Chiral sulfur diphosphazanes derived from S-(Ph2P)2N(CHMePh) and its rhodium(I), (III) and iridium(III) complexes. Crystal structures of Ph2P(S)N(CHMePh)PPh2, {Ph2P(S)}2N(CHMePh) and [(Cp*)

Article abstract of DOI:10.1016/S0022-328X(02)01317-7

The reaction of S-(Ph₂ P)₂N(CHMePh) with sulfur (1:1 molar ratio) in diethyl ether solution leads to S-Ph₂P(S)N(CHMePh)PPh₂ (1). The disulphide S-{Ph₂P(S)}₂N(CHMePh) (2), was obtained when

Full text of DOI:10.1016/S0022-328X(02)01317-7

Journal of Organometallic Chemistry 651 (2002) 90ꢁ97
/
www.elsevier.com/locate/jorganchem
Chiral sulfur diphosphazanes derived from S-(Ph2P)2N(CHMePh)
and its rhodium(I), (III) and iridium(III) complexes. Crystal
structures of Ph2P(S)N(CHMePh)PPh2, {Ph2P(S)}2N(CHMePh) and
[(Cp*)MCl{h2-P,S-Ph2PNHP(S)Ph2}]BF4, Cp*ꢀ
MꢀRh, Ir
/
h5-C5Me5;
/
Eugenio Simo´n-Manso a,*, Mauricio Valderrama a, Peter Gantzel b, Clifford P. Kubiak b
a Departamento de Qu´ımica Inorga´nica, Facultad de Qu´ımica, Pontificia Universidad Cato´lica de Chile, Casilla 306, Santiago 22, Chile
b Department of Chemistry and Biochemistry, 9500 Gilman Drive, University of California, San Diego, CA 92093-0358, USA
Received 18 July 2001; received in revised form 6 February 2002; accepted 7 February 2002
Abstract
The reaction of S-(Ph2P)2N(CHMePh) with sulfur (1:1 molar ratio) in diethyl ether solution leads to S-Ph2P(S)N(CHMePh)PPh2
(1). The disulphide S-{Ph2P(S)}2N(CHMePh) (2), was obtained when the reaction was carried out in tetrahydrofuran with an excess
of sulfur (1:5 molar ratio). 1 reacts with the solvated rhodium (I) complex [Rh(cod)Sx]BF4 to afford the cationic complex
[Rh(cod){h2-S,P-Ph2P(S)N(CHMePh)PPh2}]BF4 (3). However, when the above reaction was carried out with 2, cleavage of the CÃ
/
N bond of the ligand occurred, to yield the complex [Rh(cod)(h2-S,S-{Ph2P(S)}2NH)]BF4 (4). Reactions of 1 with the fragments of
Rh (III) and Ir (III) [Cp*MClSx]BF4 lead to cleavage of the CÃ
N bond of the ligand yielding cationic complexes, [(Cp*)MCl{h2-
P,S-Ph2PNHP(S)Ph2}]BF4 (MꢀRh, 5; Ir, 6]. Crystal structures of 1, 2, 5 and 6 have been determined by X-ray diffraction methods.
/
/
Compounds 1 and 2 crystallize in the same space group P2(1)2(1)2(1). The molecular structure of 1 shows a nearly trigonal planar
nitrogen atom bound to two different phosphorus atoms and to the chiral carbon atom. Compound 2 acquires a twisted
conformation with the two sulfur atoms adopting mutually trans positions with respect to the PNP backbone. # 2002 Elsevier
Science B.V. All rights reserved.
Keywords: Chiral diphosphazanes; Chalcogenide compounds; Rhodium and Iridium complexes; Synthesis; Crystal structures
1. Introduction
In contrast, there are few examples of metal com-
plexes containing these ligands as neutral derivatives
[9,10]. Similarly, little attention has been paid to the
transition metal coordination chemistry of neutral
chalcogenides derived from substituted diphosphazanes
In the last decade, the coordination chemistry of the
mono and dichalcogenides derived from bis(diphenyl-
phosphino)amine, Ph2PNHP(E)Ph2 and {Ph2P(E)}2NH
(EꢀO, S, Se), has received considerable attention.
/
(Ph2P)2NR (RꢀMe, Ph) [11].
/
These compounds are easily deprotonated, and in their
anionic form are versatile ligands, able to form inor-
Recently, the synthesis and X-ray crystal structure of
the chiral diphosphazane N,N-bis(diphenylphosphino)-
N-{(S)-a-methylbenzyl}amine was described [12,13].
However, to the best of our knowledge, no chalcogenide
derivatives of this chiral diphosphazane have been
reported to date. Following our interest in the coordina-
tion properties of diphosphazanes and their chalcogen-
ganic (carbon free) chelate rings [1ꢁ8].
/
* Corresponding author. Present address: Department of Chemistry
and Biochemistry, University of California, San Diego (UCSD), 9500
ide derivatives [2,14ꢁ16], we report here the synthesis of
/
Gilman Drive, Dept. 0358, La Jolla, CA 92093-0358, USA. Fax: ꢂ1-
/
the ligands S-Ph2P(S)N(CHMePh)PPh2 and S-
{Ph2P(S)}2N(CHMePh), and some of their complexes
619-534-5383.
E-mail address: emismon@chem.ucsd.edu (E. Simo´n-Manso).
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 1 3 1 7 - 7

E. Simo´n-Manso et al. / Journal of Organometallic Chemistry 651 (2002) 90ꢁ
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91
with rhodium and iridium organometallic fragments.
The molecular structures of S-Ph2P(S)N(CHMePh)-
PPh2, S-{Ph2P(S)}2N(CHMePh) and [(Cp*)MCl{h2-
from chloroform-methanol. Yield 669 mg (59%). M.p.
115ꢁ117 8C. Anal. Calc. for C32H29NP2S2: C, 69,45; H,
5.24; N, 2.53; S, 11.57. Found: 69.67; H, 5.41; N, 2.59; S,
/
P,S-Ph2PNHP(S)Ph2}]BF4 (Mꢀ
/Rh, Ir) were deter-
10.47%. 1H-NMR (CDCl3, ppm): d 1.73 (d, 3 H,
mined by single-crystal X-ray diffraction. A variable-
temperature 31P{1H}-NMR spectroscopy study of com-
pounds S-(Ph2P)2N(CHMePh) and S-{Ph2P(S)}2-
N(CHMePh), is also reported.
3J(HH)ꢀ
/
7.2 Hz, Me), 5.34 (m, 1 H, CH) and 7.50
(m, 25 H, Ph). 31P{1H} (CDCl3, ppm): d 68.4 (s, br, PS).
37.5 [c 2.4,
FTIR (KBr, cmꢄ1): n(PS), 647 (s). [a]Dꢀ
/
CHCl3].
2. Experimental
2.3. [Rh(cod){h2-S,P-
Ph2P(S)N(CHMePh)PPh2}]BF4 (3)
All reactions were carried out under purified nitrogen
using Schlenk-tube techniques. Solvents were dried,
distilled, and stored under a nitrogen atmosphere. The
starting materials, S-(Ph2P)2N(CHMePh), [{Rh(m-
A mixture of the complex [{Rh(m-Cl)(cod)}2] (50 mg;
0.1 mmol), S-Ph2P(S)N(CHMePh)PPh2 (106 mg; 0.2
mmol) and NaBF4 (22 mg; 0.2 mmol) in acetone (15
cm3) was stirred for 1 h and solid NaCl was filtered off.
This solution was concentrated to a small volume and
the complex precipitated as a brown solid by addition of
diethyl ether. Yield 90 mg (55%). Anal. Calc. for
C40H41BF4NP2RhS: C, 58.63; H, 5.01; N, 1.71; S,
Cl)(cod)}2] (codꢀ
/
1,5-cyclooctadiene) and [{(Cp*)-
MCl(m-Cl)Cl}2](Mꢀ/Rh, Ir) were prepared according
to published methods [2,17]. Elemental analyses (C, H,
N and S) were conducted with a Fisons EA 1108
microanalyzer. FTIR spectra were recorded on a Bruker
1
1
Vector-22 spectrophotometer using KBr pellets. H and
3.91. Found: C, 59.67; H, 5.15; N, 1.61; S, 4.32%. H-
31P{1H}-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. Optical rotations were measured with an
Optical Activity LTD polarimeter equipped with a
sodium lamp at 18 8C.
NMR (CDCl3, ppm): d 1.10 (d, 3 H, 3J(HH)ꢀ
/
7.22 Hz,
2.33 (m, 8 H, CH2, cod), 2.92 (s, br, 1 H,
CH, cod), 3.34 (s, br, 1 H, ÄCH, cod), 5.0 (m, 1 H,
CH), 5.72 (s, br, 2 H, ÄCH, cod) and 6.31 (d), 6.99 (t),
7.3ꢁ
8.2 (m) assigned to aromatic H-rings. 31P{1H}
Me), 1.96ꢁ
/
Ä
/
/
/
/
(CDCl3, ppm): d 69.8 [d, 2J(PP)ꢀ
/
66.1 Hz, PS] and
1
103.0 [dd, J(RhP)ꢀ
/
155.7 Hz, P]. FTIR (KBr, cmꢄ1):
n(PS), 596(m), 588 (m).; n(BF4), ca. 1100(s), 520(m).
2.1. S-Ph2P(S)N(CHMePh)PPh2 (1)
A solution of S-(Ph2P)2N(CHMePh) (1.0 g; 2.05
mmol) and sulfur (66 mg; 2.05 mmol) in diethyl ether
was heated under reflux for 45 min. During this time a
white solid formed. The reaction mixture was evapo-
rated to dryness and the residue was treated with diethyl
ether (5 ml). The white solid was filtered, washed with
2.4. Reaction of [{Rh(m-Cl)(cod)}2] with S-
{Ph2P(S)}2N(C*HMePh)
A suspension of the dinuclear complex [{Rh(m-
Cl)(cod)}2] (62 mg; 0.1 mmol) in acetone (10 ml) was
treated with silver tetrafluoroborate (39 mg; 0.2 mmol).
The mixture was stirred for 30 min in the absence of
light and the AgCl formed was filtered off through
Kieselguhr. A solution of S-{Ph2P(S)}2N(CHMePh)
(107 mg; 0.2 mmol) in acetone (10 ml) was added to
the yellow filtrate, containing the solvated complex
[Rh(cod)(Me2CO)x]ꢂ. After stirring for 1 h at room
temperature (r.t.), the mixture was evaporated to dry-
ness and the residue was extracted with dichloro-
methane. Careful addition of diethyl ether induced
precipitation of an orange solid. The solid obtained
was characterized as. [Rh(cod)(h2-S,S-{Ph2P(S)}2-
NH)]BF4 (4). Yield 65 mg (67%). Anal. Found: C,
51.42; H, 4.23; N, 1.81; S, 8.77. Calc. for
C32H33BF4NP2RhS2: C, 51.42; H, 4.45; N, 1.87; S,
diethyl ether (2ꢃ
/
5 ml) and air-dried. Yield 718 mg
(67%). M.p. 172ꢁ174 8C. Anal. Calc. for C32H29NP2S:
/
C, 73.70; H, 5.57; N, 2.69; S, 6.14. Found: 73.59; H,
5.59; N, 2.73; S, 6.00%. 1H-NMR (CDCl3, ppm): d 1.84
(d, 3 H, 3J(HH)ꢀ
/
6.96 Hz, Me), 5.19 (m, 1 H, CH) and
7.50 (m, 25 H, Ph). 31P{1H} (CDCl3, ppm): d 51.4 [d,
2J(PP)ꢀ
14.8 Hz, P] and 71.1 (d, PS). FTIR (KBr,
cmꢄ1): n(PS), 673 (m). [a]Dꢀ
68.75 [c 2.4, CHCl3]
/
/
ꢄ
/
2.2. S-{Ph2P(S)}2N(CHMePh) (2)
A solution of S-(Ph2P)2N(CHMePh) (1.0 g; 2.05
mmol) and sulfur (329 mg; 10.25 mmol) in tetrahydro-
furan (40 ml) was heated under reflux for 2.5 h. The
reaction mixture was cooled to ꢄ
/
20 8C and the excess
8.58%. 1H-NMR (CDCl3, ppm): d 1.9ꢁ
CH2, cod), 4.04 (s, br, 2 H, ÄCH, cod), 4.62 (s, br, 2 H,
CH, cod). 31P{1H} (CDCl3, ppm): d 35.9 (s). FTIR
(KBr, cmꢄ1): n(PS), 555 (s); n(BF4), ca. 1100(s), 510(m).
/2.4 (m, 8 H,
sulfur was filtered off. The solution was evaporated to
dryness and the solid obtained was washed with
methanol (15 ml). The compound was crystallized
/
Ä
/

92
E. Simo´n-Manso et al. / Journal of Organometallic Chemistry 651 (2002) 90ꢁ97
/
Table 1
Crystallographic data and structure refinement for compounds 1 and 2
Compound
1
2
Empirical formula
Formula weight
C
32H29NP2S
C32H29NP2S2
553.62
23
521.56
23
Temperature ( 8C)
˚
Wavelength (A)
Moꢁ
/
Ka (0.71073)
MoꢁKa (0.71073)
/
Crystal system
Space group
Unit cell dimensions
Orthorhombic
P2(1)2(1)2(1)
Orthorhombic
P2(1)2(1)2(1)
˚
a (A)
10.969(5)
15.131(7)
16.964(9)
2746(2)
4
9.499(2)
15.588(4)
19.598(5)
2901.8(12)
4
˚
b( A)
˚
c (A)
3
V (A )
˚
Z
Dcalc (Mg mꢄ3
Absorption coefficient (mmꢄ1
F(000)
)
1.262
0.256
1096
1.267
0.316
1160
)
Crystal size (mm)
u Range for data collection (8)
Index ranges
0.80ꢃ
1.80ꢁ22.50
0ꢀhꢀ11, ꢄ
2222
2211 (Rint
/
0.50ꢃ
/
0.30
0.60ꢃ
1.67ꢁ22.50
4ꢀhꢀ12, ꢄ
2413
2352 (Rintꢀ0.0299)
/
0.50ꢃ0.50
/
/
/
/
/
/
1ꢀkꢀ
/
/
16, 1ꢀ
/
lꢀ
/
18
ꢄ/
/
/
/1ꢀ
/
kꢀ
/
20, 0ꢀ
/
lꢀ25
/
Reflections collected
Independent reflections
Refinement method
ꢀ/
0.0352)
/
Full-matrix least-squares on F2
Full-matrix least-squares on F2
Data/restraints/parameters
Goodness-of-fit on F2
2210/07266
1.059
2349/0/275
1.041
Final R indices [I ꢀ
R indices (all data)
Absolute structure parameter
Largest difference peak and hole (e A
/
2s(I)]
R1ꢀ
R1ꢀ
0.02(18)
0.204 and ꢄ
/
0.0448, wR2ꢀ
/
0.0921
R1ꢀ
R1ꢀ
0.020(17)
0.256 and ꢄ0.276
/
0.0468, wR2ꢀ
/
0.1089
/
0.0587, wR2ꢀ
/
0.1006
/
0.0534, wR2ꢀ
/
0.1140
ꢄ/
ꢄ3
˚
)
/
0.195
/
2.5. [(Cp*)MCl{h2-P,S-Ph2PNHP(S)Ph2}]BF4
(MꢀRh 5, Ir 6]
2.5.2. Complex 6
Yield 172 mg, 61%. (Found: C, 47.2; H, 4.2; N, 1.8; S,
3.5. C34H36BClF4NP2IrS requires C, 47.1; H, 4.2; N,
/
1.6; S, 3.7%). nmax cmꢄ1 (KBr): 585 (PS), 1100 and 520
A solution of the binuclear complex [{(Cp*)MCl(m-
Cl)}2] (0.16 mmol; Rh, 100 mg; Ir, 126 mg) and AgBF4
(82 mg; 0.32 mmol) in a mixture chloroform-acetone
(5:15 cm3), was stirred for 2 h at r.t. in the absence of
light. The precipitated silver chloride was removed by
filtration. (S)-a-Ph2PN(CHMePh)P(S)Ph2 (167 mg; 0.32
mmol) dissolved in boiling diethyl ether (40 cm3) was
added to the resulting solution. After stirring the
reaction mixture for 30 min, the solution was filtered,
evaporated to a small volume and the complex pre-
cipitated by adding diethyl ether. The complexes were
crystallized by diffusion of diethyl ether into a chloro-
form solution of compounds.
4
(BF4). dH (CDCl3, 295 K) 1. 57 [d, 15 H, J(HP)ꢀ
/2.48
Hz, C5Me5], 6.4ꢁ
/
7.7 (m, 20 H, Ph). dP (CDCl3, 295 K)
32.5 Hz, PIr], 69.1 [d, PS].
2
60.8 [d, J(PP)ꢀ
/
2.6. X-ray structure determination of compounds 1, 2, 5
and 6
Suitable crystals for the X-ray diffraction studies were
obtained by slow evaporation of a chloroform-methanol
solution (1 and 2) and by vapor diffusion of ether into
chloroform solution of 5 and 6. Intensity crystal data
were collected on a Siemens R3m/V diffractometer using
graphiteꢁ
/
monochromated MoꢁKa radiation in Wyck-
/
off v scan mode. The structures were solved by direct
methods, and all of the non-hydrogen atoms refined
with anisotropic displacement parameters. Refinement
was by full-matrix least-squares methods on F2. Calcu-
lations were performed using the program SHELXTL-PC
[18]. Phenyl rings were treated as idealized D6h sym-
2.5.1. Complex 5
Yield 180 mg, 72%. (Found: C, 52.4; H, 4.5; N, 1.9; S,
4.0. C34H36BClF4NP2RhS requires C, 52.4; H, 4.7; N,
1.8; S, 4.1%). nmax cmꢄ1 (KBr): 588 (PS), 1100 and 520
4
(BF4). dH (CDCl3, 295 K) 1.5 [d, 15 H, J(HP)ꢀ
/
3.68
Hz, C5Me5], 7.6 (m, 20 H, Ph). dP (CDCl3, 295 K) 87.2
˚
metric rings with CÃ
/
Cꢀ
/
1.395 A and CÃ
/
CÃ
/
Cꢀ1208.
/
1
2
[dd, J(RhP)ꢀ
/
139 Hz, J(PP)ꢀ39 Hz, PRh], 69.0 [d,
/
Crystal data and details of measurements and refine-
ments are summarized in Tables 1 and 3.
PS].

E. Simo´n-Manso et al. / Journal of Organometallic Chemistry 651 (2002) 90ꢁ
/97
93
3. Results and discussion
temperature, were broad singlet resonances at d 52.5
and 68.4 ppm, respectively. Variable temperature ex-
periment (Fig. 1) showed split of the signal into two
sharp spin-coupled doublets (AB system) below 233 K
for S-(Ph2P)2N(CHMePh) and two uncouplet singlets
below 213 K for 2, respectively. This type of line-width/
temperature behavior is characteristic of the exchange
broadening by equilibrium involving minor component
3.1. Synthesis of sulfur diphosphazanes
The synthetic method of Krishnamurthy et al. [12]
was used to synthesize the starting chiral diphosphazane
S-(PPh2)2N(CHMePh). The chiral diphosphazene S-
(Ph2P)2N(CHMePh) reacts with
a
stoichiometric
[23ꢁ25] (Scheme 1). Steric interactions prevent confor-
/
amount of elemental sulfur in diethyl ether solution at
reflux temperature, to give S-Ph2P(S)N(CHMePh)PPh2
(1) as an insoluble solid. The conversion is produced
in moderate yield (67%) and minor amounts of
mer of C2v? from participating to any significant extend
in conformational equilibrium [4].
Variable-temperature 31P{1H}-NMR experiments of
the chiral phosphazene and its sulfur derivative 2 show
that, on cooling, the broad resonances (for starting
compound and its sulfur derivative 2) split into two
broad signals. At 233 and 213 K, respectively, the
exchange is sufficiently slow to separate two sharp
disulphide
[Ph2P(S)]2N(CHMePh)
and
starting
(Ph2P)2N(CHMePh) compounds were detected in the
diethyl ether solution. Compound 1 is soluble in toluene,
chlorinated solvents, tetrahydrofuran and acetone. Its
31P{1H}-NMR spectrum in CDCl3 solution showed two
sharp doublets at d 51.4 and 71.1 ppm, assigned to
phosphorus (III) and phosphorus (V) centers, respec-
doublet signals at d 55.0 and 47.4 ppm [2J(PP)ꢀ
25.59
/
Hz] for the starting compound and to uncoupled singlets
at 73.7 and 62.5 ppm in case of 2. Coalescence
temperatures of these processes are 293 and 276 K,
respectively. The free energy of activation DG%Tc for
conformational changes between C2v and Cs conformers
were calculated using approximated rate constant at the
coalescence point for the coalescence of singlets asso-
ciated with uncoupled diasterotopic atoms or groups. a)
2
tively, with a J(PP) coupling of 14.8 Hz. Evaporation
of the solution gave the disulphide compound S-
[Ph2P(S)]2N(CHMePh) (2) in low yield (34%) when the
reaction was carried out in a 1:2 molar ratio. At reflux
temperature, a large amount (30%) of compound 1 was
formed. Compound 2 was obtained in highest yield
(59%) when the reaction was performed under refluxing
tetrahydrofuran with an excess of sulfur (1:5 molar
ratio). The 31P{1H}-NMR spectrum of 2 in CDCl3
solution showed a broad singlet at d 68.4 ppm at room
temperature.
kcꢀ
AB spin system to a singlet b) kcꢀ
6J2), Dn is the difference of P signals (sꢄ1) and J is the
coupling parameter [19]. DG%Tc 12.92 kcal molꢄ1 for
the starting ligand and 11.93 kcal molꢄ1 for 2. These
quantities lie in the range for other PÃN rotational
barriers 9.4ꢁ
12.7 kcal molꢄ1 in case of bulky alkyls and
/
(p â2ꢄ1)Dn and for the coalescence of the coupled
(p â2ꢄ1)â(Dn2ꢂ
/
/
ꢀ
/
Both compounds were isolated as stable white solids.
The IR spectra showed the characteristic absorption
/
/
band assigned to the n(PÄ
/
S) moiety (1, 674; 2, 647
cmꢄ1).
amides of main group elements [26].
The variable temperature 31P-NMR spectra of S-
(Ph2P)2N(CHMePh) and 2 are very similar to those
reported for of non chiral PriN(PPh2)2 [25]. At low
temperature, the presence of two different phosphorus
3.2. Variable temperature NMR studies
The 31P{1H}-NMR spectra of the starting ligand S-
(Ph2P)2N(CHMePh) and its sulfur derivative 2, at room
resonances is ascribed to hindered PÃ
/
N rotation and
preference for Cs configuration. To support this, both of
the ligands crystallize in the Cs conformation and low
coupling parameter (JPP
ꢀ25.59Hz) for the starting
/
compound and the absence of coupling in 2 are
indicative that at low temperature in solution the most
stable conformer should be the Cs as have been shown
by X-ray diffraction in other studies [4].
The room temperature spectra of S-(Ph2P)2-
N(CHMePh) and 2 are, however, less really explained.
The presence of chiral R*group on nitrogen makes the
phosphorus atoms diastereotopic, yet only one reso-
nance, albeit a broad one, is observed at room tempera-
tures for both of the compounds. This may be due to
accidental degeneracy of the resonances or to an
inability to resolve the two peaks due to 14N spin
coupling witch is incompletely collapsed by 14N quad-
rupolar relaxation and/or by the exchange broadening
Fig. 1. Variable temperature 31P{1H}-NMR. (a) S-(Ph2P)2-
N(CHMePh); (b) S-(Ph2P(S))2N(CHMePh), 2.

94
E. Simo´n-Manso et al. / Journal of Organometallic Chemistry 651 (2002) 90ꢁ97
/
Scheme 1.
Table 2
Selected bond distances (A) and angles (8) for compounds 1 and 2
˚
1
2
˚
Bond distances (A)
P(1)Ã
P(2)Ã
N(1)Ã
P(2)ÃS(1)
/
N(1)
1.749(4)
1.695(4)
1.499(6)
1.955(2)
P(1)Ã
P(1)Ã
P(2)Ã
P(2)Ã
N(1)Ã
/
N(1)
S(1)
N(1)
S(2)
1.700(4)
1.945(2)
1.716(4)
1.927(2)
1.524(7)
/N(1)
/
/C(1)
/
/
/
/C(1)
Bond angles (8)
P(1)Ã
P(1)Ã
P(2)Ã
N(1)Ã
N(1)Ã
/
N(1)Ã
N(1)Ã
N(1)Ã
P(1)Ã
P(2)Ã
/
P(2)
C(1)
C(1)
S(1)
S(2)
124.3(2)
123.2(3)
111.4(3)
115.4(2)
113.7(2)
P(2)Ã
N(1)Ã
P(1)ÃN(1)Ã
P(2)ÃN(1)Ã
/
N(1)Ã
/
P(1)
S(1)
C(1)
C(1)
112.0(2)
117.2(2)
121.5(3)
121.9(3)
/
/
/
P(2)Ã
/
/
/
/
/
Fig. 2. ORTEP plot (50% probability ellipsoids) for compound
Ph2P(S)N(CHMePh)PPh2.
/
/
/
/
/
/
The molecular structure of 1 shows a nearly trigonal
planar nitrogen atom bound to two different phospho-
rus atoms, PIII(1) and PV(2), and to a chiral carbon
atom. As expected, the PVÃ
/
N bond distance is shorter
N, 1.695(4) A] than the PIIIÃ
N bond [P(1)ÃN,
1.749(4) A] and compares well with those found in the
N, average
˚
[P(2)Ã
/
/
/
˚
related compounds [Ph2P(S)]2NH [PÃ
/
˚
1.676(7) A] [20] and (Ph2P)2N(CHMePh) [PÃ
/
N, average
˚
˚
S bond distance [1.955(2) A] is
indicative of the double bond character and is similar to
1.7192 A] [13]. The PÃ
/
˚
those found in P4S10 [PÄ
[Ph2P(S)]2NH [PÃS, average 1.916(3) A] [19]. The PÃ
NÃP bond angle [PÃNÃP, average 112.08] is smaller
than the PÃNÃP angle of the starting compound
(Ph2P)2N(CHMePh) [PÃ P, average 120.048] [13].
/
S, 1.960 A] [21] and
˚
/
/
Fig. 3. ORTEP plot (50% probability ellipsoids) for compound
{Ph2P(S)2N(CHMePh)}.
/
/
/
/
/
/
NÃ
/
by equilibrium involving minor component of Cs con-
former afford mentioned.
Compound 2 acquires a twisted conformation with
the two sulfur atoms adopting a mutually trans relation-
ship with respect to the PNP skeleton. The PÃ
/
S [1.945(2)
˚
and 1.927(2) A] and PÃ
/
N bond distances [1.700(4) and
3.3. Molecular structures of 1 and 2
˚
1.716(4) A], compare well with those showed in the
similar compound [Ph2P(S)]2NH [PÃS, average 1.916(3)
N, average 1.676(7) A] [20]. The PÃNÃP bond
angle [124.3(2)8] is smaller than the PÃNÃP angle of the
related compound [Ph2P(S)]2NH [PÃNÃP, 131.7(5)8]
[21]. However, it compares well with the value found
in the starting compound (Ph2P)2N(CHMePh) [PÃNÃP,
average 120.048] [13].
/
Figs. 2 and 3 display the molecular structures of
compounds 1 and 2, respectively. Crystallographic Data
and Structure Refinement for Compounds 1 and 2 and
Selected bond lengths and bond angles for the structures
are shown in Tables 1 and 2. From a crystallographic
point of view, the crystal lattices and packing are
identical in the space group P212121.
˚
˚
A, PÃ
/
/
/
/
/
/
/
/
/

E. Simo´n-Manso et al. / Journal of Organometallic Chemistry 651 (2002) 90ꢁ
/97
95
3.4. Synthesis of the metal complexes
Compound 1 reacts with the solvated complex
[Rh(cod)Sx]BF4 (prepared in situ from [{Rh(m-
Cl)(cod)}2] and silver tetrafluoroborate in acetone or
tetrahydrofuran) to give the cationic complex
[Rh(cod){h2-S,P-Ph2P(S)N(C*HMePh)PPh2}]BF4 (3).
As expected, in this compound, the mono sulphide (1)
derivative behaves as heterobifunctional chelate ligand.
Its 31P{1H}-NMR spectrum shows a doublet resonance
at d 69.8 [2J(PP)ꢀ
103.0 ppm [1J(RhP)ꢀ
PIII(PÃ
the expected resonances of the diolefin cod and the co-
ordinated chiral ligand in the required proportions,
supporting the proposed formulation.
In contrast, when the above reaction was carried out
with the disulphide ligand S-{Ph2P(S)}2N(CHMePh),
the coordination of the phosphine-sulphide groups to
the metal center occurs simultaneously with the cleavage
/
66.1 Hz] and a doublet of doublets at
/
155.7 Hz], assigned to PV(PS) and
1
Fig. 5. ORTEP plot (50% probability ellpsoids) for [(Cp*)RhCl{k2-P, S-
Ph2PNHP(S)Ph2}]BF4, 5.
/
Rh), respectively. The H-NMR spectrum shows
lower fields. The 31P-NMR spectrum on a well shaped
crystals, obtained by diffusion of ether into chloroform
solution of the complex doesn’t show the afford men-
tioned duplicated pattern. This could be explained by
the existence in solution of structural conformer at a five
membered chelate ring and its interconversion during
the crystallization process.
Addition of a base (NEt3) leads to loss of the acidic
imine proton in both complexes to give neutral species,
as shown by comparison of the 31P-NMR chemical shift
with the one of iridium neutral complex [Cp*IrCl{h2-
P,S-Ph2PNP(S)Ph2}] [31]. When both forms (neutral
and cationic) are present in solution a fast proton
exchange occurs at NMR time scale to give broad 31P
signal at room temperature. Lowering the temperature
of the carbonÃ
/
nitrogen bond of the ligand, affording the
cationic complex [Rh(cod)(h2-S,S-{Ph2P(S)}2NH)]BF4
(4). This complex was fully characterized by elemental
analysis, IR and NMR spectroscopies. Same complex
was obtained by reaction of disulphide ligand
HN{P(S)Ph2}2 [22] with the solvated complex
[Rh(cod)Sx]BF4.
On the other hand, the reaction of compound 1 with
solvated complex [Cp*MClSx]BF4, MꢀRh, Ir (pre-
/
pared in situ from binuclear complexes [{Cp*MCl(m-
Cl)}2] and silver tetrafluoroborate in acetone or tetra-
hydrofuran) give the cationic complexes [Cp*MCl{h2-
to ꢄ50 8C make the proton exchange process, at
/
nitrogen atom, slow enough to resolve the spectra in
to sharp signals corresponding to cationic and neutral
species, respectively.
S,P-Ph2P(S)NHPPh2}]BF4, MꢀRh (5), Ir (6) with the
/
1
consequent loss of the chiral R* group, shown by H-
NMR and X diffraction studies.
The 31P-NMR spectra of the crude product for both
complexes 5 and 6 (Fig. 4) show a duplicated pattern
3.5. Molecular structures of 5 and 6
Figs. 5 and 6 display the molecular structures of
compounds 5 and 6, respectively. Crystallographic
information and relevant bond lengths and bond angles
are given in Tables 3 and 4, respectively. In both
(relative intensity ꢁ60:40), having the same coupling
parameters with the less intense signals, appearing at
/
Fig. 4. 31P-MR spectra of the crude product (a) rhodium and (b)
irridium complexes. Notice the duplicated pattern of the spectra.
Fig. 6. ORTEP plot (50% probability ellpsoids) for [(Cp*)IrCl{k2-P, S-
Ph2PNHP(S)Ph2}]BF4, 6.

96
E. Simo´n-Manso et al. / Journal of Organometallic Chemistry 651 (2002) 90ꢁ97
/
Table 3
Crystallographic data and structure refinement for compounds 5 and 6
Compound
5
6
Empirical formula
Formula weight
Temperature (8C)
C
34H36BClF4NP2RhS
C34H36BClF4IrNP2S
867.10
22
777.81
23
˚
Wavelength (A)
Moꢁ
/
Ka (0.71073)
MoꢁKa (0.71073)
/
Crystal system
Space group
Unit cell dimensions
Orthorhombic
Pca2(1)
Orthorhombic
Pca2(1)
˚
a (A)
16.791(5)
10.966(3)
19.010(6)
3500.4(19)
4
16.752(4)
10.957(2)
18.959(4)
3480.0(12)
4
˚
b( A)
˚
c (A)
3
V (A )
˚
Z
Dcalc (Mg mꢄ3
Absorption coefficient (mmꢄ1
F(000)
)
1.476
0.762
1584
1.655
4.112
1712
)
Crystal size (mm)
u Range for data collection (8)
Index ranges
0.35ꢃ
1.86ꢁ27.50
1Bh B21, 0B
4411
4138 (Rint
/
0.35ꢃ
/
0.20
0.80ꢃ
1.86ꢁ27.53
15h 521, ꢄ
4416
4416 (Rintꢀ0.0376)
/
0.30ꢃ0.10
/
/
/
ꢄ/
/
/
/
k B
/
14, ꢄ
/
24B
/
l B
/
0
ꢄ/
/
/
/
45
/
k 5
/
14, ꢄ
/
245
/
l 50
/
Reflections collected
Independent reflections
Refinement method
ꢀ/
0.0318)
/
Full-matrix least-squares on F2
Full-matrix least-squares on F2
Data/restraints/parameters
Goodness-of-fit on F2
4137/1/277
1.028
4118/1/152
1.022
Final R indices [I ꢀ
R indices (all data)
Absolute structure parameter
Largest difference peak and hole (e A
/
2s(I)]
R1ꢀ
R1ꢀ
0.08(9)
0.637 and ꢄ
/
0.0661, wR2ꢀ
/
0.1316
R1ꢀ
R1ꢀ
0.03(2)
2.729 and ꢄ0.761
/
0.0641, wR2ꢀ
/
0.1405
/
0.1215, wR2ꢀ
/
0.1626
/0.1215, wR2ꢀ
/
0.1744
ꢄ3
˚
)
/
0.512
/
structures Rh and Ir atoms have distorted coordination
spheres. The centroid of the pentamethylcyclopentadie-
nyl ligand occupies the center of three octahedral sites.
The heterobifunctional chelate ring bonded to the metal
center through a phosphorus and sulfur atoms and a
chlorinate atom complete the coordination sphere.
Complexes 5 and 6 crystallize as a racemic mixture S
and R [50:50%] imposed by space group Pca2(1)
requirement [27].
Finally, the coordination reaction of the disulphide
ligand 2 with the solvated compound [Cp*MClSx]BF4
was carried out with a simultaneously cleavage of the
CÃ/N bond to afford the recently described neutral
complexes [Cp*MCl((SPPh2)2N)] [2]. In this case the
ligand is co-ordinated in its very stable bidentate anionic
Table 4
˚
Selected bond distances (A) and angles (8) for complexes
[Cp*RhCl{k2-P,S(Ph2P
P,S(Ph2PNHP-
(S)Ph2)}]BF4, 6
NHP(S)Ph2)}]BF4,
5;
[Cp*IrCl{k2-
The distances RhÃ
/
P and RhÃ
/
Cl [RhÃ
/
P, 2.293(4);
˚
RhÃ
/
Cl, 2.389(3)A] are slightly shorter than in the
neutral complex [Cp*RhCl{h2-P,Se-(Ph2PNP(Se)Ph2}]
5
6
˚
Cl, 2.3992(15) A] [31] and in the
[RhÃ
/
P, 2.3295(11); RhÃ
/
[Cp*RhCl{prophos}] [RhÃ
/
P, 2.325(1); RhÃ
S and PÃS [RhÃS, 2.404(3); PÃ
1.997(4) A] distances are very close to those in the Rh(I)
complex [(COD)Rh{Ph2P(S)}2CH2]ClO4, S,
[RhÃ
2.403(5); PÃS, 2.001(6) A] [29]. For the iridium complex
6 the IrÃP and IrÃCl distances [IrÃP, 2.263(6); IrÃCl,
2.398(5) A] are in range of the cationic complex
[Cp*IrCl{h2-P,S-Ph2PCH2P(S)Ph2}]BF4×
Me2CO [IrÃP,
Cl, 2.381(2) A] [30]. The IrÃC and IrÃ
distances [IrÃC(C5Me5)av. 2.201; IrÃS, 2.407(5)A]
are very close to the one for the mentioned before
complex [IrÃC(C5Me5)av., 2.161/2.238; IrÃS, 2.402(3)
/
Cl, 2.393(1)
˚
Bond distances (A)
˚
Rh(1)Ã
/
S(1)
2.404(3)
2.293(4)
1.650(11)
1.698(10)
1.997(4)
1.790(7)
1.777(8)
2.389(3)
2.197
Ir(1)Ã
Ir(1)Ã
P(1)Ã
P(2)Ã
P(1)Ã
P(1)Ã
P(1)Ã
Ir(1)Ã
Ir(1)Ã
/
S(1)
P(2)
2.407(5)
2.263(6)
1.64(2)
A] [28]. The RhÃ
/
/
/
/
S,
Rh(1)Ã/P(2)
/
˚
P(1)Ã
P(2)Ã
P(1)Ã
P(1)Ã
P(1)Ã
/
N(1)
/
N(1)
/
/N(1)
/
N(1)
1.69(2)
˚
/
/S(1)
/
S(1)
2.000(8)
1.781(12)
1.764(12)
2.398(5)
2.201
/
/
/
/
/C(1C)
/
C(1C)
˚
/C(1D)
/
C(1D)
Rh(1)Ã
/
Cl(1)
/
Cl(1)
C(1 ꢁ 5)av
/
/
Rh(1)Ã
/
C(1 ꢁ 5)av
/
˚
2.303(3); IrÃ
/
/
/
S
Bond angles (8)
P(1)ÃN(1)ÃP(2)
S(1)ÃRh(1)ÃP(2)
P(2)ÃRh(1)Ã
S(1)ÃRh(1)Ã
˚
/
,
/
/
/
121.1(6)
P(1)Ã
S(1)Ã
P(2)Ã
S(1)Ã
/
N(1)Ã
Ir(1)ÃP(2)
Ir(1)Ã
Ir(1)Ã
/
P(2)
122.5(11)
88.6(2)
87.7(2)
89.2(2)
/
/
88.32(12)
87.63(12)
91.59(12)
/
/
/
/
/
/
Cl(1)
/
/
Cl(1)
˚
A].
/
/Cl(1)
/
/Cl(1)

E. Simo´n-Manso et al. / Journal of Organometallic Chemistry 651 (2002) 90ꢁ
/97
97
[2] 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.
form, which is considered as non-carbon analogues of
acetylacetonate.
[3] J.D. Woollins, J. Chem. Soc. Dalton Trans. (1996) 2893, and
references therein.
4. Conclusions
[4] P. Bhattacharyya, J.D. Woollins, Polyhedron 14 (1996) 3367 (and
references therein).
[5] P. Bhattacharyya, A.M.Z. Slawin, M.B. Smith, J. Chem. Soc.
Dalton Trans. (1998) 2467.
Sulfur chalcogenide derivatives of diphosphazanes
S-Ph2P(S)N(CHMePh)PPh2
and
S-{Ph2P(S)}2N-
[6] P. Bhattacharyya, A.M.Z. Slawin, M.B. Smith, J.D. Woollins,
Inorg. Chem. 35 (1996) 3675.
(CHMePh) have been synthesized and fully character-
ized using spectroscopic techniques and by elemental
analysis. Their structures have been determined by X-
ray diffraction method. Variable temperature experi-
ments with the starting ligand and its sulfur derivative S-
{Ph2P(S)}2N(CHMePh) show exchange broadening by
equilibrium involving two conformers. Calculated bar-
[7] A.M.Z. Slawin, M.B. Smith, J.D. Woollins, J. Chem. Soc. Dalton
Trans. (1996) 1283.
[8] R. Rosler, J.E. Drake, C. Silvestru, J. Yang, I. Haiduc, J. Chem.
¨
Soc. Dalton Trans. (1996) 391.
[9] J. Cuadrado, M. Mora´n, Trans. Met. Chem. 9 (1984) 96.
[10] R.O. Day, R.R. Holmes, A. Schmidtpeter, K. Stoll, L. Howe,
Chem. Ber. 124 (1991) 2443.
riers from NMR data are DGT% c
ꢁ12.92 and 11.93 kcal
/
[11] M.S. Balakrishna, R. Klein, S. Uhlenbrock, A.A. Pinkerton, R.G.
Cavell, Inorg. Chem. 32 (1993) 5676.
molꢄ1, respectively.
The mono-sulfur chalcogenide behaves as a neutral
[12] R.P.K. Babu, S.S. Krishnamurthy, M. Nethaji, Tetrahedron:
Asymmetry 6 (1995) 427.
ligand with fragment [Rh(cod)Sx]BF4 to afford the
cationic
[13] F. Robert, Y. Gimbert, M.T. Averbuch-Pouchot, A.E. Greene,
New Cryst. Struct. 215 (2000) 233.
complex
[Rh(cod){h2-S,P-Ph2P(S)N-
(CHMePh)PPh2}]BF4 (3). However, cleavage of the
[14] E. Simo´n-Manso, M. Valderrama, V. Arancibia, Y. Simo´n-
Manso, D. Boys, Inorg. Chem. 39 (2000) 1659.
[15] M. Valderrama, R. Contreras, A. Arancibia, P. Muno´z, Bol. Soc.
˜
CÃ
/
N bond of the ligand occurred to yield the complex
[Rh(cod)(h2-S,S-{Ph2P(S)}2NH)]BF4 (4) when the
above reaction was carried out with S-{Ph2P(S)}2-
N(CHMePh).
Chil. Qu´ım. 45 (2000) 227.
[16] M. Valderrama, V. Arancibia, R. Contreras, C. Soto, J. Coord.
Chem. 54 (2001) 389.
Reactions of S-Ph2P(S)N(CHMePh)PPh2 with the
fragments of Rh (III) and Ir (III) [Cp*MClSx]BF4
[17] (a) J. Chatt, M.L. Venanzi, J. Chem. Soc. (1957) 4735.;
(b) P.M. Maitlis, Acc. Chem. Res. 11 (1978) 301.
[18] G.M. Sheldrick, SHELXTL-PC, Siemens Analytical X-Ray Instru-
ments Inc., Madison, WI, USA, 1990.
lead to cleavage of the CÃ
affording cationic complexes, [(Cp*)MCl{h2-P,S-
Ph2PNHP(S)Ph2}]BF4 (MꢀRh, 5; Ir, 6].
/N bond of the ligand
[19] D. Kost, E.H. Carlson, M. Raban, Chem. Commun. (1971)
656.
/
[20] P.B. Hitchcock, J.F. Nixon, I. Silaghi-Dumitrescu, I. Haiduc,
Inorg. Chim. Acta 96 (1985) 77.
4.1. Supporting information available
[21] A. Vasand, E.M. Wiebenga, Acta Crystallogr. 8 (1955) 217.
[22] F.T. Wand, J. Najdzionek, K.L. Leneker, H. Wasserman, D.M.
X-ray crystallographic files, in CIF format for the
structure determination at the Cambridge Crystallo-
graphic Data Centre and allocated the deposition
numbers 1, 165206; 2, 165207; 5, 165473; 6, 165474.
Braitsch, Synth. React. Inorg. Met. Org. Chem.
119.
[23] F.A.L. Anet, V.J. Basus, J. Magn. Res. 32 (1978) 339.
8 (1978)
[24] N. Okazawa, T.S. Sorenson, Can. J. Chem. 56 (1978) 2737.
[25] R. Keat, L. Manojlovic-Muir, K.W. Muir, D.S. Rycroft, J. Chem.
Soc. Dalton Trans. (1981) 2192.
Acknowledgements
[26] H. Goldwhite, P.P. Power, Org. Mag. Res. 11 (1978) 499.
[27] W. Massa, Crystal Structure Determination, Springer-Verlag,
Berlin, Heidelberg, Germany, 2000.
We are grateful for the financial support provided by
‘Fondo de Desarrollo Cient´ıfico y Tecnolo´gico (FON-
DECYT)’, Chile (Projectos No. 2980031, 4000002 and
8980007). E.S.-M. thanks Professor Joanne Stewart for
useful discussions.
[28] M.T. Pinillos, M.T. Jarauta, D. Carmona, L.A. Oro, C. Apreda,
C. Foses-Foses and, F.H. Cano, J. Organomet. Chem. 345 (1998)
C13.
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Masdeu, A. Ruiz, T. Saballs, J. Organomet. Chem. 403 (1991)
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[30] M. Valderrama, R. Contreras, D. Boys, Polyhedron (1997) 16, 11,
1811.
[31] M. Valderrama, R. Contreras, M. Munoz, M.P. Lamata, D.
˜
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