Mononuclear half-sandwich rhodium complexes containing phenylchalcogenolato ligands: A multinuclear (1H, 13C, 31P, 77Se, 103Rh, 125Te) magnetic resonance study

Article abstract of DOI:10.1016/S0022-328X(99)00216-8

Diphenyl dichalcogenides react with CpRh(PMe₃)(CO) (1) to give the cyclopentadienyl complexes CpRh(PMe₃)(EPh)₂ (E=S (2a), Se (2b) and Te (2c)) and carbon monoxide. The analogous pentamethylcyclopentadienyl complexes Cp*Rh(PMe₃)(EPh)₂ (E=S (4a), Se (4b) and Te (4c)) were prepared from Cp*Rh(PMe₃)Cl₂ (3) and the chalcogenolates, NaSPh or LiEPh (E=Se, Te). With 1,2-benzenedithiol in the presence of triethylamine, CpRh(PMe₃)(S₂C₆H₄), (6a) and Cp*Rh(PMe₃)(S₂C₆H₄) (7a) could be obtained starting from either CpRh(PMe₃)I₂ (5) or Cp*Rh(PMe₃)Cl₂ (3), respectively. The molecular geometry of Cp*Rh(PMe₃)(SePh)₂ (4b) was determined by a single crystal structure analysis which confirmed a distorted tetrahedral arrangement of the ligands. All compounds were characterised by ¹H-, ¹³C-, ³¹P-, ¹⁰³Rh- and, where possible, by ⁷⁷Se- or ¹²⁵Te-NMR spectroscopy. A negative sign of ¹J(¹⁰³Rh,¹³C_Cp) (reduced coupling constant ¹K(¹⁰³Rh,¹³C_Cp)>0) was determined by selective ¹³C{¹H,³¹P} triple resonance experiments for 2a and 4a-4c.

Full text of DOI:10.1016/S0022-328X(99)00216-8

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 585 (1999) 234–240
Mononuclear half-sandwich rhodium complexes containing
13
31
77
phenylchalcogenolato ligands: a multinuclear (1H, C, P, Se,
103Rh, Te) magnetic resonance studyꢀ
125
Max Herberhold 1, Thomas Daniel, Daniela Daschner, Wolfgang Milius,
Bernd Wrackmeyer *
Laboratorium fu¨r Anorganische Chemie der Uni6ersita¨t Bayreuth, Uni6ersita¨tstraße 30, D-95440 Bayreuth, Germany
Received 29 January 1999; received in revised form 28 February 1999
Abstract
Diphenyl dichalcogenides react with CpRh(PMe3)(CO) (1) to give the cyclopentadienyl complexes CpRh(PMe3)(EPh)2 (E=S
(2a), Se (2b) and Te (2c)) and carbon monoxide. The analogous pentamethylcyclopentadienyl complexes Cp*Rh(PMe3)(EPh)2
(E=S (4a), Se (4b) and Te (4c)) were prepared from Cp*Rh(PMe3)Cl2 (3) and the chalcogenolates, NaSPh or LiEPh (E=Se, Te).
With 1,2-benzenedithiol in the presence of triethylamine, CpRh(PMe3)(S2C6H4), (6a) and Cp*Rh(PMe3)(S2C6H4) (7a) could be
obtained starting from either CpRh(PMe3)I2 (5) or Cp*Rh(PMe3)Cl2 (3), respectively. The molecular geometry of
Cp*Rh(PMe3)(SePh)2 (4b) was determined by a single crystal structure analysis which confirmed a distorted tetrahedral
arrangement of the ligands. All compounds were characterised by 1H-, 13C-, 31P-, 103Rh- and, where possible, by 77Se- or
1
1
125Te-NMR spectroscopy. A negative sign of J(103Rh,13CCp) (reduced coupling constant K(103Rh,13CCp)\0) was determined by
selective 13C{1H,31P} triple resonance experiments for 2a and 4a–4c. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Rhodium; Chalcogens; Half-sandwich complexes; Phenylchalcogenolates; X-ray; NMR
thiolato ligands, CpIr(L)(SR)2 and Cp*Ir(L)(SR)2 [3,4],
most of the cyclopentadienyl rhodium thiolato com-
1. Introduction
plexes (CpRh and Cp*Rh) possess dinuclear structures
Although numerous organothiolato complexes of the
[5,6]. However, the synthesis of mononuclear
transition metals have been reported [1], only a limited
Cp*Rh(L)(SRF)2 (L=CO, PPh3; RF=C6F5, C6F4H-p)
number of selenolato and tellurolato analogues are
available [2]. The systematic classification of the
chalcogenolato complexes is further complicated by the
fact that even metals in the same group of the periodic
starting from the coordinatively unsaturated educts
Cp*Rh(SRF)2 has also been described [7].
In the case of the half-sandwich rhodium complexes,
103Rh-NMR spectroscopy can be applied as an addi-
table do not necessarily tend to form analogous com-
tional tool for structural studies in solution, especially
pounds. Thus, in contrast to the mononuclear half-
in combination with 77Se- and 125Te-NMR [8]. This
sandwich cyclopentadienyl iridium compounds with
paper describes the synthesis of mononuclear
phenylchalcogenolato rhodium(III) complexes of the
general
composition
CpRh(PMe3)(EPh)2
and
ꢀ Dedicated to Professor Alfred Schmidpeter, Munich, on the
occasion of his 70th birthday.
* Corresponding author. Tel.: +49-921-552542; fax: +49-921-
552157.
Cp*Rh(PMe3)(EPh)2 (E=S, Se, Te), and of two 1,2-
benzenedithiolato compounds, CpRh(PMe3)(S2C6H4)
and Cp*Rh(PMe3)(S2C6H4). The new complexes were
characterised by H-, 13C-, 31P-, 77Se-, 103Rh- and 125Te-
1
E-mail address: b.rack@uni-bayreuth.de (B. Wrackmeyer)
1 Also corresponding author.
NMR spectroscopy.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00216-8

M. Herberhold et al. / Journal of Organometallic Chemistry 585 (1999) 234–240
235
2. Results and discussion
2.1. Syntheses
When CpRh(PMe3)(CO) (1) and diphenyl disulphide
(1:1) are kept in boiling toluene for 10 h, the complex
CpRh(PMe3)(SPh)2 (2a) can be isolated in good yield. The
analogous complexes CpRh(PMe3)(SePh)2 (2b) and
CpRh(PMe3)(TePh)2 (2c) are obtained similarly when the
solution is stirred for one or two days at room temperature
(r.t.) (Scheme 1). The yields of 2a–c after recrystallization
are in the range 80–90%.
The electron impact (EI) mass spectrum of the green
bis(phenyltellurolato)complex2ccontainsonlythemolec-
ular ion and its fragments, whereas the red compounds
2aand2bshowadditionalspeciesinthehighermassregion.
The presence of the binuclear ions [CpRh(EPh)]2+ (E=S,
Se) indicates easy dimerisation which appears to become
less favoured in the order S\Se\Te. [CpRh(SPh)]2 has
been described by Connelly [6].
Although the Cp*Rh(PMe3)(EPh)2 (E=S (4a), Se (4b),
Te (4c)) can be prepared in a similar way starting from
Cp*Rh(PMe3)CO under CO elimination and formal
oxidation of rhodium(I) to rhodium(III), the Cp*Rh
complexes 4a–c were more conveniently prepared by
substitutionofchloroligandsintherhodium(III)complex
Cp*Rh(PMe3)Cl2 (3)accordingtoScheme2.Ifathree-fold
excess of NaSPh is added to a suspension of the dichloro
complex Cp*Rh(PMe3)Cl2 (3) in MeOH solution, a dark
red precipitate is formed. After extraction and recrystal-
lization, the dithiolato compound Cp*Rh(PMe3)(SPh)2
(4a) is isolated as a red solid in about 80% yield.
The red–violet phenylselenolato complex Cp*Rh-
(PMe3)(SePh)2 (4b) and the green phenyltellurolato com-
pound Cp*Rh(PMe3)(TePh)2 (4c) were prepared in THF
solution, starting from 3 and LiEPh, which had been
generatedinsitufroma1:2mixtureofE2Ph2andLi[BHEt3].
The EI mass spectra of all three Cp*Rh compounds 4a–c
contain the molecular ion. In the higher mass region the
selenium complex 4b again shows the binuclear ion
[Cp*Rh(SePh)]2+, while in the case of 4a, in addition to
[Cp*Rh(SPh)]2+, the triply bridged species [Cp*Rh-
(SPh)3RhCp*]+ is also observed. Salts of this cation can
be prepared either from [Cp*RhCl2]2 and NaSPh or from
Cp*Rh(CO)2 and S2Ph2.
Scheme 1.
The complex Cp*Rh(S2C6H4) without the PMe3 ligand
is known to exist in solution in a monomer–dimer
equilibrium, whereas only the dimeric form is found to
be present in the solid state [9].
2.2. Molecular structure of Cp*Rh(PMe3)(SePh)2 (4b)
Fig. 1 presents the molecular geometry of 4b; selected
bond distances and angles are given in Table 1. The
arrangement of the ligands around the metal corresponds
to a distorted tetrahedron with the Cp* ring occupying
one coordination site.
Most of the bond lengths observed for 4b are in good
agreementwiththoseofCp*Rh(PMe3)[(SC5H4)2Fe]which
containsachelating1,1%-ferrocenedichalcogenolateligand
[10]. However, the pentamethylcyclopenta2dienyl ligand
in 4b is more symmetrically attached to the
rhodium atom. The distances between the metal centre
and the selenium atoms are consistent with those found
in the cation [Cp*Rh(SePh)3RhCp*]+ (Rh−Se=248–
252 pm), while the bond lengths Se–C in 4b (191 pm) are
slightly shorter (by 3 pm) [11]. The angles Se(1)–Rh–P
(90.7(1)°) and Se(2)–Rh–P (83.8(1)°) are remarkably
different due to the different orientation of the selenolato
ligands in the molecule. The distance between the two
selenium atoms (359.5 pm) indicates that direct bonding
interactionsareabsent,andthehalf-sandwichcompounds
As expected, the chelate ligand 1,2-benzenedithiolate
leads to even more stable mononuclear complexes. The
diiodo complex CpRh(PMe3)I2 (5), easily accessible from
the reaction of CpRh(PMe3)(CO) (1) with iodine, was
reacted with 1,2-benzenedithiol in the presence of triethyl-
amine. After column chromatography, CpRh(PMe3)-
(S2C6H4) (6a) can be isolated as an orange–brown solid
(Scheme3).Undersimilarconditions,thedichlorocomplex
Cp*Rh(PMe3)Cl2 (3) leads to the analogue, Cp*Rh-
(PMe3)(S2C6H4) (7a) in almost quantitative yield.
Scheme 2.

236
M. Herberhold et al. / Journal of Organometallic Chemistry 585 (1999) 234–240
Table 1
Bond lengths (pm) and bond angles (°) in Cp*Rh(PMe3)(SePh)2 (4b),
with estimated S.D. values
Bond lengths
Rh–Se(1)
Rh–Se(2)
Rh–P
Rh–C(1)
Rh–C(2)
249.9(1)
Rh–C(3)
Rh–C(4)
Rh–C(5)
Se(1)–C(11)
Se(2)–C(17)
223.5(6)
224.1(7)
220.7(6)
191.4(6)
191.6(7)
249.1(1)
227.7(2)
224.9(6)
224.7(6)
Scheme 3.
Bond angles
Se(1)–Rh–Se(2)
Se(1)–Rh–P
Se(2)–Rh–P
92.2(1)
83.8(1)
90.7(1)
Rh–Se(1)–C(11)
Rh–Se(2)–C(17)
111.0(2)
114.8(2)
Cp*Rh(PMe3)(EPh)2 are therefore best described as
rhodium(III) complexes.
2.3. NMR spectroscopic characterisation
The 31P-, 103Rh-, 77Se-, and 125Te-NMR data of the
phenylchalcogenolato complexes 2a–c and 4a–c and of
the 1,2-dithiolato complexes 6a and 7a are collected in
Table 2; the 1H- and 13C-NMR data are given in
Section 3. All NMR spectra are in complete agreement
with the proposed structures.
coupling constants 1J(77Se,13C)=123.5 (4b) and
1J(125Te,13C)=353.0 Hz (4c) is in the expected range
[13]. There are hardly any data in the literature for
comparison of the magnitude of the coupling constants
between 13C and either 77Se or 125Te across more than
1
one bond. In the case of 4b, J(13C,13C) data of the
There is little variation in the 1H- and 13C-NMR data
of the cyclopentadienyl ring and of the PMe3 ligand.
The phenylchalcogenolato ligands show the usual pat-
SePh group could be obtained [1J(13Cipso,13Cortho)=
58.0, 1J(13Cortho,13Cmeta)=54.8, 1J(13Cmeta,13Cpara)=
55.7 Hz] which are very similar to known values
1J(13C,13C) for PhSeMe [1J(13Cipso,13Cortho)=58.3,
1J(13Cmeta,13Cpara)=56.3 Hz] [14]. This supports the
evidence from l13C data that the terminal Rh–Se bond
has no particular influence on the bonding situation in
the phenyl ring.
1
tern in the H- and 13C-NMR spectra. The different
chalcogens take only a small influence on l1H and
l13C(o, m, p) of the phenyl group, whereas the influ-
ence on l13C(i ) is larger, with the typical order [12] of
increasing 13C nuclear shielding in the series SBSeB
Te. This ‘heavy-atom effect’ has been observed for
similar compounds [10]. In some cases it proved possi-
ble to record 13C-NMR spectra with signal-to-noise
(S/N) ratio and high resolution sufficient to detect 77Se
or 125Te satellites (e.g. 4b and 4c). The magnitude of the
The complexes 2a and 4a–4c were studied by a series
of heteronuclear triple resonance experiments of the
type 13C{1H,31P} with selective irradiation of 31P transi-
tions in order to determine the signs of coupling con-
stants J(103Rh,13C) to the cyclopentadienyl 13C, the
phenyl 13C(i ) and the trimethylphosphane 13C nuclei
(see Fig. 2 for an example). The 13C and 31P nuclei are
the active spins, and the 103Rh nucleus is the passive
spin in all of these experiments, allowing for the com-
parison of relative signs of coupling constants [15]
J(103Rh,13C) and 1J(103Rh,31P). Since the sign of
1J(103Rh,31P) is known to be negative [16], (k(103Rh)B
1
0; the reduced coupling constant K(103Rh,31P) is posi-
tive), the absolute sign of the coupling constants
J(103Rh,13C) for these bonding situations becomes
available for the first time. In all four cases [Cp, Cp*,
C(i ) and Me3P], the sign of J(103Rh,13C) is negative
(K(103Rh,13C)\0).
There is a significant increase in the shielding of 31P
nuclei by 10.6 ppm in the series 2a–2c, which is less
pronounced (4 ppm) in the series 4a–4c. In both series,
1
the magnitude of J(103Rh,31P) increases slightly (by 4.5
and 5.4 Hz) on going from E=S to E=Te.
Both 77Se and 125Te nuclear shielding are reduced (by
about 150 and 260 ppm, respectively) when the Cp ring
is replaced by the Cp* ring. Considering the huge range
of l77Se and l125Te values and the roughly linear
Fig. 1. Molecular structure of Cp*Rh(PMe3)(SePh)2 (4b) (The hydro-
gen atoms are omitted for clarity). See Table 1 for selected distances
and bond angles.

M. Herberhold et al. / Journal of Organometallic Chemistry 585 (1999) 234–240
237
Table 2
31P-, 77Se-, 125Te- and 103Rh-NMR data a
Complex
l
31P b
l
103Rh
l
77Se c/l 125Te d
2a
2b
2c
4a
4b
4c
6a
7a
CpRh(PMe3)(SPh)2
CpRh(PMe3)(SePh)2
CpRh(PMe3)(TePh)2
Cp*Rh(PMe3)(SPh)2
Cp*Rh(PMe3)(SePh)2
Cp*Rh(PMe3)(TePh)2
CpRh(PMe3)(S2C6H4)
Cp*Rh(PMe3)(S2C6H4)
13.9 (141.7)
8.9 (143.1/17.0)
3.3 (146.2/42.0)
1.6 (144.1)
0.4 (148.5/18.3)
−2.4 (150.5/43.9)
17.9 (141.6)
388.290.2
106.590.5
−15.0 [56] (17.0)
−71.6 {110} (42.0)
−553.091
461.390.2
201.590.3
−384.090.5
52.091
134.1 [53] (18.3)
188.5 {112} (43.9)
10.8 (150.4)
−11.090.5
a All NMR spectra were measured in CDCl3 solution at r.t.
b Coupling constants (91 Hz) 1J(103Rh31P)/2J(77Se31P) and 1J(103Rh31P)/2J(125Te31P) are given in parentheses.
c Coupling constants (93 Hz) 1J(103Rh77Se) are given in square brackets.
d Coupling constants (93 Hz) 1J(125Te103Rh) are given in curly brackets.
relationship between l77Se and l125Te [13], the data are
in the expected range for terminal phenylchalcogeno-
lato ligands (see Ref. [11] for l77Se of bridging and
terminal PhSe groups linked to rhodium). The values of
the coupling constants 1J(103Rh,77Se) are similar to
known data [11], and the data 1J(125Te,103Rh) appear to
fit into the pattern known so far [13]. Examples for
The chelating benzenedithiolato ligand exerts a large
shielding effect on the 103Rh nucleus, and the influence
of the Cp versus the Cp* ring ligand is inverted in the
metallacyclic compounds. A more thorough discussion
must be based on direct structural evidence. However,
the l103Rh data of 6a and 7a indicate substantial
changes in the electronic structure of the metallacycles
when compared with analogous non-cyclic derivatives.
The ring size of the metallacycles, as well as the annel-
ation of the aromatic system may have a marked
2
2J(77Se,31P) and J(125Te,31P) across a metal centre in
such complexes are rare and cannot be discussed at
present.
The 77Se- and more so, the 125Te-NMR signals are
influence,
since
the
metallacyclic
complex
broad (e.g. 4c: h1/2
(
125Te)=260910 Hz). This broad-
Cp*Rh(PMe3)(S2fc) (fc=1,1%-ferrocenediyl), for which
the molecular structure in the solid state is known [10],
gives a 103Rh-NMR signal at l=36891, rather close
to that of 4a (l103Rh=461.390.2).
ening of the resonance signals can be traced to efficient
nuclear spin relaxation by chemical shift anisotropy
(CSA). That means that 77Se and 125Te satellites, e.g. in
31P-NMR spectra, must also be broadened. In the case
of 4c, the line width of the 125Te satellites in the 202.5
MHz 31P-NMR spectra was found to be 790.5 Hz,
which is in good agreement with a calculated line width
of 7.5 Hz [assuming that the broadening in both 125Te-
and 31P-NMR spectra arise from the same origin
(CSA)]. With high-field NMR spectrometers, the fairly
short relaxation times, T1(77Se) (ca. 10–30 ms) and
T1(125Te) (ca. 1–3 ms), for the type of compounds
studied offer distinct advantages with respect to instru-
ment time, in particular if diluted solutions are studied.
However, in the case of 125Te-NMR, the pronounced
broadening of the 125Te-NMR signals may compensate
most of the advantage in S/N gained by the short
repetition time of consecutive 90° pulses.
The ‘heavy-atom effect’, already mentioned for
l13C(i ), is also evident, but to a much larger extent, for
103Rh nuclear shielding when sulphur is replaced by
selenium and tellurium in the phenylchalcogenolato
complexes (e.g. 103Rh nuclear shielding increases by
more than 920 ppm from 2a to 2c and by 745 ppm
from 4a to 4c). Interestingly, the l103Rh values change
dramatically (from 388.2 to 52.0 and from 461.3 to
−11.0) if the two phenylthiolato groups in 2a or 4a are
replaced by the benzenedithiolato group in 6a and 7a.
Fig. 2. Heteronuclear triple resonance experiments (125.8 MHz)
13C{1H,31P} with selective irradiation of 31P transitions in the case of
Cp*Rh(PMe3)SPh2 (4a); shown is the region of the quaternary
13C(Cp*) resonance (dd, 1J(103Rh,13C)=4.9, 2J(31P,13C)=3.3 Hz).
(a) Irradiation of the low frequency part of the 31P resonance of the
31P–103Rh–13C isotopomer, showing the effect on the low-frequency
doublet, and (b) the analogous effect on the high-frequency doublet
by selective irradiation of the respective high-frequency 31P transi-
tions. This proves that the signs of 1J(103Rh,13CCp*
1J(103Rh,31P) are alike.
)
and

238
M. Herberhold et al. / Journal of Organometallic Chemistry 585 (1999) 234–240
3. Experimental
and the mixture was stirred for one day at r.t. A
dark red solution was formed which was taken to
dryness under vacuum. The residue was recrystallized
from toluene:pentane to give an orange–red solid
(153 mg (89%), m.p. (dec.) 109°C). EI MS: m/e
(relative intensity %): 650 (4, [CpRh(SePh)]2+), 558
(8, CpRh(PMe3)(SePh)2+), 401 (100, CpRh(PMe3)-
(SePh)+), 325 (98, CpRh(SePh)+), 244 (11,
3.1. General and physical methods
All reactions were carried out under an atmosphere
of argon and in carefully dried solvents. The starting
materials CpRh(PMe3)(CO) (1) [17], Cp*Rh(PMe3)Cl2
(3) [18] and CpRh(PMe3)I2 (5) [19] were prepared ac-
cording to published methods.
1
CpRh(PMe3)+). H-NMR (CDCl3, 250 MHz): 7.64 (d,
NMR: Jeol FX 90 Q, Bruker ARX 250, Jeol EX 270,
Bruker AC 300 (l1H (CHCl3/CDCl3)=7.24;
l13C(CDCl3)=77.0; l31P=0 for external H3PO4, 85%
aq.), and Bruker DRX 500 [77Se-NMR (l77Se=0 for
Me2Se with ](77Se)=19.071523 MHz); 125Te-NMR
(l125Te=0 for Me2Te with ](125Te)=31.549802
MHz). Triple resonance experiments 31P{1H,103Rh} for
the determination of l103Rh (with respect to
](103Rh)=3.16 MHz), 13C{1H,31P} for determination
of coupling signs]. The power for irradiation of 31P
transitions was carefully selected (B55 db) in order to
achieve the desired differential effects, in particular for
the 13C(PMe3) and 13C(i )-signals where the effect of
spin tickling [20] had to be observed since ꢀJ(31P,13C)ꢀꢀ
ꢀJ(103Rh,13C)ꢀ. EI MS: Varian Mat CH7; the m/e data
refer to the isotopes 32S, 80Se and 128Te; the experimen-
tal isotope patterns correspond to the natural distribu-
tion of the chalcogen isotopes. Decomposition points
were determined using a Bu¨chi 510 melting point
apparatus.
J(HH)=7.2 Hz, 4H, H(2)/H(6)), 7.05 (m, 6H, H(3)/
H(4)/H(5)), 5.22 (d, J(PH)=1.7 Hz, 5H, C5H5), 1.61
(d, J(PH)=11.0 Hz, 9H, PMe3). 13C-NMR (CDCl3,
62.9 MHz): 135.9 (C(1)), 135.4 (C(2)/C(6)), 127.9 (s,
C(3)/C(5)), 124.8 (C(4)), 91.0 (dd, J(RhC)=3.7 Hz,
J(PC)=3.7 Hz, C5H5), 19.7 (d, J(PC)=36.1 Hz,
PMe3).
3.4. CpRh(PMe3)(TePh)2 (2c)
A solution of 1 (117 mg, 0.43 mmol) in 20 ml of
toluene was treated with Te2Ph2 (176 mg, 0.43 mmol)
and the mixture was stirred for two days at r.t. The
solvent was removed from the resulting green solution
under vacuum, 20 ml of THF were added to the residue
and the suspension filtered through cellulose. The
filtrate was concentrated to about 5 ml in vacuum, 40
ml of pentane was added and the solution cooled to
−30°C. After several hours a green microcrystalline
solid precipitated which was removed by filtration
and dried under high vacuum (223 mg (79%), m.p.
(dec.) 121°C). EI MS: m/e (relative intensity %): 654
(25, CpRh(PMe3)(TePh)2+), 449 (100, CpRh(PMe3)-
(TePh)+), 373 (91, CpRh(TePh)+), 244 (90,
CpRh(PMe3)+). 1H-NMR (CDCl3, 250 MHz): 7.79
(dd, J(HH)=8.0 Hz, 4H, H(2)/H(6)), 7.14 (dd,
J(HH)=8.0 and 7.0 Hz, 4H, H(3)/H(5)), 6.99 (t,
J(HH)=7.0 Hz, 2H, H(4)), 5.23 (d, J(PH)=1.7 Hz,
5H, C5H5), 1.70 (dd, J(RhH)=0.7 Hz, J(PH)=10.4
Hz, 9H, PMe3). 13C-NMR (CDCl3, 62.9 MHz): 140.3
(C(2)/C(6)), 128.1 (C(3)/C(5)), 126.2 (C(4)), 110.5
(C(1)), 90.6 (dd, J(RhC)=3.7 Hz, J(PC)=3.7 Hz,
C5H5), 22.9 (d, J(PC)=36.7 Hz, PMe3).
3.2. CpRh(PMe3)(SPh)2 (2a)
A solution of 1 (110 mg, 0.40 mmol) in 20 ml of
toluene was treated with S2Ph2 (88 mg, 0.40 mmol) and
the mixture was heated at 110°C (reflux) for 10 h. The
dark red solution was evaporated, the red residue
washed with 20 ml of pentane and recrystallized from
toluene:pentane to give a red solid (192 mg (87%), m.p.
(dec.) 135°C). EI MS: m/e (relative intensity %): 554 (6,
[CpRh(SPh)]2+), 462 (7, CpRh(PMe3)(SPh)2+), 353 (80,
CpRh(PMe3)(SPh)+), 277 (100, CpRh(SPh)+), 244 (13,
1
CpRh(PMe3)+). H-NMR (CDCl3, 250 MHz): 7.50 (d,
J(HH)=7.2 Hz, 4H, H(2)/H(6)), 7.05 (dd, J(HH)=7.2
and 7.0 Hz, 4H, H(3)/H(5)), 6.95 (t, J(HH)=7.0 Hz,
2H, H(4)), 5.29 (d, J(PH)=1.3 Hz, 5H, C5H5), 1.54 (d,
J(PH)=11.3 Hz, 9H, PMe3). 13C-NMR (CDCl3, 126
MHz): 145.8 (dd, J(RhC)=3.7 Hz, J(PC)=0.9 Hz,
C(1)), 133.0 (d, J(RhC)=0.9 Hz, C(2)/C(6)), 127.7
(C(3)/C(5)), 123.4 (C(4)), 91.7 (dd, J(RhC)=4.1 Hz,
J(PC)=3.4 Hz, C5H5), 18.2 (dd, J(RhC)=0.7 Hz,
J(PC)=35.8 Hz, PMe3).
3.5. Cp*Rh(PMe3)(SPh)2 (4a)
A suspension of 3 (300 mg, 0.78 mmol) in 30 ml of
MeOH was treated with NaSPh (305 mg, 2.31 mmol)
and the mixture was stirred for 3 h at r.t. A dark red
suspension was formed which was taken to dryness
under vacuum. The residue was extracted three times
with 10 ml of CH2Cl2:pentane (1:1), and the combined
extracts were reduced in volume to ca. 10 ml. Then 50
ml of pentane was added and the solution cooled to
−78°C. After several hours a red microcrystalline solid
precipitated. The supernatant was decanted, the precip-
itate washed twice with portions (10 ml) of cold pen-
3.3. CpRh(PMe3)(SePh)2 (2b)
A solution of 1 (83 mg, 0.31 mmol) in 20 ml of
toluene was treated with Se2Ph2 (96 mg, 0.31 mmol)

M. Herberhold et al. / Journal of Organometallic Chemistry 585 (1999) 234–240
239
tane and dried under high vacuum to give a red mi-
3.7. Cp*Rh(PMe3)(TePh)2 (4c)
crocrystalline powder (326 mg (79%), m.p. (dec.)
131°C). EI MS: m/e (relative intensity %): 803 (1,
[Cp*Rh]2(SPh)3+), 694 (2, [Cp*Rh(SPh)]2+), 532 (1,
Cp*Rh(PMe3)(SPh)2+), 456 (2, Cp*Rh(SPh)2+), 423
(6, Cp*Rh(PMe3)(SPh)+), 347 (28, Cp*Rh(SPh)+),
314 (1, Cp*Rh(PMe3)+), 238 (9, Cp*Rh+), 76 (74,
PMe3+), 61 (100, PMe2+). 1H-NMR (CDCl3, 270
MHz): 7.37 (d, J(HH)=7.9 Hz, 4H, H(2)/H(6)), 6.96
(dd, J(HH)=7.9 and 7.3 Hz, 4H, H(3)/H(5)), 6.87 (t,
J(HH)=7.3 Hz, 2H, H(4)), 1.66 (d, J(PH)=3.1 Hz,
15H, C5Me5), 1.45 (d, J(PH)=10.4 Hz, 9H, PMe3).
13C-NMR (CDCl3, 126 MHz): 144.2 (dd, J(RhC)=
0.8 Hz, J(PC)=4.4 Hz, C(1)), 133.1 (d, J(PC)=0.8
Hz, C(2)/C(6)), 127.1 (C(3)/C(5)), 122.47 (C(4)), 100.0
(dd, J(RhC)=4.9 Hz, J(PC)=3.3 Hz, C5Me5), 15.3
(dd, J(RhC)=0.5 Hz, J(PC)=33.5 Hz, PMe3), 9.5
(d, J(PC)=1.4 Hz, C5Me5).
A solution of Te2Ph2 (279 mg, 0.68 mmol) in 10 ml
of THF was slowly treated with 1.4 ml of a 1 M
solution of Li[BHEt3] in THF, and the mixture was
stirred for 15 min at r.t. The dark red solution thus
formed was added to a suspension of 3 (219 mg, 0.57
mmol) in 10 ml of THF. After 3 h stirring at r.t. the
solvent was removed from the resulting dark green
solution under vacuum and the residue chro-
matographed on Al2O3V. With pentane an orange–
yellow band of Te2Ph2 was eluated. Subsequent
eluation with toluene gave a green zone that was
taken to dryness under vacuum. The oily residue was
stirred in 10 ml of pentane for 30 min at r.t. and
then cooled to −78°C. After several hours the super-
natant liquid was decanted and the green microcrys-
talline solid dried under high vacuum (250 mg (61%),
m.p. (dec.) 103°C).). EI MS: m/e (relative intensity
%): 724 (7, Cp*Rh(PMe3)(TePh)2+), 519 (21,
Cp*Rh(PMe3)(TePh)+), 443 (47, Cp*Rh(TePh)+),
366 (15, Cp*RhTe+), 314 (12, Cp*Rh(PMe3)+), 238
(20, Cp*Rh+), 154 (100, Ph2+). 1H-NMR (CDCl3,
500 MHz): 7.76 (d, J(HH)=7.9 Hz, 4H, H(2)/H(6)),
7.15 (t, J(HH)=6.9 Hz, 2H, H(4)), 6.97 (dd, J(H)=
7.9 and 6.9 Hz, 4H, H(3)/H(5)), 1.89 (d, J(PH)=2.9
Hz, 15H, C5Me5), 1.70 (d, J(PH)=9.8 Hz, PMe3).
13C-NMR (CDCl3, 75.0 MHz): 141.2 (C(2)/C(6)),
127.5 (C(3)/C(5)), 125.8 (C(4)), 107.9 (dd, J(TeC)=
353 Hz, J(RhC)=0.5 Hz, J(PC)=3.5 Hz, C(1)), 99.6
(dd, J(RhC)=4.4 Hz, J(PC)=3.3 Hz, C5Me5), 20.9
(dd, J(TeC)=8 Hz, J(RhC)=0.5 Hz, J(PC)=35.4
Hz, PMe3), 10.8 (d, J(PC)=0.9 Hz, C5Me5).
3.6. Cp*Rh(PMe3)(SePh)2 (4b)
A solution of Se2Ph2 (233 mg, 0.75 mmol) in 10 ml
of THF was slowly treated with 1.5 ml of a 1 M
solution of Li[BHEt3] in THF and the mixture was
stirred for 15 min at r.t. A pale yellow solution was
formed which was added to a suspension of 3 (220
mg, 0.57 mmol) in 10 ml of THF. After 3 h stirring
at r.t. the solvent from the resulting dark red solution
was removed under vacuum, and then the residue
filtered through cellulose using 20 ml of
CH2Cl2:pentane (1:10). The filtrate was concentrated
to about 5 ml in volume, 30 ml of pentane was
added and the solution cooled to −30°C. After sev-
eral hours a red–violet crystalline solid started to pre-
cipitate. The supernatant solution was decanted and
the precipitate dried under high vacuum to produce
red–violet crystals (273 mg (76%), m.p. (dec.) 119°C).
EI MS: m/e (relative intensity %): 790 (1,
[Cp*Rh(SePh)]2+), 628 (2, Cp*Rh(PMe3)(SePh)2+), 552
(3, Cp*Rh(SePh)2+), 471 (18, Cp*Rh(PMe3)(SePh)+),
3.8. CpRh(PMe3)(S2C6H4) (6a)
A solution of 5 (115 mg, 0.23 mmol) in 30 ml of
THF was treated with 1,2-benzenedithiol (41 ml, 0.23
mmol) and triethylamine (65 ml, 0.47 mmol), and the
mixture was stirred for 18 h at r.t. The solvent from
the resulting dark red solution was removed under
vacuum and the residue chromatographed on Al2O3V.
Eluation with toluene gave an orange–brown band
that was taken to dryness under vacuum to give a
red–brown solid (47 mg (53%), m.p. (dec.) 207°C). EI
MS: m/e (relative intensity %): 384 (25,
CpRh(PMe3)(S2C6H4)+), 308 (100, CpRh(S2C6H4)+),
552
(3,
Cp*Rh(SePh)2+),
471
(18,
Cp*Rh-
(PMe3)(SePh)+), 395 (100, Cp*Rh(SePh)+), 314
(5, Cp*Rh(PMe3)+), 76 (47, PMe3+), 61 (64, PMe2+).
1H-NMR (CDCl3, 500 MHz): 7.57 (d, J(HH)=7.9
Hz, 4H, H(2)/H(6)), 7.01 (m, 6H, H(3)/H(4)/H(5)),
1.76 (d, J(PH)=3.2 Hz, 15H, C5Me5), 1.58 (d,
J(PH)=10.3 Hz, 9H, PMe3). 13C-NMR (CDCl3, 126
MHz): 135.6 (J(SeC)=7.8 Hz, J(C(1)C(2))=58.0 Hz,
J(C(2)C(3))=54.8 Hz, C(2)/C(6)), 133.8 (dd,
J(RhC)=0.7 Hz, J(SeC)=123.5 Hz, J(PC)=3.9 Hz,
J(C(1)C(2))=58.0 Hz, C(1)), 127.3 (J(C(3)C(4))=
55.7 Hz, C(3)/C(5)), 124.10 (J(C(3)C(4))=55.7 Hz,
C(4)), 99.4 (dd, J(RhC)=5.2 Hz, J(SeC)=2.9 Hz,
J(PC)=3.2 Hz, C5Me5), 17.2 (dd, J(RhC)=1.0 Hz,
J(SeC)=3.2 Hz, J(PC)=34.3 Hz, PMe3), 9.8 (d,
J(PC)=1.3 Hz, C5Me5).
1
168 (14, CpRh+). H-NMR (CDCl3, 250 MHz): 7.12
(m, 2H, H(3)/H(6)), 6.61 (m, 2H, H(4)/H(5)), 5.39 (d,
J(PH)=2.2 Hz, 5H, C5H5), 1.53 (d, J(PH)=11.2 Hz,
9H, PMe3). 13C-NMR (CDCl3, 62.9 MHz): 143.9
(C(1)/C(2)), 127.2 (C(3)/C(6)), 121.8 (C(4)/C(5)), 91.3
(dd, J(RhC)=4.2 Hz, J(PC)=4.2 Hz, C5H5), 17.4
(d, J(PC)=37.9 Hz, PMe3).

240
M. Herberhold et al. / Journal of Organometallic Chemistry 585 (1999) 234–240
3.9. Cp*Rh(PMe3)(S2C6H4) (7a)
Acknowledgements
A suspension of 3 (307 mg, 0.80 mmol) in 10 ml of THF
was treated with 1,2-benzenedithiol (100 ml, 0.87 mmol)
and triethylamine (250 ml, 1.81 mmol) and the mixture
was stirred for 2 h at r.t. The solvent was removed from
the resulting dark red solution under vacuum and the
residue chromatographed on a column filled with Al2O3V.
Eluation with toluene gave an orange–red band that was
taken to dryness under vacuum to give an orange–brown
solid (337 mg (93%), m.p. (dec.) 134°C). EI MS: m/e
(relative intensity %): 454 (3, Cp*Rh(PMe3)(S2C6H4)+),
378 (100, Cp*Rh(S2C6H4)+). 1H-NMR (CDCl3, 250
MHz): 7.14 (m, 2H, H(3)/H(6)), 6.59 (m, 2H, H(4)/H(5)),
1.71 (d, J(PH)=3.2 Hz, 15H, C5Me5), 1.37 (d, J(PH)=
10.7 Hz, 9H, PMe3). 13C-NMR (CDCl3, 62.9 MHz): 144.9
(C(1)/C(2)), 127.4 (C(3)/C(6)), 121.2 (C(4)/(5)), 100.2 (dd,
J(RhC)=4.3 Hz, J(PC)=4.3 Hz, C5Me5), 14.5 (d,
J(PC)=35.9 Hz, PMe3), 9.4 (d, J(PC)=1.4 Hz, C5Me5).
Support of this work by the Deutsche Forschungsge-
meinschaft and the Fonds der Chemischen Industrie is
gratefully acknowledged.
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3.10. X-ray structure analysis of Cp*Rh(PMe3)(SePh)2
(4b)
Single crystals were grown from CH2Cl2:pentane at
−78°C. Crystal: C25H34PRhSe2, dark red prism, with the
dimensions 0.30×0.20×0.15 mm. Space group P21/c
(monoclinic) with the lattice parameters a=9.991(2),
,
b=15.608(2), c=16.661(2) A and i=96.86(2)°, V=
3
2579.5(7) A , Z=4. Dcalc 1.613 g cm3, v (Mo–Ka) 35.56
,
cm−1, min./max. transmission 0.4038/0.4869. Data col-
,
lection: Siemens P4, Mo–Ka radiation (u=0.71073 A),
graphite monochromator, T=296 K. 2q Scan range
3.0–55.0°. Collected reflections 7581, of which 5853 were
independent and 4584 independent observed [Fo\
2|(Fo)]. Control by three standard per 100 reflections,
variation in standards 91%. Refinement: R 5.64, Rw
3.82% (w−1=|2(Fo)) with 263 refined parameters, max./
min. residual electron density 0.62/−1.23 e A−3. Good-
ness-of-fit 1.22.
,
4. Supplementary material
Crystallographic data (excluding structure factors)
have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no. CCDC-
114027. Copies of these data can be obtained free of
charge on application to The Director, CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336033;
e-mail: deposit@ccdc.cam.ac.uk).
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.