Bis(diphenylphosphino)methylamine as chelate ligand in pentamethylcyclopentadienylrhodium(III) and iridium(III) compexes. Crystal structure of [(η5-C5Me5)RhC1{η2-P, P′-(PPh2)2NMe}]BF4<

Article abstract of DOI:10.1016/S0022-328X(02)02036-3

Reactions of the dimers [{(η⁵-C₅Me₅)MCl (μ-Cl)}₂] (M = Rh, Ir) with the ligand NMe(PPh₂)₂ in 1:2 molar ratio afford the mononuclear cationic complexes (M = Rh 3, Ir 4), can be prepared by N

Full text of DOI:10.1016/S0022-328X(02)02036-3

Journal of Organometallic Chemistry 665 (2003) 7ꢁ12
/
www.elsevier.com/locate/jorganchem
Note
Bis(diphenylphosphino)methylamine as chelate ligand in penta-
methylcyclopentadienylrhodium(III) and iridium(III) complexes.
Crystal structure of [(h5-C5Me5)RhCl{h2-P,P?-(PPh2)2NMe}]BF4
Mauricio Valderrama a,*, Rau´l Contreras a, Daphne Boys b
a
´ ´ ´ ´
Departamento de Quımica Inorganica, Facultad de Quımica Pontificia, Universidad Catolica de Chile, Casilla 306, Santiago 22, Chile
b
´ ´ ´
Departamento de Fısica, Facultad de Ciencias Fısicas y Matematicas, Universidad de Chile, Casilla 487-3, Santiago, Chile
Received 15 September 2002; accepted 15 October 2002
Abstract
Reactions of the dimers [{(h5-C5Me5)MCl(m-Cl)}2] (Mꢀ
mononuclear cationic complexes [(h5-C5Me5)MCl{h2-P,P?-(Ph2P)2NMe}]Cl (Mꢀ
C5Me5)MCl{h2-P,P?-(Ph2P)2NMe}]I (Mꢀ
Rh 3, Ir 4), can be prepared by N-functionalization of co-ordinated dppa ligand in
complexes [(h5-C5Me5)MCl{h2-P,P?-(Ph2P)2NH}]BF4. The tetrafluoroborate derivatives, [(h5-C5Me5)MCl{h2-P,P?-
4 with AgBF4 in acetone. All the compounds
/
Rh, Ir) with the ligand NMe(PPh2)2 in 1:2 molar ratio afford the
/
Rh 1, Ir 2). Similar iodide complexes, [(h5-
/
(Ph2P)2NMe}]BF4 (Mꢀ
/
Rh 5, Ir 6) are prepared by reaction of complexes 1ꢁ
/
described are characterised by microanalysis, IR and NMR (1H, 31P{1H}) spectroscopy. The crystal structure of complex 5 is
determined by X-ray diffraction methods. The complex exhibits a pseudo-octahedral molecular structure with a C5Me5 group
occupying three co-ordination positions and a bidentate chelate P,P?-bonded ligand and a chloride atom completing the co-
ordination sphere.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Rhodium; Iridium; Bis(diphenylphosphino)methylamine complexes; Diphosphazane complexes; Crystal structures
1. Introduction
In contrast to the great interest on the ligand
behaviour and reactivity of co-ordinated dppa, little
attention has been paid to the co-ordination chemistry
of alkyl or aryl-substituted phosphinoamines
Transition-metal chemistry of bis(diphenylphosphi-
no)amine [dppa, NH(PPh2)2] has been the subject of
increasing interest due to its versatile co-ordination
behaviour [1]. In a similar form to the widely used
ligand bis(diphenylphosphino)methane (dppm), dppa
can bind to metal centres as monodentate [2], chelate
bidentate [3] or bridging ligand [4].
Interestingly, the greater acidity of the NH proton of
the co-ordinated dppa ligand than that of the CH2
protons of dppm, may facilitate the N-functionalization
reactions. Thus, it has been recently described the N-
derivatization of the chelate or bridging dppa ligand in
mononuclear complexes [2b,2c] or heterobinuclear clus-
ters [4e,4f] affording the corresponding ethyl or methyl-
dppa derivatives.
NR(PPh2)2 (Rꢀ
Me, Ph, iPr) [5]. Although some recent
/
studies demonstrated that N-substitution increases the
chelate behaviour of the ligand, probably by constraint
of the PNP angle due to steric effects, we found some
examples where the NMe(PPh2)2 ligand acts as bridging
ligand [5b,6].
Following our interest in the co-ordination behaviour
of short-bite bidentade phosphine ligands, we report in
this paper the synthesis of cationic rhodium and iridium
compounds containing NMe(PPh2)2 (dppma) as chelate
ligand. The complexes were prepared by direct reaction
of dppma with the dimer [{(h5-C5Me5)MCl(m-Cl)}2] or
by N-functionalization of the co-ordinated dppa ligand.
The crystal structure of [(h5-C5Me5)RhCl{h2-P,P?-
(Ph2P)2NMe}]BF4, determined by single-crystal X-ray
diffraction, is also reported.
* Corresponding author. Fax: ꢂ
E-mail address: jmvalder@puc.cl (M. Valderrama).
/56-2-686-4744
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 2 0 3 6 - 3

8
M. Valderrama et al. / Journal of Organometallic Chemistry 665 (2003) 7ꢁ12
/
2. Experimental
2.2.2. Synthesis of [(h5-C5Me5)MCl{h2-P,P?-
(Ph2P)2NMe}]I (MꢀRh 3, Ir 4)
/
A mixture of complex [(h5-C5Me5)MCl{h2-P,P?-
(Ph2P)2NH}]BF4 (0.18 mmol) and potassium tert-but-
oxide (20.2 mg; 0.18 mmol) in dry CH2Cl2 (20 ml) was
stirred at r.t. for 1 h. The solution was evaporated to
dryness and the solid residue extracted with C6H5CH3.1
To this solution, methyl iodide (1 ml; 16 mmol) was
added and the mixture was heated under reflux for 1 h.
The yellow solid formed was filtered, washed with Et2O
and dried under vacuum. Complex 3: Yield: 70 mg, 46%.
Anal. Found: C, 52.5; H, 4.7; N, 1.6. C35H38ClINP2Rh
2.1. General
All reactions were carried out under purified nitrogen
using Schlenk-tube techniques. Solvents were dried,
distilled, and stored under a nitrogen atmosphere. The
starting compounds [{(h5-C5Me5)MCl(m-Cl)}2] (Mꢀ
/
Rh, Ir) and [(h5-C5Me5)MCl{h2-P,P?-(Ph2P)2NH}]BF4
were prepared by published procedures [3b,7]. The
ligands NH(PPh2)2 and NMe(PPh2)2 were prepared
following the method of Wang et al. [8]. Elemental
analyses (C, H, N) were carried out with a Fisons EA
1108 microanalyzer. FTIR spectra were recorded on a
Bruker Vector-22 spectrophotometer using KBr pellets.
The NMR spectra were recorded on a Bruker AC-200P
spectrometer. Chemical shifts are reported in ppm
relative to SiMe4 (1H) and 85% H3PO4 (31P, positive
shifts downfield) as internal and external standards,
respectively.
1
requires: C, 52.6; H, 4.8; N, 1.8%. H-NMR (CDCl3,
4
23 8C): d 1.62 [t, 15H, C5Me5, J(PH)ꢀ
/
4.2 Hz], 2.9 [t,
3H, Me, 3J(PH)ꢀ
31P{1H}-NMR (CDCl3, 23 8C): d 66.7 [d, J(PRh)ꢀ
121.9 Hz]. FTIR (KBr, cmꢃ1): n(CH, aliphatic) 2936
CH3) 839 vs. Complex 4: Yield: 92 mg, 60%.
/
9.7 Hz], 7.3ꢁ
/
7.8 (m, 20H, Ph).
1
/
m, g(NÃ
/
Anal. Found: C, 47.8; H, 4.4; N, 1.7. C35H38ClIIrNP2
1
requires: C, 47.3; H, 4.3; N, 1.6%. H-NMR (CDCl3,
4
23 8C): d 1.70 [t, 15H, C5Me5, J(PH)ꢀ
/2.81 Hz], 2.93
3
[t, 3H, Me, J(PH)ꢀ
/
10.1 Hz], 7.20ꢁ
/
7.80 (m, 20H, Ph).
31P{1H}-NMR (CDCl3, 23 8C): d 33.5 [s]. FTIR (KBr,
cmꢃ1): n (CH, aliphatic) 2912, 2983 w, g(NÃ
vs.
/
CH3) 827
2.2. Preparation of complexes
2.2.3. Synthesis of [(h5-C5Me5)MCl{h2-P,P?-
(Ph2P)2NMe}]BF4 (MꢀRh 5, Ir 6)
The complexes could be prepared by either of the two
methods described below.
/
2.2.1. Synthesis of [(h5-C5Me5)MCl{h2-P,P?-
(Ph2P)2NMe}]Cl (MꢀRh 1, Ir 2)
/
To a solution of the binuclear complex [{(h5-
C5Me5)MCl(m-Cl)}2] (0.08 mmol; Rh, 50 mg; Ir, 64
mg) in C6H5CH3 (10 ml) was added a solution of
NMe(PPh2)2 (64 mg; 0.16 mmol) in C6H5CH3 (10 ml).
After stirring the mixture for 1 h at room temperature
(r.t.) the solution was concentrated to a small volume.
Yellow solids were obtained by addition of n-hexane.
Complex 1: Yield: 109 mg, 96%. Anal. Found: C, 59.0;
H, 5.1; N, 2.0. C35H38Cl2NP2Rh requires: C, 59.3; H,
a)
A
mixture of the binuclear complex [{(h5-
C5Me5)MCl(m-Cl)}2] (0.08 mmol; Rh, 50 mg; Ir,
64 mg), NMe(PPh2)2 (64 mg; 0.16 mmol) and
NaBF4 (18 mg; 0.16 mmol) in C3H6O (20 ml) was
stirred for 1 h at r.t. The precipitated NaCl was
removed by filtration and the solution was evapo-
rated to a small volume. The complexes were
crystallised by careful addition of Et2O (5: yield:
109 mg, 90%; 6: yield: 135 mg, 84%).
1
5.4; N, 2.0%. H-NMR (CDCl3, 23 8C): d 1.67 [t, 15H,
C5Me5, 4J(PH)ꢀ
/
4.2 Hz], 2.91 [t, 3H, Me, 3J(PH)ꢀ
/
9.7
7.80 (m, 20H, Ph). 31P{1H}-NMR (CDCl3,
23 8C): d 66.9 [d, 1J(PRh)ꢀ
120 Hz]. FTIR (KBr,
CH3) 841 vs.
b) To a suspension of complex 3 or 4 (0.1 mmol) in
C3H8O (15 ml) was added AgBF4 (20 mg; 0.1
mmol). After stirring the mixture at r.t. for 1 h,
the solid AgCl formed was filtered off and the
solution evaporated to a small volume. The com-
plexes were precipitated by addition of Et2O (5:
Yield 72 mg, 95%; 6: Yield 78 mg, 92%).
Hz], 7.25ꢁ
/
/
cmꢃ1): n(CH, aliphatic) 2984 w, g(NÃ
/
Complex 2: Yield: 70 mg, 55%. Anal. Found: C, 52.8; H,
4.9; N, 1.8. C35H38Cl2IrNP2 requires: C, 52.7; H, 4.8; N,
1.8%. 1H-NMR (CDCl3, 23 8C): d 1.70 [t, 15H, C5Me5,
4J(PH)ꢀ
7.20ꢁ
d 33.5 [s]. FTIR (KBr, cmꢃ1): n(CH, aliphatic) 2914 w,
g(NÃCH3) 817 vs.
/
2.8 Hz], 2.92 [t, 3H, Me, J(PH)ꢀ
/10.1 Hz],
3
/
7.80 (m, 20H, Ph). 31P{1H}-NMR (CDCl3, 23 8C):
Complex 5: redꢁorange crystals. Anal. Found: C,
/
55.7; H, 5.1; N, 1.7. C35H38BClF4NP2Rh requires: C,
1
55.3; H, 5.0; N, 1.8%. H-NMR (CDCl3, 23 8C): d 1.63
/
1
For the iridium compound, the intermediate neutral complex [(h5-C5Me5)MCl{h2-P,P-(Ph2P)2N}] was obtained by evaporation of the
C6H5CH3 solution to a small volume and cooling to ꢃ20 8C [yield: 122 mg, 91%. Anal. Found: C, 53.8; H, 4.5; N, 1.8. C34H35ClIrNP2 requires: C,
54.6; H, 4.7; N, 1.9%. 1H-NMR (CDCl3, 23 8C): d 1.47 [t, 15H, C5Me5, 4J(PH)ꢀ 7.80 (m, 20H, Ph). 31P{1H}-NMR (CDCl3, 23 8C): d
2.5 Hz], 7.20ꢁ
25.08 (s)].
/
/
/
ꢃ/

M. Valderrama et al. / Journal of Organometallic Chemistry 665 (2003) 7ꢁ
/12
9
[t, 15H, C5Me5, 4J(PH)ꢀ
/
4.2 Hz], 2.91 [t, 3H, Me,
7.80 (m, 20H, Ph). 31P{1H}-
Table 1
Crystal data and structure refinement for complex [(h5-
3J(PH)ꢀ
/
9.7 Hz], 7.20ꢁ
/
C5Me5)RhCl{h2-P,P?-(Ph2P)2NMe}]BF4 (5)
1
NMR (CDCl3, 23 8C): d 66.9 [d, J(PRh)ꢀ
/
122 Hz].
FTIR (KBr, cmꢃ1): n(CH, aliphatic) 2919 w, g(NÃ
CH3) 837 s, n(BF4) 1050 vs,br.
/
Empirical formula
Formula weight
Temperature (K)
C35H38BClF4NP2Rh
759.77
297(2)
Complex 6: yellow crystals. Anal. Found: C, 49.8; H,
4.7; N, 1.6. C35H38BClF4IrNP2 requires: C, 50.0; H, 4.5;
N, 1.7%. 1H-NMR (CDCl3, 23 8C): d 1.67 [t, 15H,
˚
Wavelength (A)
MoꢁKa (0.71073)
/
Crystal system
Space group
Unit cell dimensions
Orthorhombic
P212121
C5Me5, 4J(PH)ꢀ
Hz], 7.20ꢁ
23 8C): d 33.7 [s]. FTIR (KBr, cmꢃ1): n(CH, aliphatic)
2905 w, g(NÃCH3) 831 s, n(BF4) 1050 vs,br.
/
2.8 Hz], 2.9 [t, 3H, Me, 3J(PH)ꢀ
/
10.1
7.70 (m, 20H, Ph). 31P{1H}-NMR (CDCl3,
˚
/
a (A)
12.045(2)
15.060(3)
18.815(3)
3413.0(10)
4
˚
b (A)
˚
c (A)
/
3
Volume (A )
˚
Z
2.3. X-ray crystallography of complex [(h5-
C5Me5)RhCl{h2-P,P?-(Ph2P)2NMe}]BF4 (5)
Dcalc (Mg mꢃ3
)
1.479
0.720
Absorption coefficient (mmꢃ1
F(000)
Crystal size (mm)
)
1552
0.30ꢄ0.14ꢄ0.07
Suitable crystals for X-ray structure determination
were obtained from a slow diffusion of diethyl ether into
a solution of complex 5 in acetone. Intensity data were
collected at room temperature on a Siemens R3m/V
u Range for data collection (8) 1.73ꢁ
/27.57
Index ranges
05h 515, ꢃ195k 58,
05l 524
4680
Reflections collected
Independent reflections
Refinement method
4595 (Rintꢀ0.0312)
Full-matrix least-squares on F2
4595/0/398
diffractometer with graphite monochromated Moꢁ
/
Ka
˚
radiation (lꢀ
/
0.71073 A) in the u ꢁ
/
2u scan mode.
Data/restraints/parameters
Final R indices [I ꢀ2s(I)]
R indices (all data)
Semiempirical corrections based on c scans were
applied for absorption. The structure was solved by
Patterson and refined on F2 by full-matrix least-squares
calculations with SHELXL-97 [9]. A riding model was
R1ꢀ0.0507, wR2ꢀ0.0781
R1ꢀ0.1128, wR2ꢀ0.0893
ꢃ0.01(5)
Absolute structure parameter
Goodness-of-fit on F2
0.815
Largest difference peak and hole 0.452 and ꢃ0.507
applied to H atoms, placed at calculated positions with
˚
0.96 A and isotropic UꢀUeq of attached atoms.
ꢃ3
˚
(e A
)
CÃ
/
Hꢀ
/
/
Anion BF4 was refined as a rigid group. The absolute
structure of the compound could be determined with
spectroscopy. Their solid-state IR spectra in KBr pellets
show the characteristic absorption’s n(CH, aliphatic)
Flack parameter equal to ꢃ0.01(5). Relevant crystal
data and refinement parameters are summarised in
Table 1.
/
and g(NÃ
/
CH3) of the co-ordinated dppma ligand [5b].
The H-NMR spectra of rhodium complexes (1, 3), in
1
deuterated chloroform, exhibit two triplet resonances at
d 1.67 [4J(PH)ꢀ
ppm attributed to the C5Me5 and Me groups, respec-
/
4.2 Hz] and 2.91 [3J(PH)ꢀ
9.7 Hz]
/
3. Results and discussion
tively. The 31P{1H}-NMR spectra show a doublet
resonance at d 66.9 [1J(PRh)ꢀ
/
120 Hz] ppm. On the
other hand, the H-NMR spectra of iridium complexes
(2, 4), exhibit two triplet resonances at d 1.70 [4J(PH)ꢀ
The synthetic routes to the complexes are summarised
in Scheme 1. The binuclear complex [{(h5-
1
/
C5Me5)MCl(m-Cl)}2] (Mꢀ
/
Rh, Ir) reacts in toluene
2.8 Hz] and 2.92 [3J(PH)ꢀ
10.1 Hz] for the C5Me5 and
/
solution with
bis(diphenylphosphino)methylamine
Me groups. The 31P{1H} NMR spectra show a singlet
resonance at d 33.5 ppm.
[dppma, NMe(PPh2)2] in 1:2 molar ratio, by cleavage
of the chloride bridges, to give cationic compounds of
the type [(h5-C5Me5)MCl{h2-P,P?-(PPh2)2NMe}]Cl
Only in the deprotonation reaction of the iridium
complex [(h5-C5Me5)IrCl{h2-P,P?-(PPh2)2NH}]BF4 we
could isolate the intermediate neutral complex [(h5-
C5Me5)IrCl{h2-P,P?-(PPh2)2N}] as a dark-orange solid,
by evaporation of the toluene solution and cooling to
(MꢀRh 1, Ir 2).
/
Similar compounds can be prepared by N-derivatiza-
tion of the co-ordinated dppa ligand. Thus, the reaction
of the cationic complexes [(h5-C5Me5)MCl{h2-P,P?-
ꢃ
20 8C. As expected, in the 31P{1H}-NMR spectrum
the singlet resonance of the equivalent phosphorus
/
(PPh2)2NH}]BF4 (MꢀRh, Ir) [3b] with potassium
/
tert-butoxide in dry dichloromethane causes the depro-
tonation of the co-ordinated dppa ligand. The neutral
intermediate formed readily reacts with methyl iodide in
toluene solution to give the cationic complexes [(h5-
atoms of the anionic bidentate ligand is shifted to high
field, d ꢃ25.08 ppm, relative to the starting cationic
/
complex (d 16.8 ppm). In the case of the rhodium
compound, the reaction with potassium tert-butoxide
always gives a dark-red solution for which all the
attempts to isolate a pure complex were unsuccessful.
C5Me5)MCl{h2-P,P?-(Ph2P)2NMe}]I(Mꢀ
/
Rh 3, Ir 4).
4 were isolated as stable yellow solids
and characterised by elemental analysis, IR and NMR
Complexes 1ꢁ
/

10
M. Valderrama et al. / Journal of Organometallic Chemistry 665 (2003) 7ꢁ
/12
Scheme 1. (i) dppa, AgBF4; (ii) dppma; (iii) Kt BuO, MeI; (iv) AgBF4.
When the deprotonation reaction was carried out in
deuterated dichloromethane
NMR spectra of these complexes are similar to those
above described for complexes 1ꢁ
4. The 1H-NMR
spectra of complex 5 and 6 exhibit the expected triplet
resonances assigned to the C5Me5 and MeN groups, and
the 31P{1H}-NMR spectra showed a doublet and a
singlet resonance, respectively.
/
a
doublet resonance
100.0 Hz] was observed
centred at d 9.1 ppm [1J(PRh)ꢀ
/
in the 31P{1H}-NMR spectrum, demonstrating the
formation of the corresponding neutral complex in
solution (starting complex d 49.8 ppm, 1J(PRh)ꢀ
118.4 Hz).
/
Complexes 1ꢁ
/
4 reacted with the stoichiometric
3.1. X-ray diffraction study of [(h5-C5Me5)RhCl{h2-
P,P?-(Ph2P)2NMe}]BF4 (5)
amount of AgBF4 in acetone solution to form the
corresponding tetrafluoroborate derivatives [(h5-
C5Me5)MCl{h2-P,P?-(PPh2)2NMe}]BF4 (Mꢀ
/
Rh 5, Ir
The molecular structure of the cation of complex 5,
including the atom numbering scheme, is shown in Fig.
1. The most relevant bond distances and angles are
collected in Table 2. In this complex, the rhodium atom
exhibits a distorted octahedral co-ordination sphere
with the pentamethylcyclopentadienyl ligand formally
occupying three octahedral sites. A chloride atom and a
chelate bidentate ligand bonded to the metal centre
through two phosphorus atoms complete the co-ordina-
tion sphere.
6). Alternatively, complexes 5 and 6 can be prepared by
reaction of the dimeric complexes [{(h5-C5Me5)MCl(m-
Cl)}2] with the ligand dppma in acetone, in the presence
of sodium tetrafluoroborate. These compounds were
isolated as stable microcrystalline redꢁorange (5) or
/
yellow (6) solids. Their IR spectra in KBr pellets show
the characteristic bands of the co-ordinated dppma
ligand together with a broad band at 1050 cmꢃ1
corresponding to the uncoordinated BF4 anion. The

M. Valderrama et al. / Journal of Organometallic Chemistry 665 (2003) 7ꢁ
/12
11
˚
values 1.711(3) and 1.702(3) A reported for the free
N bond distances
are comparable to those found in some palladium and
dppma ligand [4h]. However, the PÃ
/
platinum complexes, [PdCl2(dppma)] [average 1.688(4)
˚
A], [Pt(CN)2(dppma)] [average 1.690(1) A] and
˚
˚
[PtCl2(dppma)] [average 1.6845(6) A] [5e]. On the other
hand, the P(1)ÃNÃP(2) angle [102.6(4)8] is smaller than
the PÃNÃP angle of the free dppma ligand [114. 58(14)8]
/
/
/
/
[4h] and is similar to those found in the related
complexes [PdCl2(dppma)] [100.4(2)8], [Pt(CN)2-
(dppma)] [100.0(6)8] and [PtCl2(dppma)] [102.4(3)8]
[5e]. Angles involving the P atoms reflect a tetrahedral
geometry, and it is noteworthy that the P(1)Ã
and RhÃPÃN are smaller than the RhÃPÃC and NÃ
C angles.
/
NÃ
/
P(2)
/
/
/
/
/
PÃ
/
Fig. 1. ORTEP view of the structure of the complex cation 5 with atom
numbering scheme (thermal ellipsoids at 40% probability level).
4. Conclusions
Table 2
Selected bond lengths (A) and angles (8) for complex [(h5-
In this communication we have described the synth-
compounds
˚
esis
of
[(h5-C5Me5)MCl{h2-P,P?-
Rh 5, Ir 6). We have shown
C5Me5)RhCl{h2-P,P?-(Ph2P)2NMe}]BF4 (5)
(Ph2P)2NMe}]BF4 (Mꢀ
/
Bond lengths
that in the complexes [(h5-C5Me5)MCl{h2-P,P?-
RhÃCl
2.376(2)
2.297(2)
2.303(2)
1.679(7)
1.682(7)
1.469(9)
1.801(9)
1.815(9)
RhÃC(1)
2.183(10)
2.216(8)
2.196(9)
2.208(9)
2.239(9)
1.810(9)
1.816(8)
(PPh2)2NH}]BF4 (MꢀRh, Ir), the amine proton of
/
RhÃP(1)
RhÃP(2)
P(1)ÃN
RhÃC(2)
the co-ordinated dppa ligand is easily removed by bases
to form neutral complexes, in which the N-atom
possesses a sufficient electron density to form N-methyl
derivatives (3, 4) by reaction with methyl iodide.
RhÃC(3)
RhÃC(4)
RhÃC(5)
P(2)ÃC(211)
P(2)ÃC(221)
P(2)ÃN
NÃC(1N)
P(1)ÃC(111)
P(1)ÃC(121)
Bond angles
5. Supplementary material
ClÃRhÃP(1)
86.05(8) ClÃRhÃP(2)
69.55(9) P(1)ÃNÃP(2)
88.85(9)
102.6(4)
121.6(3)
118.6(3)
93.6(3)
P(1)ÃRhÃP(2)
RhÃP(1)ÃC(111)
RhÃP(1)ÃC(121)
RhÃP(1)ÃN
P(1)ÃNÃC(1N)
NÃP(1)ÃC(111)
NÃP(1)ÃC(121)
119.3(3)
122.5(3)
93.9(3)
RhÃP(2)ÃC(211)
RhÃP(2)ÃC(221)
RhÃP(2)ÃN
Crystallographic data for the structural analysis has
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 193540 for compound 5.
Copies of this information may be obtained free of the
charge from The Director, CCDC, 12 Union Road,
129.1(6)
111.1(4)
106.7(4)
P(2)ÃNÃC(1N)
NÃP(2)ÃC(211)
NÃP(2)ÃC(221)
127.6(6)
112.6(4)
107.6(4)
C(111)ÃP(1)ÃC(121) 102.4(4)
C(211)ÃP(2)ÃC(221) 102.3(4)
Cambridge, CB2 1 EZ, UK (Fax: ꢂ44-1223-336033; e-
/
mail: deposit@ccdc.cam.ac.uk. or www: http://
www.ccd.cam.ac.uk).
The RhÃ
/
C(ring) distances span the range 2.183(10)ꢁ
/
˚
2.239(9) A and compare well with those found in other
pentamethylcyclopentadienylrhodium(III) complexes,
[(h5-C5Me5)RhCl{h2-P,O-Ph2PCH2CHMeCH2OH}}]-
Acknowledgements
5
2
˚
BF4 [2.114(4)ꢁ
P,Se-Ph2PNP(Se)Ph2}] [2.171(4)ꢁ
[(h5-C5Me5)Rh(OH2)(prophos)]SbF6 [1.650(9)ꢁ
/
2.229(4) A] [10], [(h -C5Me5)RhCl{h -
We thank ‘Fondo de Desarrollo Cient´ıfico y Tecno-
lo´gico, Chile’ (Grant No. 8980007) for financial support.
˚
/
2.2230(4) A] [2a] and
2.232(9)
Cl
/
˚
˚
A] [11]. The RhÃ
/
P [2.297(2) and 2.303(2) A] and RhÃ
/
˚
[2.376(2) A] distances are similar to those found in
References
related rhodium(III) complexes, such as and [(h5-
C5Me5)RhCl(prophos)]BF4
2.335(1), RhÃClꢀ
C5Me5)RhCl{h2-P,S-Ph2PNHP(S)Ph2}]BF4 [RhÃ
[RhÃ
/
Pꢀ
2.393(1) A] [12] and [(h5-
Pꢀ
/
2.314(1)
and
[1] P. Bhattacharyya, J.D. Woollins, Polyhedron 14 (1995) 3367 (and
references therein).
[2] (a) M. Valderrama, R. Contreras, P. Munoz, M.P. Lamata, D.
˜
˚
/
/
/
/
Carmona, F.J. Lahoz, S. Elipe, L.A. Oro, J. Organomet. Chem.
633 (2001) 182;
(b) M. Valderrama, R. Contreras, V. Arancibia, P. Munoz, Bol.
˜
˚
2.389(3) A] [13].
2.293(4) and RhÃ
The PÃN bond lengths of the co-ordinated chelate
ligand [average 1.680(7) A] are slightly smaller than the
/
Clꢀ
/
/
˚
Soc. Chil. Qu´ım. 45 (2000) 227;

12
M. Valderrama et al. / Journal of Organometallic Chemistry 665 (2003) 7ꢁ12
/
(c) J. Geicke, I.-P. Lorenz, P. Murschel, K. Polborn, Z.
¨
Chim. Acta 254 (1997) 329;
(h) A.F. Cotton, F.E. Kuhn, Inorg. Chim. Acta 252 (1996) 257.
¨
Naturforch. Teil. B 52 (1997) 593;
[5] (a) M.S. Balakrishna, R. Ramaswamy, R.M. Abhyankar, J.
Organomet. Chem. 560 (1998) 131;
(b) A.F. Cotton, F.E. Kuhn, A. Yokochi, Inorg. Chem. 252
¨
(d) R Uso´n, J. Fornies, R. Navarro, J.I. Cebollada, J. Organomet.
Chem. 304 (1986) 381.
[3] (a) M. Valderrama, V. Arancibia, R. Contreras, C. Soto, J.
Coord. Chem. 54 (2001) 389;
(1996) 251;
(c) R.P.K. Babu, S.S. Krishnamurthy, M. Nethaji, Tetrahedron:
Asymmetry 6 (1995) 427;
(b) M. Valderrama, R. Contreras, M.P. Lamata, F. Viguri, D.
Carmona, F.J. Lahoz, S. Elipe, L.A. Oro, J. Organomet. Chem.
607 (2000) 3;
(d) M.S. Balakrishna, R. Klein, S. Uhlenbrock, A. Pinkerton,
R.G. Cavell, Inorg. Chem. 32 (1993) 5676;
(c) J. Geicke, G.J. Lorenz, M. Engel, K. Polborn, Inorg. Chim.
Acta 269 (1998) 157;
(e) C.S. Browning, D.H. Farrar, D. Frankel, Acta Crystallgr.
Sect. C 48 (1992) 806.
(d) C.S. Browning, D.H. Farrar, J. Chem. Soc. Dalton Trans. 1
(1995) 521.
[6] E. Simo´n-Manso, Doc. Thesis, Pontificia Universidad Cato´lica de
Chile, Santiago, Chile, 2000.
[4] (a) E. Simo´n-Manso, M. Valderrama, V. Arancibia, Y. Simo´n-
Manso, D. Boys, Inorg. Chem. 39 (2000) 1650;
(b) G. Sa´nchez-Cabrera, E. Garc´ıa-Ba´ez, M. Rosales-Hoz, J.
Organomet. Chem. 599 (2000) 313;
[7] P.M. Maitlis, Acc. Chem. Res. 11 (1978) 301.
[8] F.T. Wang, J. Najdzionek, K.L. Leneker, H. Wasserman, D.M.
Braitsch, Synth. React. Inorg. Metal-Org. Chem. 8 (1978) 119.
[9] G.M. Sheldrick, SHELXL-97, Program for the refinement of crystal
(c) N. Nawar, J. Organomet. Chem. 602 (2000) 137;
(d) Y. Gimbert, F. Roberts, A. Durif, M.T. Averbuch, N. Kann,
A.E. Greene, J. Org. Chem. 64 (1999) 3494;
structures, University of Gottingen, Gottingen, Germany.
¨ ¨
[10] M. Valderrama, R. Contreras, G. Araos, D. Boys, J. Organomet.
Chem. 619 (2001) 1.
(e) I. Bachert, I. Bartusseck, P. Braunstein, E. Guillon, J. Rose, G.
Kickelbick, J. Organomet. Chem. 580 (1999) 257;
(f) I. Bachert, P. Braunstein, M.K. McCart, F. Fabrizi De Biani,
F. Laschi, P. Zanello, G. Kickelbick, U. Schubert, J. Organomet.
Chem. 537 (1999) 47;
[11] D. Carmona, C. Cativiela, R. Garc´ıa-Correas, F.J. Lahoz, E. San
Jose´, F. Viguri, J. Chem. Soc. Chem. Commun. (1966) 1247.
[12] D. Carmona, F.J. Lahoz, L.A. Oro, M.P. Lamata, F. Viguri, E.
San Jose´, Organometallics 15 (1996) 2961.
[13] E. Simo´n-Manso, M. Valderrama, P. Gantzel, C.P. Kubiak, J.
Organomet. Chem. 651 (2002) 90.
(g) C.S. Browning, D.H. Farrar, D.C. Frankel, J.J. Vittal, Inorg.