, 63.77; H, 6.49. 1H NMR (400 MHz, THF-d8):
δ 0.97-2.21 (m, 30H, PCy2/Py2PCH2CH2CH2/Ph2PCH2CH2-
PPh2), 2.58 (“t”, 2H, CH2SPh), 7.84-8.06 (m, 25H, HPh). 13C
3
(d, J(13C, 31P) = 15.0 Hz, CH2SPh), 50.4 (“t”, N = 43.9 Hz,
NMR (100 MHz, THF-d8): δ 21.0 (d, J(13C, 31P)=15.2 Hz,
1
PPh2CH2PPh2), 125.9-138.3 (CPh). 31P NMR (81 MHz, THF-
d8): δ -42.1 (m, 2J(31P, 31P)=98.8 Hz, 2J(31P, 31P)=388.5 Hz,
1J(31P, 103Rh) = 118.9 Hz, P (dppm) trans to P), -15.8
(m, 2J(31P, 31P) = 31.5 Hz, 2J(31P, 31P) = 98.8 Hz, 1J(31P,
103Rh) = 156.2 Hz, P (dppm) trans to Cl), 23.1 (m, 2J(31P,
31P) = 31.5 Hz, 2J(31P, 31P) = 388.5 Hz, 1J(31P, 103Rh) =
133.3 Hz, PPh2).
CH2PCy2), 25.1/35.4 (m/m, Ph2PCH2CH2PPh2), 25.8 (s, CH2-
CH2CH2), 26.6 (s, C4, PCy2), 29.5/30.6 (s/d, J(13C, 31P)=2.7 Hz
1
C3/C2, PCy2), 34.4 (d, J(13C, 31P)=17.7 Hz, C1, PCy2), 34.8
3
(d, J(13C, 31P) = 12.6 Hz, CH2SPh), 125.3-137.1 (CPh). 31P
2
NMR (81 MHz, THF-d8): δ 24.0 (ddd, J(31P, 31P)=35.5 Hz,
2J(31P, 31P)=342.9 Hz, 1J(31P, 103Rh)=127.5 Hz, PCy2), 58.9
2
2
1
(ddd, J(31P, 31P) = 32.6 Hz, J(31P, 31P) = 342.9 Hz, J(31P,
103Rh)=135.4 Hz, P (dppe) trans to P), 71.2 (ddd, 2J(31P, 31P)=
32.6 Hz, 2J(31P, 31P) = 35.5 Hz, 1J(31P, 103Rh) = 192.7 Hz,
P (dppm) trans to Cl).
∧
R=Ph, L2 = P P = dppe (5b). Yield: 393 mg (90%, route B).
Anal. Found: C, 64.40; H, 5.15. Calcd for C47H44ClP3SRh
(872.22): C, 64.73; H, 5.09. 1H NMR (400 MHz, THF-d8):
δ 1.77-1.89/2.36-2.10 (m/m, 4H, PPh2CH2CH2PPh2), 2.05-
2.07 (m, CH2CH2CH2), 2.42 (m, 2H, CH2CH2CH2PPh2), 2.96
∧
R=Cy, L2=P P=dppp (7c). Yield: 216 mg (48%, route A).
Anal. Found: C, 64.33 H, 6.52. Calcd for C48H59ClP3SRh
(“t”, N=14.5 Hz, 2H, CH2SPh), 6.94-8.07 (m, 35H, HPh). 13
C
1
(899.34): C, 64.11; H, 6.61. H NMR (400 MHz, benzene-d6):
NMR (100 MHz, THF-d8): δ 26.5/35.8 (m/m, Ph2PCH2CH2-
2
PPh2), 27.2 (d, J(13C, 31P)= 4.8 Hz, CH2CH2CH2), 28.4 (d,
δ 0.95-2.28 (m, 32H, Cy2PCH2CH2/Ph2PCH2CH2CH2PPh2),
2.65 (“t”, 2H, CH2SPh), 7.87-7.98 (m, 25H, HPh). 13C NMR
(100 MHz, benzene-d6): δ 19.2 (s, Ph2PCH2CH2CH2PPh2), 20.2
1J(13C, 31P) = 22.7 Hz, CH2CH2CH2PPh2), 35.4 (d, 3J(13C,
31P) = 15.8 Hz, CH2SPh), 126.0-138.4 (CPh). 31P NMR (81
1
(d, J(13C, 31P)= 15.7 Hz, CH2PCy2), 25.9 (s, CH2CH2SPh),
2
2
MHz, THF-d8): δ 23.8 (ddd, J(31P, 31P) = 357.2 Hz, J(31P,
31P) = 35.6 Hz, J(31P, 103Rh) = 131.6 Hz, PPh2), 56.8 (ddd,
1
26.1/31.5 (m/m, Ph2PCH2CH2CH2PPh2), 26.6 (s, C4, PCy2),
3
2J(31P, 31P)=357.2 Hz, 2J(31P, 31P)=33.6 Hz, 1J(31P, 103Rh)=141.6
Hz, P (dppe) trans to P), 73.9 (ddd, 2J(31P, 31P)=33.6 Hz, 2J(31P,
31P)=35.6 Hz, 1J(31P, 103Rh)=183.2 Hz, P (dppe) trans to Cl).
29.8/31.1 (s/s, C2/C3, PCy2), 34.9 (d, J(13C, 31P) = 13.9 Hz,
CH2SPh), 35.0 (d, 1J(13C, 31P)=16.7 Hz C1, PCy2), 125.3-138.2
(CPh). 31P NMR (81 MHz, benzene-d6): δ 12.4 (ddd, 2J(31P,
31P)=56.2 Hz, 2J(31P, 31P)=338.6 Hz, 1J(31P, 103Rh)=129.1 Hz,
∧
R=Ph, L2=P P=dppp (5c). Yield: 355 mg (80%, route B).
2
2
P (dppp) trans to P), 24.6 (ddd, J(31P, 31P)=35.7 Hz, J(31P,
Anal. Found: C, 64.64; H, 5.16. Calcd for C48H46ClP3SRh
(886.25): C, 65.06; H, 5.23. 1H NMR (400 MHz, THF-d8):
δ 1.63-1.78 (m, 2H, PPh2CH2CH2CH2PPh2), 2.08 (m, 6H,
PhSCH2CH2CH2PPh2, PhSCH2CH2), 2.24 (m, 2H, PhSCH2-
CH2CH2), 2.95 (“t”, N = 14.4 Hz, 2H, CH2SPh), 6.82-7.90
(m, 35H, HPh). 13C NMR (100 MHz, THF-d8): δ 20.5 (s, br,
PPh2CH2CH2CH2PPh2), 27.6 (d, 2J(13C, 31P) = 5.5 Hz,
PhSCH2CH2), 27.8/32.7 (m/m, PPh2CH2CH2CH2PPh2), 29.0
31P)=338.7 Hz, J(31P, 103Rh) = 128.4 Hz, PCy2), 32.3 (ddd,
1
2J(31P, 31P)=35.7 Hz, 2J(31P, 31P)=56.2 Hz, 1J(31P, 103Rh) =
184.4 Hz, P (dppp) trans to Cl).
∧
R=Cy, L2=P P=dmpe (7d). Yield: 251 mg (79%, route A).
Anal. Found: C, 50.43 H, 7.76. Calcd for C27H49ClP3SRh
(637.04): C, 50.91; H, 7.75. 1H NMR (400 MHz, THF-d8):
δ 1.10-2.05 (m, 22H, PCy2), 1.37/1.43 (d/d, J(1H, 31P)=8.1/
2
1
3
(d, J(13C, 31P)=24.2 Hz, PhSCH2CH2CH2), 35.4 (d, J(13C,
31P) = 16.1 Hz, CH2SPh), 125.9-138.7 (CPh). 31PNMR(81 MHz,
THF-d8): δ 12.3 (ddd, 2J(31P, 31P)=351.5 Hz, 2J(31P, 31P)=55.5
Hz, 1J(31P, 103Rh)=133.3 Hz, P (dppp) trans to P), 25.5 (ddd,
2J(31P, 31P) = 351.5 Hz, 2J(31P, 31P)=53.9 Hz, 1J(31P, 103Rh)=
133.3 Hz, PPh2), 34.5 (ddd, 2J(31P, 31P)=55.5 Hz, 2J(31P, 31P)=
53.9 Hz, 1J(31P, 103Rh)=176.4 Hz, P (dppp) trans to Cl).
R=Ph, L2 =cod (6). Yield: 248 mg (85%, route A). Anal.
Found: C, 58.32; H, 5.51. Calcd for C29H33PClSRh (582.98): C,
58.75; H, 5.71. 1H NMR (400 MHz, CDCl3): δ 1.87-1.93/
2.28-2.35 (m/m, 4H/4H, 4 ꢁ CH2, cod), 2.15-2.25 (m, 2H,
CH2CH2CH2), 2.61-2.67 (m, 2H, CH2PPh2), 3.10 (m, 2H, CH2-
SPh), 4.15 (s, br, 4H, 4 ꢁ CH, cod), 7.14-7.59 (m, 15H, HPh).
13C NMR (100 MHz, CDCl3): δ 25.9 (s, CH2CH2CH2), 26.9
(d, 1J(13C, 31P)=25.2 Hz, CH2PPh2), 31.0 (s, br, 4 ꢁ CH2, cod),
35.4 (d, 3J(13C, 31P)=15.0 Hz, CH2SPh), 78.6-78.9 (m, 4 ꢁ CH,
cod), 126.2-133.5 (CPh). 31P NMR (81 MHz, CDCl3): δ 26.2
(d, 1J(31P, 103Rh)=147.1 Hz, PPh2).
9.3 Hz, 12H, PCH3), 1.66 (m, 2H, CH2PCy2), 1.73 (m, 4H,
Me2PCH2CH2PMe2), 1.86 (m, 2H, CH2CH2CH2), 3.07 (m, 2H,
CH2SPh), 7.09 (m, 1H, p-H, SPh), 7.23 (m, 2H, m-H, SPh), 7.34
(m, 2H, o-H, SPh). 13C NMR (100 MHz, THF-d8): δ 14.7/19.8
(d/d, 1J(13C, 31P)=24.3 Hz/1J(13C, 31P) = 22.9 Hz, PCH3), 22.4
(d, 1J(13C, 31P) = 14.6 Hz, CH2PCy2), 26.1/35.6 (m/m, Me2-
PCH2CH2PMe2), 27.0 (s, CH2CH2CH2), 27.6 (s, C4, PCy2),
30.4/31.4 (s/d, J(13C, 31P) = 3.6 Hz, C3/C2, PCy2), 35.7
(d, 3J(13C, 31P) = 12.4 Hz, CH2SPh), 36.2 (d, 1J(13C, 31P) =
16.8 Hz, C1, PCy2), 126.0 (s, p-C, SPh), 129.4 (s, m-C, SPh),
129.5 (s, o-C, SPh), 138.1 (s, i-C, SPh). 31P NMR (81 MHz,
2
2
THF-d8): δ 27.2 (ddd, J(31P, 31P)=351.6 Hz, J(31P, 31P)=
34.1 Hz, 1J(31P, 103Rh)=128.1 Hz, PCy2), 40.5 (ddd, 2J(31P, 31P) =
2
1
34.1 Hz, J(31P, 31P) = 34.2 Hz, J(31P, 103Rh)=182.4 Hz, P
2
2
(dmpe) trans to Cl), 46.8 (ddd, J(31P, 31P)=34.2 Hz, J(31P,
31P)=351.6 Hz, 1J(31P, 103Rh)=131.7 Hz, P (dmpe) trans to P).
R=Cy, L2 =cod (8). Yield: 154 mg (52%, route A). Anal.
Found: C, 58.66 H, 7.57. Calcd for C29H45ClPSRh (595.07): C,
58.53; H, 7.62. 1H NMR (200 MHz, THF-d8): δ 0.98-1.22/
1.36-1.75/2.05-2.18 (m/m/m, 34H, CH2CH2CH2PCy2/4 ꢁ
CH2, cod), 2.64 (m, 2H, CH2SPh), 3.46/5.58 (s/s, br/br, 2H/
2H, 4 ꢁ CH (cod)), 6.83-6.87 (m, 1H, p-H, SPh), 6.95-7.00
(m, 2H, m-H, SPh), 7.20-7.22 (m, 2H, o-H, SPh). 13C NMR
(100 MHz, THF-d8): δ 17.2 (d, 1J(13C, 31P)=17.0 Hz, CH2PCy2),
24.9 (s, CH2CH2CH2), 26.5 (s, br, 4 ꢁ CH2, cod), 27.4 (s, C4,
∧
R=Cy, L2=P P=dppm (7a). Yield: 369 mg (85%, route A).
Anal. Found: C, 63.22 H, 6.29. Calcd for C51H60ClP3SRh
(871.29): C, 63.41; H, 6.36. 1H NMR (400 MHz, THF-d8):
δ 0.97-2.04 (m, 26H, PCy2/CH2CH2CH2PCy2), 2.73 (“t”, 2H,
CH2SPh), 3.92 (“t”, 2H, Ph2PCH2PPh2), 7.06-7.99 (m, 25H,
1
HPh). 13C NMR (100 MHz, THF-d8): δ 22.7 (d, J(13C, 31P)=
13.9 Hz, CH2PCy2), 26.4 (s, CH2CH2CH2), 27.4 (s, C4, PCy2),

Article
Organometallics, Vol. 29, No. 24, 2010 6759
PCy2), 27.5 (d, 2J(13C, 31P)=4.7 Hz, C2, PCy2), 29.8 (d, 3J(13C,
31P)=19.4 Hz, C3, PCy2), 33.9 (d, 1J(13C, 31P)= 21.0 Hz, C1,
PCy2), 35.0 (d, 3J(13C, 31P)=11.3 Hz, CH2SPh), 67.3/103.1 (m/m,
4 ꢁ CH, cod), 126.0 (s, p-C, SPh), 129.1 (s, m-C, SPh), 129.3 (s, o-
C, SPh), 136.4 (s, i-C, SPh). 31P NMR (81 MHz, THF-d8):
δ 23.7 (d, 1J(31P, 103Rh)=144.5 Hz, PCy2).
(s, PhSCH2CH2CH2), 27.0 (dd, 1J(13C, 31P)=23.1 Hz, 3J(13C,
31
P
)=3.2 Hz, PhSCH2CH2CH2), 25.6/28.8 (m/m, Ph2PCH2-
trans
CH2CH2PPh2), 35.2 (dd, 3J(13C, 31P)/3J(13C, 31Ptrans)=8.2/3.6
Hz PhSCH2), 128.1-133.1 (CPh). 31P NMR (81 MHz, THF-d8):
δ -142.9 (sept, J(31P, 19F)=709.6 Hz, PF6-), 8.9 (m, J(31P,
31P)=38.5 Hz, 2J(31P, 31P)=338.5 Hz, 1J(31P, 103Rh)=130.7 Hz,
PPh2), 11.2 (m, 2J(31P, 31P)=53.3 Hz, 2J(31P, 31P)=338.5 Hz,
1J(31P, 103Rh)=134.1 Hz, P (dppp) trans to P), 21.3 (ddd, 2J(31P,
31P)=53.3 Hz, 2J(31P, 31P)=38.5, 1J(31P, 103Rh)=160.5 Hz, P
(dppp) trans to S). 19F NMR (188 MHz, THF-d8): δ -73.4
(d, 1J(19F, 31P)=709.6 Hz, PF6-).
1
2
3.3. Preparation of [Rh(R2PCH2CH2CH2SPh-KP,KS)L2][PF6]
(9-12). Route A. To the respective rhodium complex [(RhL2)-
(μ-Cl)2)] (3, 4; 0.25 mmol) in THF (3 mL) was added a solution
of R2PCH2CH2CH2SPh (1, 2; 0.50 mmol) in THF (2 mL),
and the mixture was stirred for 1 h. Then Tl[PF6] (174.68 mg,
0.5 mmol) suspended in THF (3 mL) was added. The mixture
was stirred for 30 min, and the precipitated TlCl was filtered off.
The filtrate was reduced almost to dryness, and n-pentane (3 mL)
was added. The precipitated solid was filtered off, washed with
n-pentane (3 ꢁ 3 mL), and dried in vacuo.
R=Ph, L2=cod (10). Yield: 256.1 mg (86%, route A). HRMS
(ESI): m/z calcd for [C29H33PRhS]þ 547.5166, found for [M]þ
1
547.5155. H NMR (400 MHz, CD2Cl2): δ 2.05-2.22/2.35-
2.46 (m/m, 6H/4H, CH2CH2CH2/4 ꢁ CH2, cod), 2.75 (m, 2H,
CH2PPh2), 3.48 (m, 2H, CH2SPh), 3.83/4.65 (s/s, br/br, 2H/2H,
4 ꢁ CH, cod), 7.46-7.70 (m, 15H, HPh). 13C NMR (125 MHz,
Route B. To a stirred solution of [{Rh(cod)}2(μ-Cl)2] (123.3 mg,
0.25 mmol) in THF (5 mL) was added a solution of R2PCH2-
CH2CH2SPh (1, 2; 0.50 mmol) in THF (2 mL), and the mixture
was stirred for 1 h before the respective diphosphane (0.50
mmol) dissolved in THF (3 mL) was added slowly. After
5 h Tl[PF6] (174.68 mg, 0.5 mmol) suspended in THF (3 mL)
was added, and the mixture was stirred for 30 min. The
precipitated TlCl was filtered off, the filtrate was reduced almost
to dryness, and n-pentane (3 mL) was added. The precipitated
solid was filtered off, washed with n-pentane (3 ꢁ 5 mL), and
dried in vacuo.
1
CD2Cl2): δ 22.7 (s, br, CH2CH2CH2), 25.7 (d, J(13C, 31P)=
26.3 Hz, CH2PPh2), 29.28/29.29/32.19/32.22 (s/s/s/s, 4 ꢁ CH2
(cod)), 39.4 (d, 3J(13C, 31P)=3.5 Hz, CH2SPh), 86.3/105.0 (d/dd,
1J(13C, 103Rh)=11.0/10.1 Hz, 2J(13C, 31Ptrans)=7.1 Hz, 4 ꢁ CH,
cod), 129.6-134.0 (CPh). 31P NMR (80 MHz, CD2Cl2):
δ -142.8 (sept, 1J(31P, 19F)=709.6 Hz, PF6-), 12.3 (d, 1J(31P,
103Rh) = 140.0 Hz, PPh2). 19F NMR (188 MHz, CD2Cl2):
δ -73.4 (d, 1J(19F, 31P)=709.6 Hz, PF6-).
∧
R=Cy, L2=P P=dppm (11a). Yield: 431 mg (88%, route A).
HRMS (ESI): m/z calcd for [C46H55P3RhS]þ 835.2287, found
for [M]þ 835.2299. 1H NMR (400 MHz, CD2Cl2): δ 0.94-2.18
(m, 26H, CH2CH2CH2PCy2), 2.87 (m, 2H, CH2SPh), 4.03 (“t”,
∧
R=Ph, L2=P P=dppm (9a). Yield: 411 mg (85%, route A).
HRMS (ESI): m/z calcd for [C46H43P3RhS]þ 823.1348; found
for [M]þ 823.1359. 1H NMR (500 MHz, CD2Cl2): δ 2.00-2.09
(m, 2H, CH2CH2CH2), 2.53 (s, br, 2H, Ph2PCH2CH2), 3.21
(m, 2H, PhSCH2), 4.01 (“t”, N=19.8 Hz, 2H, Ph2PCH2PPh2),
6.76-7.49 (m, 35H, HPh). 13C NMR (125 MHz, CD2Cl2): δ 22.8
N=9.8 Hz, 2H, Ph2PCH2PPh2), 7.04-7.80 (m, 25H, HPh). 13
C
1
NMR (100 MHz, CD2Cl2): δ 17.3 (dd, J(13C, 31P)=17.6 Hz,
3J(13C, 31Ptrans)=2.9 Hz, CH2PCy2), 25.1 (s, CH2CH2CH2), 26.3
(s, C4, PCy2), 28.6/30.6 (s/d, J(13C, 31P)=3.1 Hz, C3/C2, PCy2),
1
3
(s, br, CH2CH2CH2), 27.2 (dd, J(13C, 31P)=21.9 Hz, J(13C,
37.4 (d, 1J(13C, 31P) = 23.1 Hz, C1, PCy2), 40.0 (dd, 3J(13C,
31
)=2.1 Hz, Ph2PCH2CH2), 40.3 (dd, 3J(13C, 31P)/3J(13C,
)=4.8/2.0 Hz (the two coupling constants given may be
31
trans
trans
31P)/3J(13C,
P
) = 5.5/4.1 Hz, CH2SPh), 49.8 (“t”, N =
trans
P
P
31
23.1 Hz, Ph2PCH2PPh2), 129.0-135.8 (CPh). 31P NMR
(80 MHz, CD2Cl2): δ -143.0 (sept, 1J(31P, 19F) = 708.6 Hz,
PF6-), -28.3 (ddd, 2J(31P, 31P)=85.2 Hz, 2J(31P, 31P)=275.1
Hz, 1J(31P, 103Rh)=111.2 Hz, P (dppm) trans to P), -14.1 (ddd,
reversed here and also in complexes 9b/c and 11b/c), PhSCH2),
50.8 (“t”, N = 45.0 Hz, Ph2PCH2PPh2), 128.3-135.2 (CPh).
1
31P NMR (81 MHz, CD2Cl2): δ -142.7 (sept, J(31P, 19F) =
709.5 Hz, PF6-), -30.8 (ddd, 2J(31P, 31P)=87.6 Hz, 2J(31P, 31P)=
2J(31P, 31P)=85.2 Hz, J(31P, 31P)=32.3 Hz, J(31P, 103Rh)=
144.7 Hz, P (dppm) trans to S), 17.9 (ddd, 2J(31P, 31P)=32.3 Hz,
2J(31P, 31P)=275.1, 1J(31P, 103Rh)=127.3 Hz, PCy2). 19F NMR
(188 MHz, CD2Cl2): δ -73.7 (d, 1J(19F, 31P)=708.6 Hz, PF6-).
2
1
1
290.5 Hz, J(31P, 103Rh)=113.8 Hz, P (dppm) trans to P), -
18.3 (ddd, 2J(31P, 31P)=32.0 Hz, 2J(31P, 31P)=87.6 Hz, 1J(31P,
103Rh)=140.8 Hz, P (dppm) trans to S), 10.3 (ddd, 2J(31P, 31P)=
32.0 Hz, 2J(31P, 31P)=290.5, 1J(31P, 103Rh)=131.4 Hz, PPh2).
19F NMR (188 MHz, CD2Cl2): δ -73.4 (d, 1J(19F, 31P) =
709.5 Hz, PF6-).
∧
R=Cy, L2=P P=dppe (11b). Yield: 413 mg (82%, route A).
HRMS (ESI): m/z calcd for [C47H57P3RhS]þ 849.2443; found
for [M]þ 849.2439. 1H NMR (500 MHz, THF-d8): δ 0.95 -2.26
(m, 30H, CH2CH2CH2PCy2/Ph2PCH2CH2PPh2), 3.01 (s, br,
2H, CH2SPh), 7.10-8.33 (m, 25H, HPh). 13C NMR (125 MHz,
∧
R=Ph, L2=P P=dppe (9b). Yield: 432 mg (88%, route B).
HRMS (ESI): m/z calcd for [C47H45P3RhS]þ 837.1504, found
for [M]þ 837.1490. 1H NMR (500 MHz, CD2Cl2): δ 1.89-2.00/
2.09-2.32 (m 4H, PH2PCH2CH2PPh2), 1.98-2.05 (m, 2H,
CH2CH2CH2), 2.32 (m, 2H, Ph2PCH2CH2CH2), 2.91 (m, 2H,
PhSCH2), 6.85-7.63 (m, 35H, HPh). 13C NMR (125 MHz,
CD2Cl2): δ 15.0 (dd J(13C, 31P)=17.7 Hz, J(13C,
P
trans
)=
1
3
31
2.7 Hz CH2PCy2), 23.3 (s, CH2CH2CH2), 25.3-25.7/32.2-32.9
(m/m, Ph2PCH2CH2PPh2), 26.2 (s, C4, PCy2), 29.0/31.5 (d/d,
1
J(13C, 31P)=4.7/4.8 Hz, C3/C2, PCy2), 37.8 (d, J(13C, 31P)=
CD2Cl2): δ 21.5 (s, CH2CH2CH2), 26.0 (dd, 1J(13C, 31P)=24.1
21.2 Hz, C1, PCy2), 39.0 (dd, 3J(13C, 31P)/3J(13C, 31Ptrans)=6.4/
5.1 Hz, CH2SPh), 128.8-134.5 (CPh). 31P NMR (80 MHz, THF-
31
Hz, 3J(13C,
P
) = 2.1 Hz, Ph2PCH2CH2), 27.6-27.9/
trans
32.9-33.3 (m/m, Ph2PCH2CH2PPh2), 36.3 (dd, 3J(13C, 31P)/3J-
1
d8): δ -142.7 (sept, J(31P, 19F)=708.8 Hz, PF6-), 13.1 (ddd,
31
(13C,
P
trans
) = 8.7/3.7 Hz, PhSCH2), 128.3-133.4 (CPh).
2J(31P, 31P)=34.3 Hz, 2J(31P, 31P)=264.4 Hz, 1J(31P, 103Rh)=
124.5 Hz, PCy2), 56.3 (ddd, 2J(31P, 31P)=31.9 Hz, 2J(31P, 31P)=
264.4 Hz, 1J(31P, 103Rh)=126.4 Hz, P (dppe) trans to P), 71.2
(d“t”, 2J(31P, 31P) = 34.3 Hz, 2J(31P, 31P) = 31.9 Hz, 1J(31P,
103Rh)=170.2 Hz, P (dppe) trans to S). 19F NMR (188 MHz,
THF-d8): δ -74.0 (d, 1J(19F, 31P)=708.8 Hz, PF6-).
31P NMR (81 MHz, CD2Cl2): δ -142.3 (sept, J(31P, 19F) =
710.3 Hz, PF6-), 7.2 (ddd, 2J(31P, 31P)=33.4 Hz, 2J(31P, 31P)=
1
286.2 Hz, J(31P, 103Rh)=130.0 Hz, PPh2), 59.9 (ddd, J(31P,
1
2
31P)=31.5 Hz, 2J(31P, 31P)=286.2 Hz, 1J(31P, 103Rh)=128.7 Hz,
P (dppe) trans to P), 66.8 (ddd, J(31P, 31P)=31.5 Hz, J(31P,
2
2
31P)=33.4, 1J(31P, 103Rh)=167.2 Hz, P (dppe) trans to S). 19
F
∧
R=Cy, L2=P P=dppp (11c). Yield: 393 mg (78%, route A).
NMR (188 MHz, THF-d8):δ-73.4(d,1J(19F, 31P)=710.3 Hz, PF6-).
HRMS (ESI): m/z calcd for [C48H59P3RhS]þ 863.2600, found
for [M]þ 863.2600. 1H NMR (500 MHz, CD2Cl2): δ 1.00-2.13/
2.23/2.45/2.56 (m/m/m/m, 32H, CH2CH2PCy2, Ph2PCH2CH2-
CH2PPh2), 2.94 (m, 2H, CH2SPh), 7.17-7.75 (m, 25H, HPh).
13C NMR (100 MHz, CD2Cl2): δ 12.7 (dd, 1J(13C, 31P) =
18.3 Hz, 3J(13C, 31Ptrans)=2.6 Hz, CH2PCy2), 19.0 (s, Ph2PCH2-
CH2CH2PPh2), 22.2 (s, PhSCH2CH2), 24.9/28.3 (m/m, Ph2-
PCH2CH2CH2PPh2), 26.3 (s, C4, PCy2), 29.5/33.1 (d/d, J(13C,
∧
R=Ph, L2=P P=dppp (9c). Yield: 388 mg (78%, route A).
HRMS (ESI): m/z calcd for [C48H47P3RhS]þ 851.1661, found
for [M]þ 851.1661. 1H NMR (500 MHz, CD2Cl2): δ 1.81 (m 4H,
PhSCH2CH2CH2, Ph2CH2PCH2CH2PPh2), 2.20 (s, br, 2H,
PhSCH2CH2CH2), 2.25-2.33 (m, 4H, Ph2CH2PCH2CH2PPh2),
2.71 (s, br, 2H, PhSCH2), 6.98-7.59 (m, 35H, HPh). 13C NMR
(125 MHz, CD2Cl2): δ 18.6 (s, Ph2CH2PCH2CH2PPh2), 21.0

6760 Organometallics, Vol. 29, No. 24, 2010
Block et al.
31P) = 6.1 Hz/J(13C, 31P) = 5.4 Hz, C2/C3, PCy2), 35.4 (dd,
∧
R=Ph, L2=P P=dppe (13b). Yield: 352 mg (84%, route B).
Anal. Found: C, 67.72; H, 5.55. Calcd for C47H44P3SRh
31
3J(13C, 31P)/3J(13C,
P
) = 7.9/3.9 Hz, CH2SPh), 36.9
trans
(d, J(13C, 31P)=19.4 Hz, C1, PCy2), 128.6-136.1 (CPh). 31P
NMR (80 MHz, CD2Cl2): δ -142.9 (sept, 1J(31P, 19F) =
710.1 Hz, PF6-), 6.5 (ddd, 2J(31P, 31P) = 55.3 Hz, 2J(31P,
31P)=267.2 Hz, 1J(31P, 103Rh)=120.8 Hz, P (dppp) trans to P),
19.0 (ddd, 2J(31P, 31P)=55.3 Hz, 2J(31P, 31P)=32.8 Hz, 1J(31P,
103Rh)=161.7 Hz, P (dppp) trans to S), 16.3 (ddd, 2J(31P, 31P)=
32.8 Hz, 2J(31P, 31P)=267.2, 1J(31P, 103Rh)=125.4 Hz, PCy2).
19F NMR (188 MHz, CD2Cl2): δ -73.4 (d, 1J(19F, 31P) =
710.1 Hz, PF6-).
1
1
(836.76): C, 67.46; H, 5.30. H NMR (500 MHz, benzene-d6):
δ 1.74-2.66 (m, 8H, Ph2PCH2CH2PPh2, CHCH2CH2), 3.07
(m, 1H, CHSPh), 6.77-8.00 (m, 35H, HPh). 13C NMR (100 MHz,
benzene-d6): δ 28.1 (s, CHCH2CH2), 28.7-29.2/33.1-33.4
(m/m, Ph2PCH2CH2PPh2), 33.6 (dd, 1J(13C, 31P) = 17.1 Hz,
3J(13C, 31Ptrans)=2.7 Hz, CHCH2CH2), 41.9-42.8 (m, CHSPh),
123.4-143.2 (CPh). 31P NMR (81 MHz, benzene-d6): δ 58.6 (m,
2J(31P, 31P)=27.9 Hz, 2J(31P, 31P)=304.0 Hz, 1J(31P, 103Rh)=
162.3 Hz, PPh2), 60.2 (m, 2J(31P, 31P)=27.9 Hz, 2J(31P, 31P)=
1
R=Cy, L2=P P=dmpe (11d). Yield: 265 mg (71%, route A).
25.0 Hz, J(31P, 103Rh)=123.6 Hz, P (dppe) trans to C), 63.1
∧
HRMS (ESI): m/z calcd for [C27H49P3RhS]þ 601.1817, found
(m, 2J(31P, 31P)=304.0 Hz, 2J(31P, 31P)=25.0, 1J(31P, 103Rh)=
165.9 Hz, P (dppe) trans to P).
for [M]þ 601.1819. H NMR (400 MHz, CD2Cl2): δ 1.08/1.58
1
(d/d, 2J(1H, 31P)=8.7/8.4 Hz, 12H, PCH3), 1.15-2.09/2.28 (m/s, -
/br, 30H, CH2CH2CH2PCy2/Me2PCH2CH2PMe2), 2.90 (m,
2H, CH2SPh), 7.43 (m, 2H, m-H, SPh), 7.52 (m, 1H, p-H, SPh),
7.86 (m, 2H, o-H, SPh). 13C NMR (100 MHz, CD2Cl2):
∧
R=Ph, L2=P P=dppp (13c). Yield: 352 mg (84%, route A).
Anal. Found: C, 66.84; H, 5.79. Calcd for C48H46P3SRh
1
(850.79): C, 67.76; H, 5.45. H NMR (400 MHz, THF-d8): δ
1.11-1.22/1.55-1.79 (m/m, 1H/1H, CHCH2CH2), 1.55-1.79/
1.86-1.94 (m/m, 1H/1H, Ph2PCH2CH2CH2PPh2), 1.94-2.07/
2.40-2.55 (m/m, 2H/2H, Ph2PCH2CH2CH2PPh2), 2.17-2.25/
2.58-2.68 (m/m, 1H/1H, CHCH2CH2), 3.33 (m, 1H, CHSPh),
6.68-7.89 (m, 35H, HPh). 13C NMR (100 MHz, THF-d8): δ 20.7
(s, Ph2PCH2CH2CH2PPh2), 30.3 (s, CHCH2CH2) 31.5-31.7/
δ 13.6/17.6 (d/d, J(13C, 31P)=22.9/25.4 Hz, PCH3), 16.0 (d,
1
1J(13C, 31P) = 17.3 Hz, CH2PCy2), 23.1 (s, CH2CH2CH2),
25.1-25.6/35.0-36.0 (m/m, Me2PCH2CH2PMe2), 26.3 (s, C4,
PCy2), 29.4/32.3 (d/d, J(13C, 31P)=3.8/6.1 Hz, C3/C2, PCy2),
36.7 (d, 3J(13C, 31P)=6.7 Hz, CH2SPh), 39.2 (d, 3J(13C, 31P)=
22.5 Hz, C1, PCy2), 129.6 (s, m-C, SPh), 130.2 (s, p-C, SPh),
134.2 (s, o-C, SPh), 136.0 (s, i-C, SPh). 31P NMR (80 MHz,
34.9-35.3 (m/m, Ph2PCH2CH2CH2PPh2), 34.8 (dd, 1J(13C,
31
31P) = 24.4 Hz, 1J(13C,
P ) = 5.7 Hz, CHCH2CH2),
trans
THF-d8): δ -142.8 (sept, J(31P, 19F)=708.5 Hz, PF6-), 18.2
45.9-46.7 (m, CHSPh), 123.4-143.5 (CPh). 31P NMR (81 MHz,
THF-d8): δ 18.2 (m, 2J(31P, 31P)=21.9 Hz, 2J(31P, 31P)=47.9 Hz,
1J(31P, 103Rh)=119.1 Hz, P (dppm) trans to C), 21.0 (m, 2J(31P,
31P)=293.1 Hz, 2J(31P, 31P)=47.9 Hz, 1J(31P, 103Rh)=162.1 Hz,
P (dppm) trans to P), 57.7 (ddd, 2J(31P, 31P)=293.1 Hz, 2J(31P,
31P)=21.9, 1J(31P, 103Rh)=164.6 Hz, PPh2).
1
(ddd, J(31P, 31P) = 37.0 Hz, J(31P, 31P) = 272.3 Hz, J(31P,
2
2
1
103Rh) = 125.1 Hz, PCy2), 36.9 (ddd, J(31P, 31P) = 37.0 Hz,
2
2J(31P, 31P)=32.8 Hz, 1J(31P, 103Rh)=159.9 Hz, P (dmpe) trans
to S), 37.4 (ddd, 2J(31P, 31P)=272.3 Hz, 2J(31P, 31P)=32.8 Hz,
1J(31P, 103Rh)=124.1 Hz, P (dmpe) trans to P). 19F NMR (188
MHz, THF-d8): δ -73.8 (d, 1J(19F, 31P)=708.5 Hz, PF6-).
R=Cy, L2=cod (12). Yield: 250 mg (71%, route A). HRMS
(ESI): m/z calcd for [C29H45PRhS]þ 559.2029, found for [M]þ
559.2021. 1H NMR (200 MHz, CD2Cl2): δ 1.24-2.56 (m, 34H,
CH2CH2CH2PCy2/4 ꢁ CH2, cod), 3.22 (m, 2H, CH2SPh), 4.44/
4.58 (m/m, 2H/2H, 4 ꢁ CH, cod), 7.45-7.52 (m, 3H, o-H/p-H,
SPh), 6.57-6.64 (m, 2H, m-H, SPh). 13C NMR (100 MHz,
CD2Cl2): δ 16.6 (d, 1J(13C, 31P) = 22.2 Hz, CH2PCy2), 24.8
(s, CH2CH2CH2), 26.3 (s, C4, PCy2) 27.1/27.3/27.4/27.6 (s/s/s/s,
4 ꢁ CH2, cod), 31.1/32.4 (s/d, J(13C, 31P)=2.6 Hz, C2/C3PCy2),
36.2 (d, 1J(13C, 31P)=21.9 Hz, C1, PCy2), 39.3 (d, 3J(13C, 31P)=
R=Ph, L2=cod (14). Yield: 248 mg (85%, route A). Anal.
Found: C, 62.02; H, 8.33. Calcd for C28H44PSRh (546.60): C,
61.53; H, 8.11. 1H NMR (200 MHz, THF-d8): δ 1.25-2.51
(m, 12H, Ph2PCH2CH2CH, 4 ꢁ CH2, cod), 2.78 (s, br, 1H,
CHSPh), 3.88-4.54 (m, 4H, 4 ꢁ CH, cod), 6.83-7.63 (m, 15H,
H
Ph). 13C NMR (50 MHz, THF-d8): δ 28.8 (s, CH2CH2CH),
31.9 (d, 1J(13C, 31P)=22.4, CH2PPh2), 31.6/31.8/32.0/33.3 (s/s/
s/s, 4 ꢁ CH2, cod), 35.5 (dd, 2J(13C, 31P) = 4.5 Hz, 1J(13C,
103Rh)=16.4 Hz, CHSPh), 70.1/73.4/76.1/79.6 (d/d/d/d, 1J(13C,
103Rh) = 13.4/13.4/10.5/10.6 Hz, 4 ꢁ CH, cod), 126.4-147.2
(CPh). 31P NMR (80 MHz, THF-d8): δ 58.6 (d, 1J(31P, 103Rh)=
168.3 Hz, PPh2).
2.5 Hz, CH2SPh), 84.2/103.1 (d/dd, 1J(13C, 103Rh) = 11.1/
31
10.6 Hz, 2J(13C,
132.4 (s/s, m-C/o-C SPh), 130.4 (s, i-C, SPh), 130.9 (s, p-C, SPh).
P
trans
) = 7.3 Hz, 4 ꢁ CH, cod), 130.2/
R=Cy, L2=P P=dppe (15b). Yield: 146 mg (35%, route A).
∧
1H NMR (400 MHz, benzene-d6): δ 1.04-2.32 (m, 30H,
Cy2PCH2CH2/Ph2PCH2CH2PPh2), 3.01 (m, 1H, CHSPh),
31P NMR (81 MHz, CD2Cl2): δ -143.0 (sept, J(31P, 19F) =
1
708.6 Hz, PF6-), 14.4 (d, 1J(31P, 103Rh) = 134.4 Hz, PCy2).
19F NMR (188 MHz, CD2Cl2): δ -73.0 (d, 1J(19F, 31P) =
708.6 Hz, PF6-).
6.78-8.07 (m, 25H, HPh). 13C NMR (50 MHz, THF-d8):
δ 22.3 (dd, 1J(13C, 31P) = 18.9 Hz, 1J(13C,
) = 6.8 Hz
trans
31
P
CH2PCy2), 27.1 (s, CH2CH2CH2), 27.2-36.6 (Ph2PCH2CH2-
3.4. Preparation of [Rh{CH(SPh)CH2CH2PPh2-KC,KP}L2]
(13b/c, 14, 15b/c, 16). Route A. To a stirred suspension of the
respective rhodium complex [(RhL2)(μ-Cl)2)] (3, 4; 0.25 mmol)
in toluene (3 mL) was added a solution of R2PCH2CH2CH2SPh
(1, 2; 0.50 mmol) in toluene (2 mL), and the mixture was stirred
for 1 h before LDA (0.5 mmol, 0.91 M in THF) was added
slowly at -78 °C. The mixture was allowed to warm to room
temperature, and the precipitated LiCl was filtered off. The
filtrate was reduced to half of its volume, and n-pentane (3 mL)
was added. The precipitated solid was filtered off, washed with
n-pentane (3 ꢁ 1 mL), and dried in vacuo.
PPh2/C4/C3/C2/C1, PCy2), 41.2-43.3 (m, CHSPh), 123.2-
2
144.5 (CPh). 31P NMR (81 MHz, THF-d8): δ 61.2 (m, J(31P,
31P)=27.4 Hz, 2J(31P, 31P)=25.6 Hz, 1J(31P, 103Rh)=124.6 Hz,
P (dppe) trans to C), 61.9 (m, 2J(31P, 31P)=25.6 Hz, 2J(31P, 31P)=
300.3 Hz, 1J(31P, 103Rh)=159.5 Hz, P (dppe) trans to P), 67.5
2
2
1
(ddd, J(31P, 31P) = 27.4 Hz, J(31P, 31P) = 300.3 Hz, J(31P,
103Rh)=155.2 Hz, PCy2).
∧
R=Cy, L2=P P=dppp (15c). Yield: 140 mg (33%, route A).
1H NMR (400 MHz, THF-d8): δ 1.04-2.55 (m, 32H, Cy2PCH2-
CH2/Ph2PCH2CH2CH2PPh2), 3.32 (m, 1H, CHSPh), 6.65-7.89
(m, 25H, HPh). 13C NMR (50 MHz, THF-d8): δ 20.0 (s,
Route B. To a stirred solution of [{Rh(cod)}2(μ-Cl)2] (123.3 mg,
0.25 mmol) in toluene (3 mL) was added a solution of R2PCH2-
CH2CH2SPh (0.50 mmol) in toluene (2 mL), followed by the
addition of the respective diphosphane (0.50 mmol) dissolved in
toluene (2 mL). After 5 h LDA (1, 2; 0.55 mL, 0.5 mmol, 0.91 M in
THF) was added slowly at -78 °C. The mixture was allowed to
warm to room temperature, and the precipitated LiCl was filtered
off. The filtrate was reduced to half of its volume, and n-pentane
(3 mL) was added. The precipitated solid was filtered off, washed
with n-pentane (3 ꢁ 1 mL), and dried in vacuo.
Ph2PCH2CH2CH2PPh2), 22.2 (dd, 1J(13C, 31P) = 19.6 Hz,
1J(13C,
P
trans
) = 7.6 Hz, CH2PCy2), 26.3 (s, CHCH2CH2),
31
26.6-30.8 (C4/C3/C2, PCy2), 27.2-27.7/31.7-32.3 (m/m, Ph2-
PCH2CH2CH2PPh2), 37.9 (d, 1J(13C, 31P)=18.3 Hz, C1, PCy2),
44.5-46.1 (m, CHSPh), 122.2-143.4 (CPh). 31P NMR (81 MHz,
THF-d8): δ 17.2 (m, 2J(31P, 31P) = 289.9 Hz, 2J(31P, 31P) =
1
46.3 Hz, J(31P, 103Rh)=154.5 Hz, P (dppp) trans to P), 18.3
(m, 2J(31P, 31P)=32.4 Hz, 2J(31P, 31P)=46.3 Hz, 1J(31P, 103Rh)=
120.9 Hz, P (dppp) trans to C), 66.3 (ddd, 2J(31P, 31P)=32.4 Hz,
2J(31P, 31P)=289.9 Hz, 1J(31P, 103Rh)=156.5 Hz, PCy2).

Article
R=Cy, L2=cod (16). Yield: 87 mg (31%, route A). 1H NMR
Organometallics, Vol. 29, No. 24, 2010 6761
31P NMR (27 °C, 81 MHz, CD2Cl2): δ 27.3 (“q”, br, PPh2), 55.9
(“t”, br, P (dppe)). 31P NMR (-80 °C, 202 MHz, CD2Cl2):
major isomer δ 30.6 (ddd, 2J(31P, 31P)=30.3 Hz, 2J(31P, 31P)=
250.2 Hz, 1J(31P, 103Rh)=80.1 Hz, PPh2), 49.5 (ddd, 2J(31P, 1P)
=30.3 Hz, 2J(31P, 31P)=15.2 Hz, 1J(31P, 103Rh)=121.2 Hz, P
(dppe)), 60.8 (ddd, 2J(31P, 31P)=15.2 Hz, 2J(31P, 31P)=250.2 Hz,
1J(31P, 103Rh)=76.3 Hz, P (dppe)); minor isomer δ 18.1 (ddd,
2J(31P, 31P)=30.2 Hz, 2J(31P, 31P)=263.9 Hz, 1J(31P, 103Rh)=
98.5 Hz, PPh2), 42.8-46.2 (m, br, P (dppe)), 67.6-70.2 (m, br,
P (dppe)).
(400 MHz, THF-d8): δ 1.17-3.00 (m, 37H, Cy2PCH2CH2CH
/4 ꢁ CH2/4 ꢁ CH, cod), 7.09-7.48 (m, 5H, HPh). 13C NMR
(50 MHz, THF-d8): δ 22.5 (d, 1J(13C, 31P)=15.9 Hz, CH2PCy2),
24.0 (s, CHCH2CH2), 26.5-30.0 (C4/C3/C2, PCy2, 4 ꢁ CH2,
cod), 38.0 (d, 1J(13C, 31P)=21.6 Hz, C1, PCy2), 38.4 (dd, 2J(13C,
31P) = 4.0 Hz, 1J(13C, 103Rh) = 20.6 Hz, CHSPh), 72.7/80.0
(m/m, 4 ꢁ CH, cod), 126.2 (s, m-C, SPh), 128.9 (s, o-C, SPh),
130.9 (s, p-C, SPh), 145.7 (s, i-C, SPh). 31P NMR (202 MHz,
THF-d8): δ 62.9 (d, 1J(31P, 103Rh)=170.0 Hz, PCy2).
3.5. Preparation of [Rh(dppm-H-K2P,P0)(R2PCH2CH2CH2-
SPh-KP,KS)] (17, 18). To a stirred suspension of [{Rh(dppm)}2-
(μ-Cl)2] (261.39 mg, 0.25 mmol) in toluene (3 mL) was added a
solution of R2PCH2CH2CH2SPh (1, 2; 0.50 mmol) in toluene
(2 mL), and the mixture was stirred for 1 h before LDA
(0.5 mmol, 0.91 M in THF) was added slowly at -78 °C. The
mixture was alowed to warm to room temperature, and the
precipitated LiCl was filtered off. The filtrate was reduced to
half of its volume, and n-pentane (3 mL) was added. The pre-
cipitated compound was filtered off, washed with n-pentane
(3 ꢁ 1 mL), and dried in vacuo.
Ph/dppp (19c). HRMS (ESI): m/z calcd for [C48H47P3RhS]þ
851.1661, found for [M - CO]þ 851.1651. IR: ν=1994 (CO),
2024 (CO) cm-1 13C NMR (100 MHz, CD2Cl2): δ 190.7 (CO).
.
31P NMR (27 °C, 81 MHz, CD2Cl2): δ 6.4 (“t”, br, P (dppp)),
24.8 (“q”, br, PPh2).
Cy/dppm (20a). HRMS (ESI): m/z calcd for [C46H55P3RhS]þ
835.2287, found for [M - CO]þ 835.2276. IR: ν=1994 (CO),
2025 (CO) cm-1 13C NMR (100 MHz, CD2Cl2): δ 190.0 (CO).
.
31P NMR (27 °C, 81 MHz, CD2Cl2): δ -20.6 (“t”, br, P (dppm)),
1
37.6 (“q”, br, PCy2), -21.2 (d, J(31P, 103Rh)=97.3 Hz, [Rh-
(dppm-κ2P,P0)2]þ).
R=Ph (17). Yield: 292 mg (71%) HRMS (ESI): m/z calcd for
[C46H42P3RhS] 822.7175, found for [M] 822.7168. 1H NMR
(500 MHz, THF-d8): δ 1.80-1.91 (m, 2H, CH2CH2CH2), 2.25
(m, 3H, CH2CH2Ph2, Ph2PCHPPh2), 2.98 (s, br, 2H, CH2SPh),
6.78-7.81 (m, 35H, HPh). 13C NMR (125 MHz, benzene-d6):
δ 22.3 (s, br, CH2CH2CH2PPh2), 28.7 (d, 1J(13C, 31P)=18.6 Hz,
CH2CH2PPh2), 31.2 (“t”, N = 102.3 Hz, Ph2PCHPPh2), 38.6
(dd, 3J(13C, 31P)/3J(13C, 31Ptrans)=7.5/3.3 Hz (the two coupling
constants may be reversed), CH2SPh), 127.4-144.7 (CPh). 31P
NMR (81 MHz, benzene-d6): δ -35.0 (ddd, 2J(31P, 31P)=60.3
Hz, 2J(31P, 31P)=301.0 Hz, 1J(31P, 103Rh)=93.6 Hz, P (dppm)
trans to P), -24.2 (ddd, 2J(31P, 31P)=23.3 Hz, 2J(31P, 31P)=60.3
Hz, 1J(31P, 103Rh)=124.2 Hz, P (dppm) trans to S), 12.8 (ddd,
2J(31P, 31P)=23.3 Hz, 2J(31P, 31P)=301.0, 1J(31P, 103Rh)=144.1
Hz, 1P, PPh2). The complex contained residual amounts of
diisopropylamine.
Cy/dppe (20b). HRMS (ESI): m/z calcd for [C47H57P3RhS]þ
849.2443, found for [M - CO]þ 849.2433. IR: ν=1994 (CO)
cm-1, 2019 (CO). 13C NMR (100 MHz, CD2Cl2): δ 189.8 (CO).
31P NMR (27 °C, 81 MHz, CD2Cl2): δ 34.5 (“q”, br, PCy2), 55.3
(“t”, br, P (dppe)).
Cy/dppp (20c). HRMS (ESI): m/z calcd for [C49H59OP3RhS]þ
891.2549, found for [M]þ 891.2547. IR: ν =1994 (CO), 2022
(CO) cm-1 13C NMR (100 MHz, CD2Cl2): δ 192.8 (CO). 31P
.
NMR (27 °C, 81 MHz, CD2Cl2): δ 6.8 (“t”, br, P (dppp)), 39.9
(“q”, br, PCy2).
Cy/dmpe (20d). HRMS (ESI): m/z calcd for [C27H49P3RhS]þ
601.1817, found for [M - CO]þ 601.1823. IR: ν=1994 (CO),
2024 (CO) cm-1 13C NMR (100 MHz, CD2Cl2): δ 192.2 (CO).
.
31P NMR (27 °C, 81 MHz, CD2Cl2): δ 28.4 (“t”, br, P (dmpe)),
42.1 (“q”, br, PCy2).
3.7. X-ray Crystallography. Data for X-ray diffraction anal-
yses of single crystals of 7b C6H6 and 18 THF were collected on
R=Cy (18). Yield: 305 mg (73%). HRMS (ESI): m/z calcd for
[C46H55P3RhS] 835.2287, found for [M] 835.2250. 1H NMR
(400 MHz, THF-d8): δ 0.60-2.23 (m, 27H, CH2CH2PCy2,
Ph2PCHPPh2), 2.71 (s, br, 2H, CH2SPh), 6.95-8.03 (m, 25H,
3
3
a Stoe-IPDS 2T diffractometer at 200(2) K and of 10 at 220(2)
K on a Stoe-IPDS diffractometer using Mo KR radiation (λ=
0.7103 A, graphite monochromator). A summary of the crystal-
lographic data, the data collection parameters, and the refine-
ment parameters is given in Table S1 (see Supporting
Information). Absorption corrections were applied numerically
H
Ph). 13C NMR (100 MHz, THF-d8): δ 19.2 (dd, 1J(13C, 31P)=
31
13.0 Hz, 3J(13C,
P
) = 2.0 Hz, CH2PCy2), 26.3 (s,
trans
CH2CH2CH2), 27.0 (s, C4, PCy2), 29.2/30.8 (s/d, J(13C, 31P)=
5.6 Hz, C2/C3, PCy2), 34.5 (’t’, N=99.2 Hz, Ph2PCHPPh2), 38.2
with X-RED3272 (Tmin/Tmax 0.63/0.96, 7b C6H6; 0.92/0.97, 10;
3
(d, J(13C, 31P)=19.4 Hz, C1, PCy2), 39.8 (dd, J(13C, 31P)/3
J(13C, 31Ptrans)=8.1/5.3 Hz (the two coupling constants may be
reversed), CH2SPh), 127.4-146.4 (CPh). 31P NMR (81 MHz,
0.79/0.87, 18 THF). The structures were solved with direct
1
3
3
methods using SHELXS-9773 and refined using full-matrix
least-squares routines against F2 with SHELXL-97.74 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.
3.8. Computational Details. DFT calculations were carried
out by the Gaussian 03 program75 package using the hybrid
functional B3LYP,76 and the 6-311þþG(3df,3pd) (P, S) and
6-31þG* (O, C, H) basis sets as implemented in Gaussian 03
were employed for main group atoms. The valence shell of
rhodium has been approximated by a split valence basis set too
(Def2-TZVPP); for its core orbitals an effective core potential
THF-d8): δ -33.1 (ddd, J(31P, 31P)=57.4 Hz, J(31P, 31P)=
281.8 Hz, 1J(31P, 103Rh)=93.1 Hz, P (dppm) trans to P), -22.0
(ddd, 2J(31P, 31P) = 26.6 Hz, 2J(31P, 31P) = 57.4 Hz, 1J(31P,
103Rh)=129.1 Hz, P (dppp) trans to S), 19.4 (ddd, 2J(31P, 31P)=
26.6 Hz, 2J(31P, 31P) = 281.8 Hz, 1J(31P, 103Rh) = 137.7 Hz,
PCy2).
2
2
∧
3.6. Reaction of [Rh(R2PCH2CH2CH2SPh-KP,KS)(P P)]-
[PF6] with Carbon Monoxide. At -78 °C carbon monoxide is
bubbled through a solution of [Rh(R2PCH2CH2CH2SPh-
κP,κS)(P P)][PF6] (9, 11; 0.03 mmol) in CD2Cl2 (1 mL) for
two minutes. Spectroscopic investigations were performed di-
rectly from the solutions obtained.
∧
(72) X-RED32 (version 1.03): Stoe Data Reduction Program; Stoe &
Cie GmbH: Darmstadt, 2002.
(73) Sheldrick, G. M. SHELXS-97, Program for Crystal Structure
∧
R/P P: Ph/dppm (19a). HRMS (ESI): m/z calcd for [C46H43-
P3RhS]þ 823.1348, found for [M - CO]þ 823.1350. IR: ν=1989
(CO), 2024 (CO) cm-1 13C NMR (100 MHz, CD2Cl2): δ 190.7
.
€
€
Solution; University of Gottingen: Gottingen, 1998.
(74) Sheldrick, G. M. SHELXL-97, Program for the Refinement of
(CO). 31P NMR (27 °C, 81 MHz, CD2Cl2): δ -25.3 (“t”, br,
P (dppm)), 29.9 (“q”, br, PPh2), -21.1 (d, 1J(31P, 103Rh) =
97.3 Hz, [Rh(dppm-κ2P,P0)2]þ), 18.3 (d, 1J(31P, þ103Rh) =
104.8 Hz, [Rh2(μ-Cl)(μ-CO)(dppm-1κP:2κP0)2(CO)2] ).
€
€
Crystal Structures; University of Gottingen: Gottingen, 1997.
(75) Frisch, M. J.; et al. Gaussian 03, revision B.04; Gaussian, Inc.:
Pittsburgh, PA, 2004.
(76) (a) Becke, A. D. Phys. Rev. A 1988, 38, 3098. (b) Becke, A. D.
J. Chem. Phys. 1993, 98, 5648. (c) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev.
B 1988, 37, 785. (d) Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch,
M. J. J. Phys. Chem. 1994, 98, 11623.
Ph/dppe (19b). HRMS (ESI): m/z calcd for [C47H45P3RhS]þ
837.1504, found for [M - CO]þ 837.1513. IR: ν=1988 (CO),
2022 (CO) cm-1 13C NMR (100 MHz, CD2Cl2): δ 190.1 (CO).
.

6762 Organometallics, Vol. 29, No. 24, 2010
Block et al.
in combination with consideration of relativistic effects has
been used.77 For complexes 13acalc and 17calc the SDD basis set
as implemented in Gaussian 03 was used. All systems were fully
optimized without any symmetry restrictions. The resulting
geometries were characterized as equilibrium structures by the
analysis of the force constants of normal vibrations. Solvent
effects were considered according to the polarized continuum
model as implemented in Gaussian 03.57
Supporting Information Available: Synthesis and NMR spec-
troscopic data of starting materials, molecular structures, ener-
gies, and Cartesian coordinates of calculated molecules and
X-ray crystallographic files (CIF) are available free of charge via
the Internet at http://pubs.acs.org.
(77) (a) Weigend, F.; Ahlrichs, R. Phys. Chem. Chem. Phys. 2005, 7,
€
3297. (b) Andrae, D.; Haussermann, U.; Dolg, M.; Stoll, H.; Preuss, H.
Theor. Chim. Acta 1990, 77, 123.