Synthesis and reactivity of dinuclear rhodium complexes with Rh=C=CHR and Rh=C=C=CRR′ units as building blocks

Article abstract of DOI:10.1016/S0022-328X(03)00521-7

The reaction of [Rh{κ²-O₂S(O)CF₃} (PⁱPr₃)₂] (1) with ethynylferrocene in the presence of KF affords the substituted vinylidene complex trans-[RhF{=C=CH(C₅H₄) Fe(C₅ H₅)}(PⁱPr₃)₂] (2) which upon treatment with the butadiyne derivative Ph₃SnC≡ C-C≡CSnPh₃ produces the chain-like compound trans-[(μ-C≡C-C≡C){Rh(=C=CH (C₅H₄)Fe(C₅H₅))(Pⁱ Pr₃)₂}₂] (7). The triflato complex 1 reacts with 1,4-C₆H₄(C≡CH)₂ to give the dinuclear compound trans-[{μ-1,4-C₆H₄ (CH=C=)₂}{Rh(η¹-OS(O) ₂CF₃)(PⁱPr₃)₂} ₂] (3) which in the presence of KF undergoes a ligand exchange to give the corresponding difluoro derivative 4. From 4 and RC≡ CSnPh₃ (R=CH₃, C₆H₅) the complexes 5 and 6, in which a C₆H₄ unit bridges two alkynyl(vinylidene)rhodium(I) fragments, are obtained. Both 6 and 7 react with CO by migratory insertion of the vinylidene units into the alkynyl-metal bonds to afford the dinuclear complexes 8 and 9, in which an unusual C₈ or C₄(C₆H₄) C₄ chain bridges the two rhodium centers. The reactions of [RhCl(PⁱPr₃)₂]₂ (10) with the functionalized diynes 1,1′,4,4′-C₆ H₄(OH)₂(C≡CH)₂ and 1,4-C₆H₄[C(Ph)(OH)C≡CH]₂ lead, via the corresponding diyne-metal species 11 and 12 as intermediates, to the formation of the bis(vinylidene) complexes 13 and 14, the latter of which reacts with acidic Al₂O₃ by elimination of water to give the novel phenylene-bridged bis(allenylidenerhodium) compound [{μ-1,4-C₆H₄(CPh=C= C=)₂}{RhCl(PⁱPr₃)₂} ₂] (15) in 80% yield.

Full text of DOI:10.1016/S0022-328X(03)00521-7

Journal of Organometallic Chemistry 684 (2003) 144ꢂ152
/
www.elsevier.com/locate/jorganchem
Synthesis and reactivity of dinuclear rhodium complexes with RhÄ
/
CÄ
/
CHR and RhÄCÄCÄCRR? units as building blocks
/
/
/
Berta Callejas-Gaspar, Matthias Laubender, Helmut Werner *
Institut fur Anorganische Chemie der Universitat Wurzburg, Am Hubland, D-97074 Wurzburg, Germany
¨ ¨ ¨ ¨
Received 10 February 2003; received in revised form 11 March 2003; accepted 23 April 2003
Dedicated with great admiration to Professor Ernst Otto Fischer on the occasion of his 85th birthday
Abstract
The reaction of [Rh{k2-O2S(O)CF3}(PiPr3)2] (1) with ethynylferrocene in the presence of KF affords the substituted vinylidene
complex trans-[RhF{ÄCÄ CÃCÅ
CH(C5H4)Fe(C5H5)}(Pi Pr3)2] (2) which upon treatment with the butadiyne derivative Ph3SnCÅ
CSnPh3 produces the chain-like compound trans-[(m-CÅCÃCÅC){Rh(ÄCÄ
CH(C5H4)Fe(C5H5))(Pi Pr3)2}2] (7). The triflato complex
1 reacts with 1,4-C6H4(CÅCH)2 to give the dinuclear compound trans-[{m-1,4-C6H4(CHÄCÄ
)2}{Rh(h1-OS(O)2CF3)(PiPr3)2}2] (3)
which in the presence of KF undergoes a ligand exchange to give the corresponding difluoro derivative 4. From 4 and RCÅCSnPh3
(RꢀCH3, C6H5) the complexes 5 and 6, in which a C6H4 unit bridges two alkynyl(vinylidene)rhodium(I) fragments, are obtained.
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
Both 6 and 7 react with CO by migratory insertion of the vinylidene units into the alkynyl-metal bonds to afford the dinuclear
complexes 8 and 9, in which an unusual C8 or C4(C6H4)C4 chain bridges the two rhodium centers. The reactions of [RhCl(Pi Pr3)2]2
(10) with the functionalized diynes 1,1?,4,4?-C6H4(OH)2(CÅ
/
CH)2 and 1,4-C6H4[C(Ph)(OH)CÅ/CH]2 lead, via the corresponding
diyne-metal species 11 and 12 as intermediates, to the formation of the bis(vinylidene) complexes 13 and 14, the latter of which reacts
with acidic Al2O3 by elimination of water to give the novel phenylene-bridged bis(allenylidenerhodium) compound [{m-1,4-
C6H4(CPhÄ
/
CÄ
/
CÄ
/
)2}{RhCl(Pi Pr3)2}2] (15) in 80% yield.
# 2003 Elsevier B.V. All rights reserved.
Keywords: Alkynyl complexes; Allenylidene complexes; Vinylidene complexes; Triflato complexes; Rhodium
1. Introduction
can be enhanced if the chloro ligand is replaced by
fluoride and that the triflato complex [Rh{k2-
O2S(O)CF3}(PiPr3)2] is a suitable starting material for
the synthesis of the required fluoro derivatives trans-
In the context of our studies on the conversion of
terminal
alkynes
HCÅ/CR
to
the
isomeric
CHR in the coordination sphere of
[RhF(Ä
/
CÄ
/
CHR)(PiPr3)2] [4].
vinylidenes:CÄ
/
rhodium(I) [1], we have recently shown that also 1,4-
bis(ethynyl)benzene and 1,3,5-tris(ethynyl)benzene can
be transformed, in the presence of [RhCl(PiPr3)2]2 as the
template, to the corresponding metal-bonded bis(viny-
lidenes) and tris(vinylidenes), respectively [2,3]. More-
over, we reported that the reactivity of the rhodium
We have now applied this methodology to prepare a
dinuclear fluororhodium(I) complex with a bridging
phenylene group between the two vinylidene-metal units
and used this compound for the synthesis of new chain-
like organometallic molecules. In the present paper we
further illustrate that dinuclear vinylidenerhodium com-
pounds with an extended bridge between the two
vinylidene-metal moieties are accessible and that one
of them can be transformed to the first complex in which
two allenylidenerhodium fragments are connected by a
1,4-C6H4 bridge.
vinylidenes of the type trans-[RhCl(Ä
/
CÄ
/
CHR)(PiPr3)2]
* Corresponding author. Fax: ꢁ
E-mail address: helmut.werner@mail.uni-wuerzburg.de (H.
Werner).
/49-931-888-4623.
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00521-7

B. Callejas-Gaspar et al. / Journal of Organometallic Chemistry 684 (2003) 144ꢂ
/152
145
2. Results and discussion
synthesis of 4 via a one-pot reaction of 1 with 1,4-
C6H4(CÅCH)2 and KF is also possible. However, we
note that attempts to prepare compound 4 by salt
/
Under rather mild conditions, the triflato compound
1 (recently prepared from [(h3-C3H5)Rh(PiPr3)2] and
CF3SO3H [5]) reacts with ethynylferrocene in acetone to
give a deeply colored intermediate which we assume is
metathesis from the dichloro counterpart trans-[{m-1,4-
C6H4(CHÄ
/
CÄ
/
)2}{RhCl(PiPr3)2}2] [2] and KF as the
precursors remained unsuccessful.
In agreement with recent studies [7], we found that the
the vinylidene complex trans-[Rh{k1-OS(O)2CF3}{Ä
/
CÄ
/
CH(C5H4)Fe(C5H5)}(PiPr3)2]. Since this species ap-
peared to be rather labile, it was treated in situ with
KF and gave, after recrystallization from pentane, the
fluoro derivative 2 in 73% isolated yield (Scheme 1). The
violet solid, which gave a correct elemental analysis, is
moderately air-sensitive and readily soluble in all
common organic solvents. Typical spectroscopic fea-
tures are the resonance at d 45.7 in the 31P-NMR
spectrum, which is split into a doublet of doublets due to
RhÃ
/
F bond of 4 is rather labile and thus upon treatment
of 4 with CH3CÅ
/
CSnPh3 and PhCÅCSnPh3 the di-
/
nuclear alkynyl(vinylidene) complexes 5 and 6 are
formed (see Scheme 1). The ligand displacement is
accompanied by a typical change of color from violet
to green and affords the products in good to excellent
yields. Both 5 and 6 are green, relatively low-melting
and air-sensitive solids, which can be stored at 0 8C
under argon for days and do not decompose in solution
(e.g. in benzene). The coordination of the alkynyl ligand
is confirmed by the appearance of two signals in the 13C-
NMR spectra at d 131.5 and 109.9 (5) and d 135.9 and
31Pꢂ19
vinylidene proton at d 1.18 in the H-NMR spectrum.
The UVꢂvis spectrum of 2 shows two maxima at l 408
/
F and 31Pꢂ103
/
Rh couplings, and the signal for the
1
/
and 553 nm which in agreement with data from the
literature are assigned to metal-to-ligand charge transfer
bands [6].
125.4 (6) for the RhÃ
as well as by the strong n(CÅ
cmꢃ1 in the IR spectrum of 6. In the UVꢂ
5 and 6, the maxima are shifted by ca. 50ꢂ
lower frequencies compared with the fluoro derivative 4,
which possibly indicates an increase in delocalization of
/
CÅ
/
C and RhÃ
C) stretching mode at 2073
vis spectra of
65 nm to
/
C Å
/
C carbon atoms
/
/
The reaction of 1 with 1,4-bis(ethynyl)benzene pro-
ceeds similarly to that with ethynylferrocene but in this
case we succeeded to isolate the bis(triflato)dirhodium
compound 3 as a dark violet solid in 85% yield.
Diagnostic for 3 are the signals in the 13C-NMR
spectrum at d 304.9 and 112.6 for the a-C and b-C
carbon atoms of the vinylidene ligands and also the
resonance at d 121.7 for the carbon atom of the CF3
group. Treatment of 3 with KF in acetone gives the
difluoro derivative 4 by ligand exchange. The direct
/
the p-electrons along the RCÅ
The reaction of the ferrocenyl-substituted vinylidene
complex 2 with half an equivalent of Ph3SnCÅCÃCÅ
/
CÃ
/
RhÄ
/
CÄ
/
CHR? chain.
/
/
/
CSnPh3 affords a green solution together with a white,
nearly insoluble solid, which by comparison of the IR
and 19F-NMR spectra was identified as Ph3SnF [8].
From the green solution, after evaporation of the
Scheme 1. Tfꢀ
/
CF3SO2; Lꢀ
/
Pi Pr3; [Fe]ꢀ
ÃC5H4FeC5H5.
/
/

146
B. Callejas-Gaspar et al. / Journal of Organometallic Chemistry 684 (2003) 144ꢂ152
/
Scheme 2. Lꢀ
/
Pi Pr3; [Fe]ꢀ
ÃC5H4FeC5H5.
/
/
solvent and recrystallization of the residue from acetone,
the dinuclear complex 7 was isolated as a green air-
sensitive solid in 48% yield (Scheme 2). Characteristic
features of 7 are the 13C-NMR resonances for the a- and
[Rh(CO)(PiPr3)2] moieties is coordinated to the b-C
atom of a butenynyl unit and that these units are linked
together by a C6H4 bridge. The stereochemistry around
each rhodium center is thus quite analogous to that of
b-carbon atoms of the RhÄ
observed at d 309.9 and 108.6 as doublets of triplets
due to 13Cꢂ103Rh and 13Cꢂ31
P couplings. The signal for
/
CÄ/C units, which are
the mononuclear complex trans-[Rh{C(CÅ
CHPh)(CO)(PiPr3)2] formed from trans-[Rh(CÅ
CPh)(ÄCÄ
CHPh)(PiPr3)2] and CO [9].
Besides 1,4-C6H4(CÅCH)2, the reactions of the func-
tionalized diynes 1,1?,4,4?-C6H4(OH)2(CÅCH)2 and 1,4-
C6H4[C(Ph)(OH)CÅ
CH]2 with [RhCl(PiPr3)2]2 (10)
/
CPh)Ä
/
/
/
/
/
/
the two metal-bonded carbons of the C4 chain appears
at d 123.9 also as a doublet of triplets while the
resonance of the two central carbon atoms could not
be exactly located. It should be mentioned that attempts
/
/
/
(which in our previous studies was already used as
starting material) were also investigated. Treatment of
to prepare compound 7 from 4 and Me3SiCÅ
CSiMe3 failed.
Following the observation that the mononuclear
alkynyl complexes CR)(ÄCÄCHR?)-
trans-[Rh(CÅ
(PiPr3)2] react with CO to give the butenynyl com-
pounds trans-[Rh{C(CÅCR)Ä
CHR?)(CO)(PiPr3)2] by
migratory insertion of the vinylidene ligand into the
RhÃC s-bond [9], we were prompted to study also the
/
CÃ
/
CÅ
/
10 with 1,1?,4,4?-C6H4(OH)2(CÅ
/
CH)2 and 1,4-
C6H4[C(Ph)(OH)CÅCH]2 in acetone/ether at ꢃ
/
/
20 8C
/
/
/
led in each case to the precipitation of a yellow solid, the
formation of which was supported by the addition of
ether. These compounds, supposed to be the diyne
complexes 11 and 12 (Scheme 4), can only be handled
at low temperatures and, if warmed to ca. 20 8C,
rearrange smoothly to the dinuclear bis(vinylidene)
isomers 13 and 14 in excellent yields. The conversion,
which is accompanied by a characteristic change of color
from yellow to deep blue, can be facilitated by the
addition of small amounts of NEt3. The IR spectra of
the a,v-diyne complexes display two strong absorptions
at, respectively, 3585 and 2096 cmꢃ1 (11) and 3587 and
/
/
/
analogous reaction of 7 with carbon monoxide. Passing
a slow stream of CO through a solution of 7 in pentane
at room temperature led to a change of color from green
to orange and gave the dinuclear dicarbonyldirhodium
complex 8, formed by twofold migratory insertion, as an
orange air-stable solid in 78% yield. The composition of
8 is supported by the elemental analysis and the mass
2105 cmꢃ1 (12), which are assigned to the n(OH) and
spectrum. The IR spectrum of 8 displays the n(CÅ
and n(CO) stretching modes at 2065 and 1939 cmꢃ1
respectively. The signal of the vinylic RhÃCÄCH
/C)
1
C) stretching modes. In the H-NMR spectra, a
n(CÅ
/
,
doublet appears at d 3.61 (11) and d 3.83 (12) for the CÅ
/
/
/
1
CH protons and two doublets of virtual triplets at d 1.41
and 1.30 (11) and d 1.13 and 1.05 (12) for the PCHCH3
protons, the splitting pattern of the latters being
diagnostic for the trans-position of the PiPr3 ligands
[10]. In agreement with earlier observations [11], we
assume that the conversion of the diyne to the bis(viny-
lidene) compounds proceeds via the diynyl(hydrido)
protons appears in the H-NMR spectrum of 8 at d
7.55 and thus at nearly the same chemical shift (d 7.46)
as found for the analogue where instead of a ferrocenyl a
phenyl unit is linked to each of the terminal carbon
atoms of the C8 chain [7]. Since in this case the Z-
configuration at the CÄ
/
C bond has been confirmed by
an X-ray crystal structure analysis [7], we assume that
also in 8 the two metal-containing fragments are linked
in cis-disposition to the carbonÃ/carbon double bond.
Under similar conditions as used for the reaction of 7,
the dirhodium compound 6 also reacts with CO by
twofold migratory insertion (see Scheme 3). From
pentane solution, the dinuclear complex 9 has been
isolated as a yellow solid in 97% yield. In agreement
with the spectroscopic data, we assume that each of the
Scheme 3. Lꢀ
Pi Pr3.
/

B. Callejas-Gaspar et al. / Journal of Organometallic Chemistry 684 (2003) 144ꢂ
/152
147
Scheme 4. Lꢀ
Pi Pr3.
/
derivatives (shown in Scheme 4) which are generally
quite labile and in a few cases have been trapped with
pyridine [12].
n(CÄ
/
CÄ
/
C) stretching mode, characteristic for metal-
allenylidenes, appears in the IR spectrum at 1875 cmꢃ1
and thus at a very similar position as found for the
The bis(vinylidene) complexes 13 and 14 have been
isolated as blue or dark blue, relatively air-stable solids
and fully characterized by elemental analysis and
spectroscopic techniques. They are much less soluble
in common organic solvents than the mononuclear
mononuclear
analogue
trans-[RhCl(Ä
/
CÄ
/
CÄ
/
CPh2)(PiPr3)2] [13]. The 13C-NMR spectrum of 15
display in the low-field region three signals at d 250.7,
221.7 and 143.8 which are assigned to the carbon atoms
of the two RhÄ
/
CÄ
/
CÄ/C fragments. Since there is only
counterparts trans-[RhCl(Ä
/
CÄ
/
CHR)(PiPr3)2], which in-
one set of signals for the pairs of these 13C nuclei and
also only one resonance for the phosphorus atoms of the
four PiPr3 ligands, a symmetrical structure of the
dinuclear molecule can be assumed. We finally note
that, although in recent years an impressive number of
organometallic dimers and oligomers in which a con-
jugated carbon framework is spanned by transition-
metal centers has been reported [14], the dinuclear
rhodium(I) compound 15 is, to the best of our knowl-
dicates that in the lattice possibly oligomers are formed
via hydrogen bonds. Similarly to 11 and 12, the IR
spectra of 13 and 14 show a strong n(OH) stretch at
3580 (13) and 3568 cmꢃ1 (14) and also a n(CÄ
/C) mode
in the expected region. Other typical features are the
triplet resonance for the vinylidene protons at d 0.13
1
(13) and 1.00 (14) in the H-NMR spectra and the two
low-field signals for the a- and b-carbon atoms of the
RhÄ
/
CÄ
/
C units at d 287.5 and 114.1 (13) and 285.3 and
edge, the first species in which two cumulated MÄ
/
CÄ
/
CÄ
/
117.2 (14) in the 13C-NMR spectra, respectively. It
should be mentioned that in the 1H- and 13C-NMR
spectra for the protons as well as for the carbon atoms
of the bridging C6H4 fragments only a single resonance
is observed, being consistent with the proposed structure
shown in Scheme 4.
Attempts to convert the bis(vinylidene) into the
corresponding bis(allenylidene) complexes were only
successful with 14 as the starting material. The appro-
priate route was to bring a solution of 14 in chloroform
in contact with acidic Al2O3 that behaves as a proton
source and affords by elimination of water the required
product 15 in 80% isolated yield (Scheme 5). Compound
15 is a redꢂviolet solid which, probably due to the
/
absence of OH functionalities, is better soluble in
common organic solvents than the precursor 14. The
Scheme 5. Lꢀ
Pi Pr3.
/

148
B. Callejas-Gaspar et al. / Journal of Organometallic Chemistry 684 (2003) 144ꢂ152
/
C units are connected by a delocalized arene p-electron
system.
3.2. Preparation of trans-[{m-1,4-C6H4(CHÄ
/
CÄ
/
)2}{Rh(h1-OS(O)2CF3)(PiPr3)2}2] (3)
A solution of 245 mg (0.43 mmol) of 1 in 10 ml of
acetone was cooled at ꢃ78 8C and treated with 27 mg
(0.21 mmol) of 1,4-C6H4(CÅCH)2. The reaction mixture
was slowly warmed to r.t. and stirred for 12 h. The
solvent was evaporated in vacuo, the residue was
dissolved in 3 ml of pentane and the solution stored at
/
/
3. Experimental
All experiments were carried out under an atmosphere
of argon by Schlenk techniques. The starting materials 1
ꢃ
/
78 8C for 6 h. A dark violet solid precipitated which
was separated from the mother liquor, washed twice
with 2 ml of pentane (ꢃ20 8C) and dried; yield 464 mg
[5], 10 [15], (C5H5)Fe(C5H4CÅ
[17], Ph3SnCÅCÃCÅCSnPh3 [18], 1,4Ã
[19], 1,1?,4,4?-C6H4(OH)2(CÅCH)2 [20] and 1,4-
C6H4[C(Ph)(OH)CÅCH]2 [20] were prepared as de-
/
CH) [16], RCÅ
/
CSnPh3
/
/
/
/
C6H4(CÅ
/CH)2
/
/
(85%). Anal. Found: C, 44.95; H, 7.34; S, 4.80. Calc. for
C48F6H90O6P4Rh2S2: C, 45.37; H, 7.14; S, 5.03%. IR
/
scribed in the literature. NMR spectra were recorded
at room temperature (r.t.) on Bruker AC 200 and
Bruker AMX 400 instruments, IR spectra on a
1
(Nujol): n(CÄ
/
C) 1621 cmꢃ1. H-NMR (acetone-d6, 400
MHz): d 7.05 (s, 4H, C6H4), 2.52 (m, 12H, PCHCH3),
1.38 [dvt, Nꢀ13.5, J(H,H)ꢀ6.8 Hz, 72H, PCHCH3];
signal for the RhÄCÄCH proton not exactly located.
13C-NMR (acetone-d6, 100.6 MHz):
304.9 [d,
J(Rh,C)ꢀ64.5 Hz, RhÄC], 126.5 (s, C6H4), 121.7 [q,
J(F,C)ꢀ322.0 Hz, CF3], 121.5 (s, ipso-C of C6H4),
112.6 [dt, J(Rh,C)ꢀ17.6, J(P,C)ꢀ4.0 Hz, RhÄCÄC],
24.3 (vt, Nꢀ20.4 Hz, PCHCH3), 20.0 (s, PCHCH3).
19F-NMR (acetone-d6, 376.6 MHz): d ꢃ78.6 (s). 31P-
NMR (acetone-d6, 162.0 MHz): d 42.8 [d, J(Rh,P)ꢀ
134.6 Hz].
/
/
PerkinꢂElmer 1420 or an 25 FT-IR infrared spectro-
/
/
/
meter, and mass spectra on a Finnigan 90 MAT
instrument at 70 eV. Melting points were determined
by DTA. Abbreviations used: s, singlet; d, doublet; t,
triplet; q, quartet; vt, virtual triplet; dvt, doublet of
d
/
/
/
/
/
/
/
virtual triplet; m, multiplet; br, broadened signal;
1
N Ä
/
3J(P,H)ꢁ5
/
J(P,H) or J(P,C)ꢁ3
/
J(P,C).
/
/
/
3.1. Preparation of trans-[RhF{Ä
/
CÄ
/
CH(C5H4)Fe(C5H5)}(PiPr3)2] (2)
3.3. Preparation of trans-[{m-1,4-C6H4(CHÄ
/
A solution of 423 mg (0.74 mmol) of 1 in 15 ml of
acetone was cooled at ꢃ78 8C and treated with 155 mg
CÄ
/
)2}{RhF(PiPr3)2}2] (4)
/
(0.74 mmol) of ethinylferrocene. The reaction mixture
was slowly warmed to r.t. and stirred for 12 h. It was
then treated with 86 mg (1.50 mmol) of KF and stirred
for 3 h at r.t. A gradual change of color from black to
dark violet occurred. The solvent was evaporated in
vacuo and the residue was extracted with 20 ml of
pentane. The extract was concentrated to ca. 2 ml in
A solution of 109 mg (0.08 mmol) of 3 in 10 ml of
acetone was treated with 23 mg (0.34 mmol) of KF and
stirred for 3 h at r.t. A gradual change of color from
black to dark violet occurred. The solvent was evapo-
rated in vacuo and the residue was extracted twice with
40 ml of pentane each. The extract was concentrated to
ca. 2 ml in vacuo and then stored for 16 h at ꢃ78 8C. A
violet solid precipitated which were separated from the
mother liquor at low temperature, washed twice with 2
/
vacuo and then stored for 12 h at ꢃ60 8C. Violet
/
crystals precipitated which were separated from the
mother liquor, washed three times with 2 ml of pentane
(0 8C) each and dried; yield 351 mg (73%), m.p. (dec.)
64 8C. Anal. Found: C, 55.14; H, 8.03. Calc. for
ml of pentane (ꢃ20 8C) each and dried; yield 51 mg
/
(58%), m.p. (dec.) 60 8C. Anal. Found: C, 54.38; H, 9.24.
Calc. for C46F2H90P4Rh2: C, 54.65; H, 8.97%. MS
C30H52FFeP2Rh: C, 55.23; H 8.03%. IR (Nujol): n(CÄ
/
(FAB): m/z 1011 [Mꢁ], 814 [Mꢁꢃ
/
2Fꢂ
vis (hexane): lmax
398, 554 nm. 1H-NMR (C6D6, 400 MHz): d 7.13 (s, 4H,
C6H4), 2.48 (m, 12H, PCHCH3), 1.70 (br s, 2H, RhÄCÄ
CH), 1.30 [dvt, Nꢀ13.5, J(H,H)ꢀ6.8 Hz, 72H,
PCHCH3]. 13C-NMR (C6D6, 100.6 MHz): d 124.9 (s,
C6H4), 121.9 (s, ipso-C of C6H4), 112.2 (br s, RhÄCÄC),
23.3 (vt, Nꢀ 18.6 Hz, PCHCH3), 20.2 (s, PCHCH3);
signal for the RhÄC ÄC carbon atom not exactly
located. 19F-NMR (C6D6, 376.6 MHz): d ꢃ
215.5 (br
s). 31P-NMR (C6D6, 162.0 MHz): d 45.5 [dd, J(Rh,P)ꢀ
144.1, J(F,P)ꢀ11.9 Hz].
/
2PiPr3]. IR
C) 1645, n(RhF) 468 cmꢃ1. UVꢂ
vis (hexane): lmax 408,
/
C) 1619 cmꢃ1. UVꢂ
/
553 nm. 1H-NMR (C6D6, 400 MHz): d 4.02 (s, 5H,
C5H5), 3.99, 3.97 (both m, 2H each, C5H4), 2.55 (m, 6H,
(Nujol): n(CÄ
/
/
/
PCHCH3), 1.34 (dvt, Nꢀ
PCHCH3), 1.18 (m, 1H, Ä
CHC5H4). 13C-NMR (C6D6,
100.6 MHz): d 104.9 (m, RhÄCÄC), 73.1 (s, ipso-C of
C5H4), 69.3 (s, C5H5), 67.3, 66.0 (both s, C5H4), 23.5 (vt,
Nꢀ18.2 Hz, PCHCH3), 20.5 (s, PCHCH3); signal for
the RhÄC Ä
C carbon atom not exactly located. 19F-
NMR (C6D6, 376.6 MHz): d ꢃ
218.1 (br s). 31P-NMR
(C6D6, 162.0 MHz): d 45.7 [dd, J(Rh,P)ꢀ144.1,
J(F,P)ꢀ18.1 Hz].
/
13.3, J(H,H)ꢀ/7.0 Hz, 36H,
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/

B. Callejas-Gaspar et al. / Journal of Organometallic Chemistry 684 (2003) 144ꢂ
/152
149
3.4. Preparation of trans-[{m-1,4-C6H4(CHÄ
/
s, C6H5), 127.9 (s, ipso-C of C6H5), 125.4 [dt, J(Rh,C)ꢀ
/
CÄ)2}{Rh(CÅ
/
/
CCH3)(PiPr3)2}2] (5)
55.6, J(P,C)ꢀ
/
17.7 Hz, RhÃ
/
C Å
/
C], 124.7 (s, C6H4),
119.8 (s, ipso-C of C6H4), 114.5 [dt, J(Rh,C)ꢀ
J(P,C)ꢀ5.0 Hz, RhÄCÄC], 24.5 (vt, Nꢀ20.2 Hz,
PCHCH3), 19.4 (s, PCHCH3). 31P-NMR (C6D6, 162.0
MHz): d 47.5 [d, J(Rh,P)ꢀ135.6 Hz].
/17.7,
A solution of 189 mg (0.19 mmol) of 4 in 15 ml of
pentane was cooled at ꢃ30 8C and treated with 145 mg
(0.38 mmol) of CH3CÅCSnPh3. The reaction mixture
/
/
/
/
/
/
/
was slowly warmed to r.t. and stirred for 2.5 h. A change
of color from violet to green occurred. The solution was
filtered and the filtrate was brought to dryness in vacuo.
The residue was dissolved in 3 ml of acetone and the
3.6. Preparation of trans-[(m-CÅ
/
CÃ
/
CÅ
/
C){Rh(Ä
/
CÄ
/
CH(C5H4)Fe(C5H5))(PiPr3)2}2] (7)
solution was stored for 15 h at ꢃ
precipitated which were separated from the mother
liquor, washed twice with 2 ml of acetone (ꢃ20 8C)
each and dried; yield 169 mg (64%), m.p. (dec.) 40 8C.
Anal. Found: C, 59.26; H, 8.91. Calc. for C52H96P4Rh2:
/
65 8C. Green crystals
A solution of 130 mg (0.20 mmol) of 2 in 12 ml of
pentane was cooled at ꢃ30 8C and treated with 74 mg
(0.10 mmol) of Ph3SnCÅCÃCÅCSnPh3. The reaction
mixture was slowly warmed to r.t. and stirred for 1.5 h.
A change of color from violet to green and the
precipitation of a white solid occurred. The solution
was filtered and the filtrate was brought to dryness in
vacuo. The residue was dissolved in 3 ml of acetone and
/
/
/
/
/
C, 59.42; H, 9.21%. IR (Nujol): n(CÄ
/
C) 1618 cmꢃ1
.
1
UVꢂ
400 MHz): d 7.19 (br s, 4H, C6H4), 2.75 (m, 12H,
PCHCH3), 2.18 [t, J(P,H)ꢀ2.0 Hz, 6H, ÅCÃCH3], 1.51
[t, J(P,H)ꢀ3.5 Hz, 2H, RhÄCÄCH], 1.39 [dvt, Nꢀ
13.5, J(H,H)ꢀ
7.0 Hz, 72H, PCHCH3]. 13C-NMR
(C6D6, 100.6 MHz): d 289.7 [dt, J(Rh,C)ꢀ48.5,
J(P,C)ꢀ16.2 Hz, RhÄC], 131.5 [d, J(Rh,C)ꢀ10.1
Hz, RhÃCÅC], 125.8 (s, C6H4), 121.1 (s, ipso-C of
C6H4), 115.9 [dt, J(Rh,C)ꢀ11.1, J(P,C)ꢀ5.1 Hz, RhÄ
CÄCH], 109.9 [dt, J(Rh,C)ꢀ37.6, J(P,C)ꢀ18.3 Hz,
RhÃC ÅC], 25.7 (vt, Nꢀ 20.4 Hz, PCHCH3), 20.7 (s,
PCHCH3), 16.7 [d, J(Rh,C)ꢀ3.0 Hz, ÅCÃ
CH3]. 31P-
NMR (C6D6, 162.0 MHz): d 47.3 [d, J(Rh,P)ꢀ137.3
Hz].
/
vis (hexane): lmax 456, 614 nm. H-NMR (C6D6,
/
/
/
the solution stored for 15 h at ꢃ
precipitated which were separated from the mother
liquor, washed three times with 2 ml of acetone (ꢃ
/
60 8C. A green solid
/
/
/
/
/
/
/
20 8C) each and dried; yield 66 mg (48%), m.p. (dec.)
38 8C. Anal. Found: C, 58.15; H, 7.65. Calc. for
C64H104P4Fe2Rh2: C, 58.46; H, 7.97%. IR (Nujol):
/
/
/
/
/
/
/
/
n(CÄ
/
C) 1628 cmꢃ1. UVꢂ
/
vis (hexane): lmax
nm. 1H-NMR (C6D6, 400 MHz): d 4.34 (s, 10H, C5H5),
4.25, 4.20 (both m, 8H, C5H4), 3.05 (m, 12H, PCHCH3),
ꢀ637, 421
/
/
/
/
/
/
/
/
/
/
1.65 [dvt, Nꢀ
1.18 (m, 2H, Ä
MHz): d 309.9 [dt, J(Rh,C)ꢀ
RhÄC], 123.9 [dt, J(Rh,C)ꢀ39.2, J(P,C)ꢀ
RhÃC ÅC], 108.6 [dt, J(Rh,C)ꢀ11.4, J(P,C)ꢀ
RhÄCÄCH], 71.8 (s, ipso-C of C5H4), 69.1 (s, C5H5),
67.3, 66.1 (both s, C5H4), 25.5 (vt, Nꢀ22.8 Hz,
PCHCH3), 20.8 (s, PCHCH3); signal for the RhÃCÅ
carbon atom could not be exactly located. 31P-NMR
(C6D6, 162.0 MHz): d 47.8 [d, J(Rh,P)ꢀ137.4 Hz].
/
13.5, J(H,H)ꢀ
CHC5H4). 13C-NMR (C6D6, 100.6
48.0, J(P,C)ꢀ16.4 Hz,
21.5 Hz,
6.3 Hz,
/
6.4 Hz, 72H, PCHCH3],
/
/
/
/
/
/
/
3.5. Preparation of trans-[{m-1,4-C6H4(CHÄ
/
/
/
/
/
CÄ)2}{Rh(CÅ
/
/
CPh)(PiPr3)2}2] (6)
/
/
/
A solution of 152 mg (0.15 mmol) of 4 in 20 ml of
pentane was cooled at ꢃ30 8C and treated with 136 mg
(0.30 mmol) of PhCÅCSnPh3. The reaction mixture was
/
/
C
/
/
/
slowly warmed to r.t. and stirred for 3 h. A change of
color from violet to green occurred. The solution was
filtered and the filtrate was concentrated to ca. 2 ml in
3.7. Preparation of trans-[{m-(Z,Z)-C(Ä
C)2C(Ä
CH[Fe])}{Rh(CO)(PiPr3)2}2] (8) ([Fe]Ä
(C5H4)Fe(C5H5))
/
CH[Fe])(CÅ
/
/
/
vacuo. After the solution was stored for 15 h at ꢃ
a green solid precipitated which were separated from the
mother liquor, washed twice with 2 ml of pentane (ꢃ
/
78 8C,
/
A slow stream of CO was passed for 30 s through a
solution of 239 mg (0.18 mmol) of 7 in 15 ml of pentane
at r.t. A change of color from green to orange occurred.
After the solution was stirred for 5 min, the solvens was
evaporated in vacuo. The residue was recrystallized
from toluene/pentane (1:5) to give orange crystals. These
were separated from the mother liquor, washed twice
with 2 ml of pentane each and dried in vacuo; yield 194
mg (78%), m.p. (dec.) 96 8C. Anal. Found: C, 58.18; H,
7.32; Rh, 14.96. Calc. for C66H104P4Rh2Fe2O2: C, 57.81;
H, 7.60; Rh, 15.02%. MS (FAB): m/z 1370 [Mꢁ]. IR
30 8C) each and dried; yield 166 mg (94%), m.p. (dec.)
54 8C. Anal. Found: C, 63.34; H, 8.91. Calc. for
C62H100P4Rh2: C, 63.37; H, 8.58%. MS (FAB): m/zꢀ
1074 [Mꢁ], 812 [Mꢁ 2PiPr3 ꢃ
2PhCÅC]. IR (Nujol):
n(CÅC) 2073, n(CÄ vis (hexane):
C) 1632 cmꢃ1. UVꢂ
/
ꢃ
/
/
/
/
/
/
1
lmax 450, 620 nm. H-NMR (C6D6, 400 MHz): d 7.42
(m, 4H, ortho-H von C6H5), 7.17 (s, 4H, C6H4), 7.13 (m,
4H, meta-H von C6H5), 6.93 (m, 2H, para-H von C6H5),
2.74 (m, 12H, PCHCH3), 1.58 [t, J(P,H)ꢀ
RhÄCÄCH], 1.36 [dvt, Nꢀ13.8, J(H,H)ꢀ7.0 Hz, 72H,
PCHCH3]. 13C-NMR (C6D6, 100.6 MHz): d 313.0 [dt,
J(Rh,C)ꢀ49.3, J(P,C)ꢀ15.2 Hz, RhÄC], 135.9 [d,
J(Rh,C)ꢀ8.8 Hz, RhÃCÅC], 128.9, 127.1, 124.0 (all
/
3.5 Hz, 2H,
/
/
/
/
(Nujol): n(CÅ
(hexane): lmax
d8, 200 MHz): d 7.55 (br s, 2H, RhÃ
/
C) 2065, n(CO) 1939 cmꢃ1. UVꢂ
/
vis
347, 383, 448 nm. H-NMR (toluene-
CÄCH), 4.84, 4.05
1
/
/
/
ꢀ
/
/
/
/
/
/

150
B. Callejas-Gaspar et al. / Journal of Organometallic Chemistry 684 (2003) 144ꢂ152
/
(both m, 4H each, C5H4), 4.09 (s, 10H, C5H5), 2.40 (m,
3.10. Preparation of [{m-1,4-C6H4(C(Ph)(OH)CÅ
/
CH)2}{RhCl(PiPr3)2}2] (12)
12H, PCHCH3), 1.37 [dvt, Nꢀ
/
13.5, J(H,H)ꢀ
/
6.9 Hz,
6.6 Hz,
36H, PCHCH3], 1.24 [dvt, Nꢀ
/
13.1, J(H,H)ꢀ
/
36 H, PCHCH3]. 31P-NMR (toluene-d8, 81.0 MHz): d
A solution of 248 mg (0.27 mmol) of 10 in 8 ml of
ether was cooled at ꢃ
solution of 91 mg (0.27 mmol) of 1,4-
C6H4[C(Ph)(OH)CÅCH]2 in 4 ml of acetone. A yellow
solid precipitated, the formation of which was facilitated
by addition of 10 ml of pentane (ꢃ20 8C). The solid was
separated from the mother liquor, washed three times
with 3 ml of ether (ꢃ20 8C) each and dried in vacuo;
yield 258 mg (76%), m.p. (dec.) 85 8C. IR (C6H6): n(OH)
/
20 8C and treated dropwise with a
43.0 [d, J(Rh,P)ꢀ139.9 Hz].
/
/
3.8. Preparation of trans-[{m-(Z,Z)-C(CÅ
/
CPh)Ä
/
/
CHC6H4CHÄC(CÅ
/
/
CPh)}{Rh(CO)(PiPr3)2}2] (9)
/
A slow stream of CO was passed for 30 s through a
solution of 128 mg (0.10 mmol) of 6 in 10 ml of pentane
at r.t. A change of color from green to yellow occurred.
After the solution was stirred for 5 min, it was
concentrated to ca. 2 ml in vacuo. A yellow micro-
crystalline solid precipitated which was separated from
the mother liquor, washed three times with 2 ml of
pentane each and dried in vacuo; yield: 120 mg (97%),
m.p. (dec.) 76 8C. Anal. Found: C, 62.17; H, 7.90; Rh,
17.10. Calc. for C64H100P4Rh2O2: C, 62.43; H, 8.19; Rh,
1
3587, n(CÅ
/
C) 2105 cmꢃ1. H-NMR (200 MHz, C6D6):
d 7.79 (m, 4H, ortho-H of C6H5), 7.71 (s, 4H, C6H4),
7.07 (m, 4H, meta-H of C6H5), 6.93 (m, 2H, para-H of
C6H5), 3.83 [d, J(Rh,H)ꢀ
12H, PCHCH3), 1.13 [dvt, Nꢀ
36H, PCHCH3], 1.05 [dvt, Nꢀ
/
2.5 Hz, 2H, CÅ
14.8, J(H,H)ꢀ
14.4, J(H,H)ꢀ
/
CH], 2.01 (m,
/
/7.4 Hz,
/
/7.0 Hz,
36H, PCHCH3], signal for the OH proton not observed.
31P-NMR (81.0 MHz, C6D6): dꢀ
33.0 [d, J(Rh,P)ꢀ
113.8 Hz].
/
/
16.72%. IR (Nujol): n(CÅ
1595 cmꢃ1. UVꢂ
vis (hexane): lmax
1H-NMR (C6D6, 400 MHz): d 8.08 [br d, J(Rh,H)ꢀ
Hz, 2H, RhÃCÄCH], 7.56 (m, 4H, ortho-H of C6H5],
6.99 (m, 2H, para-H of C6H5), 2.40 (m, 12H, PCHCH3),
/
C) 2148, n(CO) 1944, n(CÄ
388, 416, 441 nm.
2.4
/
C)
3.11. Preparation of [{m-1,1?,4,4?-C6H4(OH)2(CHÄ
/
/
ꢀ
/
CÄ
/
)2}{RhCl(PiPr3)2}2] (13)
/
/
/
A solution of 114 mg (0.12 mmol) of 10 in 8 ml of
ether was treated dropwise with a solution of 19 mg
1.37 [dvt, Nꢀ
/
13.8, J(H,H)ꢀ/8.0 Hz, 36H, PCHCH3],
(0.12 mmol) of 1,1?,4,4?-C6H4(OH)2(CÅ/CH)2 in 2 ml of
1.11 [dvt, Nꢀ
/
13.2, J(H,H)ꢀ/7.0 Hz, 36H, PCHCH3];
acetone at r.t. A change of color from red to yellow
occurred. After 5 min, 1 ml of triethylamine was added
and the reaction mixture stirred for 12 h at r.t. The
solvent was evaporated in vacuo, and the residue was
recrystallized from acetone at 0 8C. A blue microcrystal-
line solid precipitated which was separated from the
signals for meta-H of C6H5 and those of C6H4 were
covered by the signal of the solvent. 31P-NMR (C6D6,
162.0 MHz): d 43.1 [d, J(Rh,P)ꢀ139.0 Hz].
/
mother liquor, washed twice with 3 ml of ether (ꢃ20 8C)
each and dried; yield 101 mg (78%), m.p. (dec.) 76 8C.
Anal. Found: C, 51.34; H, 8.99. Calc. for
/
3.9. Preparation of [{m-1,1?,4,4?-C6H4(OH)2(CÅ
/
CH)2}{RhCl(PiPr3)2}2] (11)
C46H92Cl2O2P4Rh2: C, 51.26; H, 8.60%. IR (C6H6):
1
A solution of 233 mg (0.25 mmol) of 10 in 10 ml of
n(OH) 3580, n(CÄ
/
C) 1715 cmꢃ1. H-NMR (400 MHz,
ether was cooled at ꢃ
solution of 41 mg (0.25 mmol) of 1,1?,4,4?-
C6H4(OH)2(CÅCH)2 in 2 ml of acetone. A yellow solid
precipitated, the formation of which was facilitated by
addition of 10 ml of pentane (ꢃ20 8C). The solid was
separated from the mother liquor, washed three times
with 3 ml of ether (ꢃ20 8C) each and dried in vacuo;
/
30 8C and treated dropwise with a
CD2Cl2): d 5.64 (s, 4H, C6H4), 2.78 (m, 12H, PCHCH3),
1.50 (s, 2H, OH), 1.31 [dvt, Nꢀ 13.6, J(H,H)ꢀ6.8 Hz,
72H, PCHCH3], 0.13 [t, J(P,H)ꢀ3.2 Hz, 2H, Ä CH].
13C-NMR (100.6 MHz, CD2Cl2):
J(Rh,C)ꢀ61.4, J(P,C)ꢀ16.1 Hz, RhÄ
C6H4), 114.1 [dt, J(Rh,C)ꢀ16.1, J(P,C)ꢀ
CÄC], 58.4 (s, i-C of C6H4), 23.9 (vt, Nꢀ
PCHCH3), 20.6 (s, PCHCH3). 31P-NMR (162.0 MHz,
CD2Cl2): d 40.9 [d, J(Rh,P)ꢀ133.8 Hz].
/
/
/
/
/
CÄ
/
d
287.5 [dt,
/
/
/
/
C Ä
/
C], 132.3 (s,
/
/
6.0 Hz, RhÄ
/
/
/
/
20.0 Hz,
yield 279 mg (76%), m.p. (dec.) 67 8C. Anal. Found: C,
50.78; H, 8.38. Calc. for C46H92Cl2O2P4Rh2: C, 51.26;
/
H, 8.60%. IR (C6H6): n(OH) 3585, n(CÅ
1H-NMR (200 MHz, C6D6): d 5.26 (br s, 4H, C6H4),
3.61 [d, J(Rh,H)ꢀ2.6 Hz, 2H, CÅCH], 2.53 (m, 12H,
PCHCH3), 1.41 [dvt, Nꢀ 13.8, J(H,H)ꢀ7.3 Hz, 36H,
PCHCH3], 1.30 [dvt, Nꢀ 12.8, J(H,H)ꢀ6.6 Hz, 36H,
PCHCH3], signal for the OH proton not observed. 31P-
NMR (81.0 MHz, C6D6): d 32.4 [d, J(Rh,P)ꢀ114.4
Hz].
/
C) 2096 cmꢃ1
.
3.12. Preparation of [{m-1,4-C6H4(C(Ph)(OH)CHÄ
/
)2}{RhCl(PiPr3)2}2] (14)
/
/
CÄ
/
/
/
/
/
This compound was prepared analogously as de-
scribed for 13, from 143 mg (0.15 mmol) of 10, 51 mg
/
(0.15 mmol) of 1,4-C6H4[C(Ph)(OH)CÅ
/
CH]2 and 3 ml
of triethylamine. The product was recrystallized from

B. Callejas-Gaspar et al. / Journal of Organometallic Chemistry 684 (2003) 144ꢂ
/152
151
CHCl3ꢂ
/
ether (2:5) at 5 8C. A dark blue microcrystalline
solid was obtained; yield 155 mg (82%), m.p. (dec.)
DTA), Mrs M.-L.S. and Dr W.B. (NMR spectra) and
Dr G.L. and Mr F.D. (mass spectra).
132 8C. Anal. Found: C, 57.12; H, 7.98. Calc. for
C60H102Cl2O2P4Rh2: C, 57.37; H, 8.19%. IR (C6H6):
1
n(OH) 3568, n(CÄ
/
C) 1644 cmꢃ1. H-NMR (400 MHz,
References
CDCl3): d 7.77 (m, 4H, ortho-H of C6H5), 7.34 (s, 4H,
C6H4), 7.22 (m, 6H, meta- and para-H of C6H5), 2.65
[1] Short reviews: H. Werner, Nachr. Chem. Tech. Lab. 40 (1992)
435; H. Werner, J. Organomet. Chem. 475 (1994) 45.
[2] H. Werner, T. Rappert, J. Wolf, Isr. J. Chem. 30 (1990) 377.
[3] H. Werner, P. Bachmann, M. Laubender, O. Gevert, Eur. J.
Inorg. Chem. (1998) 1217.
(m, 12H, PCHCH3), 2.60 (s, 2H, OH), 1.18 [dvt, Nꢀ
14.0, J(H,H)ꢀ7.2 Hz, 72H, PCHCH3], 1.00 [t,
J(P,H)ꢀ3.2 Hz, 2H, RhÄCÄ
CH]. 13C-NMR (100.6
MHz, CDCl3): d 285.3 [dt, J(Rh,C)ꢀ61.4, J(P,C)ꢀ
16.1 Hz, RhÄC ÄC], 148.4, 147.1 (both s, ipso-C of
C6H4 and C6H5), 128.3, 127.9, 125.1, 124.7 (all s, C6H4
and C6H5), 117.2 [dt, J(Rh,C)ꢀ15.1, J(P,C)ꢀ5.0 Hz,
RhÄCÄC], 67.1 (s, RhÄCÄCꢂC), 23.2 (vt, Nꢀ 19.9 Hz,
PCHCH3), 19.9 (s, PCHCH3). 31P-NMR (162.0 MHz,
CDCl3): d 41.2 [d, J(Rh,P)ꢀ132.5 Hz].
/
/
/
/
/
/
/
[4] J. Gil-Rubio, B. Weberndorfer, H. Werner, J. Chem. Soc. Dalton
¨
Trans. (1999) 1437.
/
/
[5] H. Werner, M. Bosch, M.E. Schneider, C. Hahn, F. Kukla, M.
Manger, B. Windmuller, B. Weberndorfer, M. Laubender, J.
/
/
¨
Chem. Soc. Dalton Trans. (1998) 3549.
¨
/
/
/
/
/
/
[6] E.O. Fischer, C.G. Kreiter, H.J. Kollmeier, J. Muller, R.D.
¨
Fischer, J. Organomet. Chem. 28 (1971) 237.
/
[7] J. Gil-Rubio, M. Laubender, H. Werner, Organometallics 19
(2000) 1365.
[8] H. Kriegsmann, H. Geissler, Z. Anorg. Allg. Chem. 323 (1963)
170.
[9] (a) R. Wiedemann, P. Steinert, M. Schafer, H. Werner, J. Am.
¨
3.13. Preparation of [{m-1,4-C6H4(CPhÄ
/
CÄ
/
CÄ
/
)2}{RhCl(PiPr3)2}2] (15)
Chem. Soc. 115 (1993) 9864;
A solution of 286 mg (0.23 mmol) of 14 in 5 ml of
CHCl3 was brought up on a column filled with Al2O3
(acidic, activity grade I, length of column 5 cm). A
(b) H. Werner, R. Wiedemann, P. Steinert, J. Wolf, Chem. Eur. J.
3 (1997) 127.
[10] R.K. Harris, Can. J. Chem. 42 (1964) 2275.
[11] (a) T. Rappert, O. Nurnberg, N. Mahr, J. Wolf, H. Werner,
¨
Organometallics 11 (1992) 4156;
change of color from blue to redꢂviolet occurred. The
/
elution of the generated compound was carried out first
with CHCl3 and then with ether. The combined
fractions were brought to dryness in vacuo. The residue
was dissolved in 3 ml of CHCl3 and the solution was
layered with 5 ml of ether. After the mixture was stored
(b) H. Werner, T. Rappert, R. Wiedemann, J. Wolf, N. Mahr,
Organometallics 13 (1994) 2721;
(c) H. Werner, R. Wiedemann, N. Mahr, P. Steinert, J. Wolf,
Chem. Eur. J. 2 (1996) 561;
(d) R. Wiedemann, R. Fleischer, D. Stalke, H. Werner, Organo-
metallics 16 (1997) 866.
for 15 h at 8 8C, redꢂviolet crystals were formed which
/
[12] (a) H. Werner, F.J. Garcia Alonso, H. Otto, J. Wolf, Z.
Naturforsch. 43b (1988) 722;
(b) H. Werner, U. Brekau, Z. Naturforsch. 44b (1989) 1438;
were separated from the mother liquor, washed twice
with 1 ml of acetone (0 8C) each and dried; yield 221 mg
(80%), m.p. (dec.) 143 8C. Anal. Found: C, 58.73; H,
(c) T. Rappert, O. Nurnberg, H. Werner, Organometallics 12
¨
(1993) 1359.
7.89. Calc. for C60H98Cl2P4Rh2: C, 59.07; H, 8.10%. IR
1
[13] H. Werner, T. Rappert, Chem. Ber. 126 (1993) 669.
[14] Inter alia: K. Sonogashira, K. Ohga, S. Takahashi, N. Hagihara,
J. Organomet. Chem. 188 (1980) 237; H.B. Fyfe, M. Mlekuz, D.
Zargarian, N.J. Taylor, T.B. Marder, J. Chem. Soc. Chem.
Commun. (1991) 188; W. Beck, B. Niemer, M. Wieser, Angew.
Chem. Int. Ed. Engl. 32 (1993) 923; A.J. Hodge, S.L. Ingham,
A.K. Kakkar, M.S. Khan, J. Lewis, N.J. Long, D.G. Parker, P.R.
Raithby, J. Organomet. Chem. 488 (1995) 205; O. Lavastre, J.
Plass, P. Bachmann, S. Guesmi, C. Moinet, P.H. Dixneuf,
Organometallics 16 (1997) 184; M. Younus, N.J. Long, P.R.
Raithby, J. Lewis, J. Organomet. Chem. 570 (1998) 55; T.
Weyland, K. Costuas, A. Mari, J.-F. Halet, C. Lapinte, Organo-
metallics 17 (1998) 5569; M.I. Bruce, B.C. Hall, B.D. Kelly, P.J.
Low, B.W. Skelton, A.H. White, J. Chem. Soc. Dalton Trans.
(1999) 3719; A. Sakurai, M. Akita, Y. Moro-oka, Organometal-
lics 18 (1999) 3241; R. Dembinski, T. Bartik, B. Bartik, M. Jaeger,
J.A. Gladysz, J. Am. Chem. Soc. 122 (2000) 810; F. Paul, W.E.
Meyer, L. Toupet, H. Jiao, J.A. Gladysz, C. Lapinte, J. Am.
Chem. Soc. 122 (2000) 9405.
(C6H6): n(CÄ
/
CÄ
/
C) 1858 cmꢃ1. H-NMR (400 MHz,
CDCl3): d 7.67 (m, 6H, ortho- and para-H of C6H5),
7.55 (s, 4H, C6H4), 7.08 (m, 4H, meta-H of C6H5), 2.80
(m, 12H, PCHCH3), 1.26 [dvt, Nꢀ
Hz, 72H, PCHCH3]. 13C-NMR (100.6 MHz, CDCl3): d
250.7 [dt, J(Rh,C)ꢀ15.1, J(P,C)ꢀ6.0 Hz, RhÄCÄC Ä
C], 221.7 [dt, J(RhC)ꢀ67.4, J(PC)ꢀ17.1 Hz, RhÄC Ä
CÄC], 153.3, 151.1 (both s, ipso-C of C6H4 and C6H5),
143.8 (s, RhÄCÄCÄC), 129.1, 127.2, 125.7, 122.7 (all s,
C6H4 and C6H5), 23.8 (vt, Nꢀ 19.4 Hz, PCHCH3), 20.1
(s, PCHCH3). 31P-NMR (162.0 MHz, CDCl3): d 36.9
[d, J(Rh,P)ꢀ130.6 Hz].
/
13.2, J(H,H)ꢀ7.2
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
Acknowledgements
[15] H. Werner, J. Wolf, A. Hohn, J. Organomet. Chem. 287 (1985)
¨
395.
We thank the Deutsche Forschungsgemeinschaft
(SFB 347) and the Fonds der Chemischen Industrie
for financial support. Moreover, we acknowledge sup-
port by Mrs R.S. and Mr C.P.K. (elemental analysis and
[16] G. Doisneau, G. Balavoine, T. Fillebeen-Kahn, J. Organomet.
Chem. 425 (1992) 113.
[17] (a) H. Hartmann, H. Honig, Angew. Chem. 69 (1957) 614;
(b) M. LeQuan, P. Cadiot, Bull. Soc. Chim. Fr. (1965) 35.

152
B. Callejas-Gaspar et al. / Journal of Organometallic Chemistry 684 (2003) 144ꢂ152
/
[18] J.L. Bre´fort, J.P. Corriu, P. Gerbier, C. Gue´rin, B.J.L. Henner, A.
Jean, T. Kuhlmann, F. Garnier, A. Yassar, Organometallics 11
(1992) 2500.
[19] B.C. Berris, G.H. Hovakemian, Y.H. Lai, H. Mestdagh, K.P.C.
Vollhardt, J. Am. Chem. Soc. 107 (1985) 5670.
[20] L. Strzelecki, B. Maric, Bull. Soc. Chim. Fr. (1969) 4413.