Bonding isomerism in the η1-P coordination of the P4X3 (X=S, Se) molecules toward 16e rhodium fragments stabilized by tripodal tetradentate ligands

Article abstract of DOI:10.1016/j.jorganchem.2003.09.048

The reaction of tetraphosphorus trichalcogenides P₄X₃ (X=S, Se) with the electronically and coordinatively unsaturated 16 electron systems [(EP₃)Rh]⁺ [E=N, NP₃=tris (2-diphenylphosphanylethyl)amine, (

Full text of DOI:10.1016/j.jorganchem.2003.09.048

Journal of Organometallic Chemistry 689 (2004) 164–169
www.elsevier.com/locate/jorganchem
Bonding isomerism in the g1-P coordination of the P4X3
(X ¼ S, Se) molecules toward 16e rhodium fragments stabilized
by tripodal tetradentate ligands
a
c
a,
*
Isaac de los Rios a,b, Fabrizio Mani , Maurizio Peruzzini , Piero Stoppioni
a
Dipartimento di Chimica, Universitaꢀ di Firenze, via della Lastruccia n. 3, 50019 Sesto Fiorentino, Firenze, Italy
Departamiento de Ciencia de los Materiales e Ing. Met. y Quimica Inorganica, Universidad de Cadiz, Apartado 40, Puerto Real 11510, Spain
b
c
ICCOM CNR, via Madonna del Piano, 50019 Sesto Fiorentino, Firenze, Italy
Received 23 July 2003; accepted 30 September 2003
Abstract
The reaction of tetraphosphorus trichalcogenides P4X3 (X ¼ S, Se) with the electronically and coordinatively unsaturated 16
electron systems [(EP3)Rh]þ [E ¼ N, NP3 ¼ tris(2-diphenylphosphanylethyl)amine, (1); E ¼ P, PP3 ¼ tris(2-diphenylphosphanyl-
ethyl)phosphane, (2)] in tetrahydrofuran affords new tetraphosphorus trichalcogenide derivatives of formula [(EP3)Rh(P4X3)]
CF3SO3 [E ¼ N; X ¼ Se (3), S (5). E ¼ P; X ¼ Se (4), S (6)]. In the P4Se3 derivatives 3 and 4 the heptatomic cage is bound to the metal
through the apical phosphorus atom. The P4S3 derivatives 5 and 6 are obtained as pairs of coordination isomers, with the cage
linked to the metal either through the apical or through one of the basal P atoms; the former isomer is predominant and its amount
depends on the nature of the trans-disposed apical donor (N or P) of the tripodal ligand. The monometal species [(NP3)Rh(g1-
P4S3)]CF3SO3 (5) reacts with 1 affording the dimetal compound [{(NP3)Rh}2(l; g1:1-Papical,-Pbasal-P4S3)](CF3SO3)2, where the cage
exhibits both modes of bonding. All of the compounds have been characterized by 31P NMR spectra and elemental analyses.
Ó 2003 Elsevier B.V. All rights reserved.
Keywords: Rhodium complexes; Tetradentate tripodal ligands; Tetraphosphorustrichalcogenides; 31P NMR spectra
1. Introduction
cage topology is no longer evident [8]. Among the nu-
merous compounds originating from these processes
there are complexes which may be formally considered
as resulting from the initial interaction of the metal
fragment with the intact molecule, followed by stepwise
disruption of P–P and/or P–X bonds (Scheme 1 II–IV)
[9–11].
Nevertheless the primary complexation of the cages
has been described in a few instances and, until recently,
it had been accomplished through the apical phosphorus
[12,13]. Only very recently rhenium complexes have been
described which contain the intact cage bound to the
metal through either the apical or one of the basal P
atoms, the latter being predominant [14]. Soon thereaf-
ter, polymeric weakly coordinated silver–P4S3 adducts
in which the intact cage interacts with the metal through
one sulfur and both the apical and one basal P atoms
have been reported [15]. Due to the several potential
coordination sites, to the E–E and E–X reactive edges as
The mixed cage molecules E4X3 (E ¼ P, As; X ¼ S,
Se) (Scheme 1, I) possess a unique structure exhibiting a
pseudotetrahedral array of pnicogen atoms, where a
homocyclic-E3 unit is connected via three bridging
chalcogen atoms to a single pnicogen in apical position
[1]. The behaviour of such molecules towards transition
metal fragments has been widely studied and a variety of
compounds containing units which originate from the
disruptive fragmentation of the heptatomic cages, par-
ticularly P4S3 and As4S3, have been described [2–7].
Very often the reactions proceed through complicated
multistep thermal and/or photochemical degradation
and aggregation to form metal complexes, mostly in low
yield, containing EmXn groups for which the original
* Corresponding author. Tel.: +39-554573281; fax: +39-554573385.
E-mail address: piero.stoppioni@unifi.it (P. Stoppioni).
0022-328X/$ - see front matter Ó 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2003.09.048

I. de los Rios et al. / Journal of Organometallic Chemistry 689 (2004) 164–169
165
P
S
S
S
S
S
PPh3
P
S
P
P
P
S
Pt
P
P
E
P
P
P
PPh3
Cl
P
S
X
X
E
X
P
P
Ph3P
Ir
Ir
P
E
CO
Cl CO
M
X
P
S
Pt
Pt
E
E
X
P
Ph3P
E
X
P
S
E
P
S
P
PPh3
S
P
S
M = Rh, Ir
S
P
P
S
E = As, P
X = S, Se
Scheme 1.
well as to the faces of different geometries exhibited by
such closo-molecules, the course of the reaction of P4X3
with metal fragments is always difficult to be predicted.
In part this is due to the small number of stable com-
plexes containing the intact molecules; furthermore,
these complexes are either poorly soluble [10,12] or too
reactive to be isolated and characterized by standard
techniques [15]. Hence, systematic studies aimed at
gaining insight into the factors favouring the coordina-
tion and the specific activation modes of such complexes
are sparse and worth to be further expanded.
In continuing our research activity in this field, we
have investigated the reactivity of P4X3 (X ¼ S, Se) to-
wards coordinatively and electronically unsaturated
trigonal pyramidal rhodium fragments, stabilized by
tripodal tetradentate ligands, which are known to be
excellent precursors for the activation of H–H, C–H,
[16] S–H [17] as well as P–P bonds in the P4 molecule
[18]. Thus, the [(EP3)Rh]þ [E ¼ N (1) and P (2)] species
react with P4X3 yielding adducts of formula
[(EP3)Rh(g1-P4X3)]CF3SO3 [E ¼ N; X ¼ Se (3), S (5).
E ¼ P; X ¼ Se (4), S (6)]. Remarkably, while P4Se3 de-
rivative solutions contain the intact cage bound to the
metal fragment through the apical P atom, the P4S3
compounds exhibit a mixture of Rh-g1-Papical and Rh-
g1-Pbasal coordination isomers, the former being pre-
dominant. All of the compounds have been character-
ized by 31P{1H} NMR measurements. The monometal
species [(NP3)Rh(g1-P4S3)]CF3SO3 (5) affords with
[(NP3)Rh]þ (1) a dinuclear compound of formula
[{(NP3)Rh}2(P4S3)](CF3SO3)2 (7) which combines the
Rh-g1-Papical and Rh-g1-Pbasal coordination modes. A
preliminary account on these compounds has been given
[19].
ethyl)amine; E ¼ P, PP3 ¼ tris(2-diphenylphosphanyl-
ethyl)phosphane] [16], react promptly at room
temperature with the stoichiometric amount of P4X3
(X ¼ S, Se) in toluene to yield, after workup, brown
microcrystals of formula [(EP3)Rh(P4X3)]CF3SO3
[E ¼ N, X ¼ Se, (3), S (5); E ¼ P, X ¼ Se (4), S (6)].
The P4S3 derivatives are obtained in fairly higher
yield than the P4Se3 ones (see Section 3). The solids are
stable under inert atmosphere and may be handled in
the air for a limited time; they are soluble in deoxy-
genated CH2Cl2, THF and (CH3)2CO and the solutions
are stable up to ꢀ45 °C, at higher temperatures they
decompose unspecifically providing very complicated
31P NMR spectra which denied simple analysis. The
elemental analysis confirms the formation of 1:1 adducts
between the [(EP3)Rh]þ (1, 2) synthon and the P4X3
molecule. The formation of the compounds is sketched
in Scheme 2, where the labelling scheme used for the
different phosphorus nuclei is also defined. The com-
pounds have been characterized by 31P{1H} NMR
measurements. The NMR data are collected in Table 1
where the data of the uncoordinated P4X3 cages are
provided for comparison. The intensity ratios of the
31P{1H} signals are in accordance with the proposed
formulae.
2.1. 31P NMR characterization of the P4Se3 coordination
compounds
The 31P{1H} NMR spectrum of the tetraphosphorus
triselenide 4 consists of a first-order A3CFM3Z splitting
pattern that yields a quartet for the apical phosphorus
(PC) of the tripodal PP3 ligand and a doublet for the
three terminal atoms (PA); both signals are twice dou-
bled by coupling with the rhodium and with the apical
PF of the cage. The four phosphorus atoms of the
heptatomic cage forms the FM3 part of the spin system
(Table 1). The apical P4Se3 phosphorus atom, PF, which
couples with all the eight NMR active nuclei of the
complex cation, yields a weak multiplet which is mark-
edly downfield shifted with respect to the free molecule.
The three magnetically equivalent PM atoms exhibit a
2. Results and discussion
The rhodium fragments 1 and 2, Scheme 2, which
form by electrophilic attack of CF3SO3Me on the hy-
dride complexes [(EP3)RhH] in THF following methane
elimination [E ¼ N, NP3 ¼ tris(2-diphenylphosphanyl-

166
I. de los Rios et al. / Journal of Organometallic Chemistry 689 (2004) 164–169
+
A
P
Se
P F
PM
P4Se3
THF
A
+
P
PA
Rh
E
M
Se
C
Z
H
P
PM
Se
M
Rh
PA
Z
N
P
E = N (3), P (4)
P
Q
(1)
+
P
P
+
+
A
P
S
P M
P
A
E
O
Rh
P
Rh
Z
E
P
M
A
F S
S
C
PM
P
P4S3
THF
A
(2)
P
S
A
P
PM
A
S
P
E
P
B
Rh
F
C
Q P
Z
S
M
P
A
E = N (5); A = 90%, B = 10%
Scheme 2.
doublet due to the coupling with PF and their chemical
shift is only marginally affected by coordination. The
PP3Rh fragment has chemical shifts and coupling con-
stants that parallel those reported for several trigonal
bipyramidal rhodium(I) complexes with coligands such
as P4, [18] CO, PPh3 [16] and XH (X ¼ S, Se, Te) [17] in
the fifth position. In addition the cage presents NMR
parameters in the range of those observed for the [(tri-
phos)Re(CO)2(g1-Papical-P4Se3)]CF3SO3 complex which
is the only solution characterized compound containing
the intact cage bound to the metal through the apical P
atom, although such isomer formed in low amount [14].
The same coordination geometry consistent with a tri-
gonal bipyramidal geometry around the rhodium(I) and
the intact cage bound through the apical P atom, may be
safely assigned to the NP3 derivative 3 that exhibits an
A3FM3Z spin system in the 31P{1H} NMR spectrum in
accordance with the presence of the NMR inactive ni-
trogen in the apical position of the tripodal ligand. The
31P{1H} NMR spectra of the complexes 3 and 4 do not
change with the temperature in the range investigated
(from )50 to +40, experiment in a sealed NMR tube)
which allows to exclude dynamic behaviour. Due to the
limited solubility of the compounds 77Se NMR spectra
were not recorded.
with the spectra of the P4Se3 derivatives, the presence of
two species, whose ratio depends on the ligand: the most
abundant compound is ꢀ90% for 5 and ꢀ80% for 6.
These data are interpreted as due to the existence of a
pair of coordination isomers which differ for the bond-
ing mode of the P4S3 molecule to the metal fragment, i.e.
through the apical P or through one of the basal P at-
oms (Scheme 2). The 31P,31P COSY NMR spectra of 5
and 6, showing two sets of correlated peaks, support
such interpretation. The major isomer of 6 exhibits a
first order A3CFM3Z spin system (Table 1) and its
spectral features parallel those of the P4Se3 derivative 4;
they are accordingly indicative of a trigonal bipyramidal
coordination around the metal with the apical phos-
phorus of the intact cage occupying the axial position
trans to the apical phosphorus of the PP3 ligand.
The minor isomer exhibits an A3CFM2QZ spin sys-
tem (Table 1) which is consistent with a trigonal bipy-
ramidal geometry around the metal and the P4S3 cage
molecule being bound to the metal through one of the
basal phosphorus atoms. The signals of the tripodal PP3
ligand show minor deviations with respect to those ob-
served in the major isomer and in 4. The four phos-
phorus atoms of the heptatomic cage form the FM2Q
part of the spin system (Table 1). The two equivalent
uncoordinated basal PM atoms yield a broad doublet of
doublets characterized by a large one-bond coupling
(230.0 Hz, Table 1) to PQ and a small one with PF. In-
spection of Table 1 shows also that PQ exhibits a notable
downfield shift with respect to the three equivalent P
atoms of the free cage, whereas PM is only moderately
2.2. 31P NMR characterization of the P4S3 coordination
compounds
The 31P{1H} NMR spectra of the [(EP3)
Rh(P4S3)]CF3SO3 [E ¼ N (5), P (6)] indicate, at variance

I. de los Rios et al. / Journal of Organometallic Chemistry 689 (2004) 164–169
167
Table 1
31P{1H} NMR data of the free and coordinated P4Se3 and P4S3 ligandsa
Compound
Chemical shift, d (ppm)
Coupling constant, J(Hz)
PF
PM
PQ
2J(PF–PM
)
2J(PF–PQ)
1J(PM–PQ)
P4Se3
3 E ¼ Nb
30.7 (q)
)114.1 (d)
)104.3 (d)
)102.3 (d)
)127.3 (d)
)110.2 (d)
)140.8 (dd)
)109.6 (d)
)139.6 (ddm)
)116.6 (dm)
72.0
26.5
29.3
70.0
22.0
65.5
28.0
64.5
102.8 (m)
106.2 (m)
65.1 (q)
4 E ¼ Pb
P4S3
5 E ¼ Nb major isomer
5 minor isomer
6 E ¼ Pc major isomer
6 minor isomer
7b
140.2 (dm)
97.1 (dt)
1J(PF-Rh) 131.0
14.7 (m)
43.5
46.0
238.5
1J(PQ-Rh) 130.0
136.4 (m)
88.9 (dt)
144.9 (dm)
11.7 (m)
14.5 (m)
230.0
205.5
1J(PF-Rh) 119.0
a The NMR spectra were recorded at room temperature (20 °C) with a Varian Gemini g300bb spectrometer. Key: d ¼ doublet, t ¼ triplet,
q ¼ quartet, m ¼ multiplet.
b Spectrum recorded in CD2Cl2.
c Spectrum recorded in (CD3)2CO.
shielded. The uncoordinated PF atom appears as a
doublet of triplets which is slightly downfield shifted
with respect to the free molecule.
The monometal species [(NP3)Rh(g1-P4S3)]CF3SO3
(5) dissolved in THF reacts with 1 to form (Scheme 3),
after workup, the dimetal compound [{(NP3)Rh}2
(l; g1:1-Papical,-Pbasal-P4S3)](CF3SO3)2 (7). The 31P NMR
spectrum of the compound (Table 1) yields an
A3A03FM2QZZ0 spin system, consistent with double
metallation of the P4S3 molecule, which holds the two
non-equivalent [{(NP3)Rh}]þ metal units together and is
responsible for the FM2Q part of the spin system. The
apical and the basal phosphorus atoms of P4S3 bound to
the metals undergo a significant downfield shift upon
coordination; the same trend, although less pronounced,
The 31P{1H} NMR spectra of 5 have been run at
different temperatures (from )80 to + 40 °C) and, re-
markably, the relative amount of the two isomers does
not change, ruling out any exchange process between the
two species. The signals due to the major isomer do not
change in the range of the investigated temperatures,
while those of the minor isomer start broadening below
)10 °C, but do not resolve even at the lowest reached
temperature. Anyhow, the inequivalence of the two
basal uncoordinated phosphorus atoms is suggested by
the broad doubling of their resonance. The reversibility
of this process points to the presence of a dynamic be-
haviour which should feature a low activation barrier
suggesting limited changes in the stereochemistry of the
coordinated cage.
The results obtained from the NMR analysis of iso-
lated samples of 3 and 5, have been combined by 31P
NMR studies on the reaction of 1 and P4X3 in solution.
In fact, the ortho-metallated hydride 1, Scheme 2, ex-
hibits an AMQZ 31P{1H} NMR spectrum with the PQ
atom, involved in a four-membered metalloring, at high
field ()34.08 ppm), well apart from the other phospho-
rus atoms of NP3. Such feature is a valuable probe to
follow the reaction of 1, which easily restores the 16-
electron fragment [(NP3)Rh]þ by addition of suitable
substrates [16]. In the case at hand, the fast disappear-
ance of the high field PQ signal in the reaction of 1 with
P4S3 suggests that the reaction completes to yield the
two isomers in a ratio similar to that observed by dis-
solving 5. In contrast, 31P{1H} NMR analysis of the
reaction of 1 at room temperature with P4Se3 provides
evidence only for the apical isomer and, interestingly,
some ortho-metallated species remains always unre-
acted. These results suggest that the P4Se3 molecule is a
weaker donor with respect to P4S3.
has been observed for the [{(triphos)Re(CO)2}2(l; g1:1
-
P
apical,-Pbasal-P4Se3)]2þ cation [14]. Although polymetal-
lic cluster compounds containing two [9] or three [10]
bridging P4S3 units, formed through activation of a P–P
bond, and tetrametallic compounds containing the
P4Se3 unit, resulting from the cleavage of P–P and P–Se
bonds, [8] have been described, the present dimetal
species exhibits the intact P4S3 molecule in bridging
position between two transition metal fragments, in
analogy with the recently reported P4S3 silver adducts
[15].
The [(NP3)Rh]þ and the [(PP3)Rh]þ fragments are
known to promote the activation of C–H, H–H, [16] S–
H [17] bonds and, significant for the present work, the
[(NP3)Rh]þ moiety may also induce one P–P breaking of
the P4 molecule [18]. Notwithstanding, no insertion of
the metal fragment into a P–P or P–X bond of the cage
occurs in the complexes here reported. This study, in
connection with the results described for rhenium com-
plexes with P4X3, [14] provides experimental evidence
that both types of phosphorus atoms in the P4X3 cage
have comparable coordinating properties and that sub-
tle geometric and electronic effects due to the metal-li-
gand fragments determine whether the apical or the
basal donor is preferred for coordination. The P–X or
P–P activation of the sterically demanding P4X3 cage

168
I. de los Rios et al. / Journal of Organometallic Chemistry 689 (2004) 164–169
N
P
+
P
S
S
P
P
P
AP
Rh
P
P
P
A
Rh
N
P
A
S
P
F
P
S
S
P
+ [(NP3)Rh]+
THF
(1)
S
P
M
M
PQ
P
+
S
S
P
P
P
Rh
N
PA'
A'
PA'
S
Rh
P
N
P
P
Scheme 3.
should involve a trigonal pyramidal ! pseudooctahe-
dral rearrangement of the metal fragment with an ex-
cessive opening of one of the P–Rh–P angles formed by
peripheral P atoms of the tripodal ligand [20].
solved in THF (30 cm3). The solution was stirred for 20
min and then added to P4Se3 (97 mg, 0.27 mmol) dis-
solved in toluene (30 cm3). The resulting solution was
stirred for 2 h while turning dark red; it was concen-
trated to ꢀ35 cm3 at reduced pressure and then cooled
to )20 °C. Brown crystals separated within seven days.
The solid was collected by filtration, washed with tolu-
ene, petroleum ether and dried. Yield 55%. C43H42
F3NO3P7RhSSe3 (1266.4). Calc.: C, 40.8; H, 3.34; N,
1.10. Found: C, 40.6; H, 3.30; N, 1.06%. 31P{1H} NMR
(CD2Cl2, 298 K): 33.8 (3P, PA, dd, 1J(PA-Rh) 122.5,
2J(PA–PF) 16.5).
3. Experimental section
3.1. General
All reactions and manipulations were performed
under an atmosphere of dry oxygen-free argon. THF
and toluene were freshly distilled from sodium. The 31P-
{1H} NMR spectra were measured on a Varian Gemini
g300bb spectrometer, equipped with a variable-temper-
ature unit, operating at 121.46 MHz. Chemical shifts are
relative to H3PO4 85% as external standards at 0.00
ppm. Analytical data for carbon and hydrogen were
obtained from the Microanalytical Laboratory of the
Department of Chemistry of the University of Firenze.
The hydride complexes [(NP3)RhH] and [(PP3)RhH]
were prepared according to the literature methods [16].
P4S3 was purchased from Fluka AG and recrystallized
from toluene prior the use; P4Se3 was prepared by
melting red phosphorus and grey selenium as described
in the literature [21]. CF3SO3Me (Aldrich) was used as
purchased and stored at 0 °C. The 31P{1H} NMR data
of the tripodal ligands in the compounds are reported in
3.2.2. [(PP3)Rh(P4Se3)]CF3SO3(4)
The compound was prepared through the procedure
described for 3 by adding CF3SO3Me to [(PP3)RhH].
Yield 50%. C43H42F3O3P8RhSSe3 (1283.4). Calc.: C,
40.2; H, 3.30; P, 19.3. Found: C, 39.8; H, 3.20; P, 19.0%.
31P{1H} NMR (CD2Cl2, 298 K): d 156.4 (1P, PC, ddq,
2
2
1J(PC-Rh) 127.0, J(PC–PA) 20.0, J(PC–PF) 36.0), 53.4
1
2
(3P, PA, ddd, J(PA-Rh) 131.5, J(PA–PF) 17.0).
3.2.3. [(NP3)Rh(P4S3)]CF3SO3,(5)
1 (0.3 mmol), prepared as described for the synthesis
of 3, was added at room temperature to the stoichiom-
etric amount of P4S3 in THF (25 cm3). Toluene (10 cm3)
was added and the resulting dark brown solution was
concentrated at reduced pressure and cooled to )20 °C.
The dark red crystals which separated within seven days
were collected, washed with toluene, petroleum ether
and dried.
1
this section. The uninformative H and 13C{1H} signals
of the ligands are not reported.
3.2. Syntheses
Yield 85%. C43H42F3NO3P7RhS4 (1125.7). Calc.: C,
45.9; H, 3.76; N, 1.24; P, 19.3. Found: C, 45.4; H, 3.54;
N, 1.20; P, 19.2%. 31P{1H} NMR (CD2Cl2, 298 K);
major isomer: d 32.4 (3P, PA, dd, 1J(PA-Rh) 134.5,
3.2.1. [(NP3) Rh(P4Se3)]CF3SO3, (3)
Neat CF3SO3Me (0.30 mmol) was added at room
temperature to [(NP3)RhH] (204 mg, 0.27 mmol) dis-

I. de los Rios et al. / Journal of Organometallic Chemistry 689 (2004) 164–169
169
1
2J(PA–PF) 35.5). Minor isomer: 33.8 (3P, PA, dd, J(PA-
Rh) 135.0, J(PA–PQ) 35.5).
References
2
[1] J.G. Riess, in: A.H. Cowley (Ed.), Rings, Cluster and Polymers,
vol. 232, ACS Symposium Series, 1983, p. 17.
[2] M. Di Vaira, P. Stoppioni, M. Peruzzini, Comments Inorg. Chem.
11 (1990) 1.
3.2.4. [(PP3)Rh(P4S3)]CF3SO3,(6)
Complex 6 was prepared as described above for 5 by
using 2 (0.3 mmol) in place of 1. Yield 80%.
C43H42F3O3P8RhS4 (1142.7). Calc.: C, 45.2; H, 3.70; S,
11.2. Found: C, 44.5; H, 3.62; S, 10.5%. 31P{1H}NMR
((CD3)2CO, 298 K); maior isomer: d 158.6 (1P, PC, ddq,
[3] M. Di Vaira, P. Stoppioni, Coord. Chem. Rev. 120 (1992) 259.
[4] J. Wachter, Angew. Chem., Int. Ed. 37 (1998) 751.
[5] L.Y. Goh, Coord. Chem. Rev. 185/186 (1999) 257.
[6] O.J. Scherer, Chem. Unserer Zeit (2000) 374.
[7] K.H. Whitmire, Adv. Organomet. Chem. 42 (1998) 2.
[8] L.Y. Goh, W. Chen, R.C.S. Wong, Organometallics 18 (1999)
306.
2
2
1J(PC-Rh) 120.5, J(PC–PA) 22.0, J(PC–PF) 32.5), 52.7
1
2
(3P, PA, ddd, J(PA-Rh) 133.0, J(PA–PF) 36.0). Minor
1
2
[9] C.A. Ghilardi, S. Midollini, A. Orlandini, Angew. Chem., Int. Ed.
Engl. 22 (1983) 790.
isomer: 161.8 (1P, PC, ddq, J(PC-Rh) 102.5, J(PC–PA)
21.0, 2J(PC–PQ) 39.0), 51.0 (3P, PA, ddd, 1J(PA-Rh)
[10] M. Di Vaira, M. Peruzzini, P. Stoppioni, J. Chem. Soc., Dalton
Trans. (1985) 291.
2
132.5, J(PA–PQ) 41.0).
[11] M. Di Vaira, M. Peruzzini, P. Stoppioni, J. Chem. Soc., Chem
Commun. (1983) 904;
3.2.5. [{(NP3)Rh}2(P4S3)](CF3SO3)2(7)
The [(NP3)Rh]þ fragment (1) (0.25 mmol), prepared
as described for the synthesis of (3), was added at room
temperature to a solution of 3 (250 mg; 0.22 mmol) in
THF (20 cm3). The resulting solution was stirred for 2 h
and toluene (15 cm3) was added. Brown microcrystals
were obtained by slowly evaporating the resulting so-
lution. The solid was filtered out and washed with tol-
uene and light petroleun before being dried. Yield 60%.
C86H84F6N2O6P10Rh2S5 (2031.3). Calc.: C, 50.8; H,
4.17; N, 1.38; S, 7.89. Found: C, 50.2; H, 4.07; N, 1.28;
S, 7.50%. 31P{1H}NMR (CD2Cl2, 298 K): d 34.1 (3P,
M. Di Vaira, B.E. Mann, M. Peruzzini, P. Stoppioni, Inorg.
Chem. 27 (1988) 3725.
[12] M. Di Vaira, M. Peruzzini, P. Stoppioni, Inorg. Chem. 22 (1983)
2196;
M. Di Vaira, M. Peruzzini, P. Stoppioni, J. Organomet. Chem.
258 (1983) 373.
[13] A.W. Cordes, R.D. Joyner, R.D. Shores, E.D. Dill, Inorg. Chem.
13 (1974) 132.
[14] E. Guidoboni, I. de los Rios, A. Ienco, L. Marvelli, C. Mealli, A.
Romerosa, R. Rossi, M. Peruzzini, Inorg. Chem. 41 (2002)
659.
[15] A. Adolf, M. Gonsior, I. Krossing, J. Am. Chem. Soc. 124 (2002)
7111.
[16] C. Bianchini, D. Masi, A. Meli, M. Peruzzini, F. Zanobini, J. Am.
Chem. Soc. 110 (1988) 6411.
1
2
0
PA, dd, J(PA-Rh) 134.0, J(PA–PF) 35.0), 33.7 (3P, PA ,
1
2
0
dd, J(PA -Rh) 135.5, J(PA –PQ) 37.5).
0
[17] M. Di Vaira, M. Peruzzini, P. Stoppioni, Inorg. Chem. 30 (1991)
1001.
[18] M. Di Vaira, M.P. Ehses, M. Peruzzini, P. Stoppioni, Eur.
J. Inorg. Chem. (2000) 2193.
Acknowledgements
[19] M. Di Vaira, I. de los Rios, F. Mani, M. Peruzzini, P. Stoppioni,
Inorg. Chem. Commun. 5 (2002) 879.
We acknowledge financial support by the Italian
ꢀ
Thanks are expressed to INTAS for supporting this re-
search (project 00-00018).
[20] C. Mealli, C.A. Ghilardi, A. Orlandini, Coord. Chem. Rev. 120
(1992) 361.
[21] M. Peruzzini, P. Stoppioni, Gazz. Chim. Ital. 118 (1988) 581.
Ministero dellÕistruzione, dellÕUniversitae della Ricerca.