Phenylantimony(III) derivatives of tetraphenyldichalcogenoimidodiphosphinic acids. Crystal and molecular structure of PhSb[(XPPh2)(SPPh2)N]2 (X=O, S)

Article abstract of DOI:10.1016/S0022-328X(01)01198-6

The reactions between PhSbCl₂ and M[(XPPh₂)(YPPh₂)N] (M=Na, K; X, Y=O, S), using 1:1 and 1:2 molar ratios, have been investigated. PhSbCl[(XPPh₂)(YPPh₂)N] and PhSb[(XPPh₂)(YPPh₂)N]₂ were isolated as microcrystalline powders and were characterized using IR and NMR (¹H, ³¹P) spectroscopy. On standing in chloroform solution the chloro derivative PhSbCl[(SPPh₂)₂N] was found to rearrange to PhSb[(SPPh₂)₂N]₂. The molecular structures of PhSb[(XPPh₂)(SPPh₂)N]₂ (X=O, S) were investigated by X-ray diffraction. The crystals of both compounds contain monomeric units with asymmetric chelating ligand fragments, resulting in a square pyramidal CSbX₂S₂ core with an apical phenyl group. The antimony lone pair of electrons appears to be stereochemically active and is located trans to the phenyl group, as suggested by the displacement of the metal atom from the best basal plane formed by the chalcogens in the opposite direction with respect to the apical carbon. For the monothio derivative, the molecule displays different ligand behaviour, i.e. O- and S-primary coordinations, respectively.

Full text of DOI:10.1016/S0022-328X(01)01198-6

Journal of Organometallic Chemistry 642 (2002) 113–119
www.elsevier.com/locate/jorganchem
Phenylantimony(III) derivatives of
tetraphenyldichalcogenoimidodiphosphinic acids. Crystal and
molecular structure of PhSb[(XPPh2)(SPPh2)N]2 (X=O, S)
Ioan Ghesner a, Laura Opris a, Gabor Balazs c, Hans J. Breunig c, John E. Drake b,
Anca Silvestru a, Cristian Silvestru a,*
a Facultatea de Chimie si Inginerie Chimica, Uni6ersitatea Babes-Bolyai, RO-3400 Cluj-Napoca, Romania
b Department of Chemistry and Biochemistry, Uni6ersity of Windsor, Windsor, Ontario, Canada N9B 3P4
c Institut fu¨r Anorganische und Physikalische Chemie, Uni6ersita¨t Bremen, Postfach 330440, D-28334 Bremen, Germany
Received 12 June 2001; accepted 30 August 2001
Abstract
The reactions between PhSbCl2 and M[(XPPh2)(YPPh2)N] (M=Na, K; X, Y=O, S), using 1:1 and 1:2 molar ratios, have been
investigated. PhSbCl[(XPPh2)(YPPh2)N] and PhSb[(XPPh2)(YPPh2)N]2 were isolated as microcrystalline powders and were
characterized using IR and NMR (1H, 31P) spectroscopy. On standing in chloroform solution the chloro derivative
PhSbCl[(SPPh2)2N] was found to rearrange to PhSb[(SPPh2)2N]2. The molecular structures of PhSb[(XPPh2)(SPPh2)N]2 (X=O,
S) were investigated by X-ray diffraction. The crystals of both compounds contain monomeric units with asymmetric chelating
ligand fragments, resulting in a square pyramidal CSbX2S2 core with an apical phenyl group. The antimony lone pair of electrons
appears to be stereochemically active and is located trans to the phenyl group, as suggested by the displacement of the metal atom
from the best basal plane formed by the chalcogens in the opposite direction with respect to the apical carbon. For the monothio
derivative, the molecule displays different ligand behaviour, i.e. O- and S-primary coordinations, respectively. © 2002 Elsevier
Science B.V. All rights reserved.
Keywords: Phenylantimony(III) compounds; Imidodiphosphinato ligands
lone pair are considered, the distorted coordination
polyhedron can be described as either pseudo-trigonal
bipyramid or pseudo-octahedron. Thus, in the case of
the monomeric PhSb[S(S)P(OPri)2]2 the dithiophospho-
rus ligands are asymmetric monometallic biconnective,
with cis short and long metal–sulfur distances, respec-
tively, forming the basal plane of a square pyramid.
The antimony lone pair of electrons was suggested to
be stereochemically active, occupying the axial position
trans to the phenyl group [2]. In the molecule of the
related PhSb[S(O)CCH3]2 the monothio ligands are pri-
mary bonded to the metal center through the sulfur
atoms and the oxygen atoms are involved in secondary
intramolecular Sb···O interactions, thus resulting in a
similar distorted square pyramidal CSbS2O2 core [3].
However, intermolecular Sb···S interactions trans to the
phenyl group give weak dimer associations in solid
state and therefore it was suggested that the lone pair is
probably inactive in this case.
1. Introduction
The use of organophosphorus ligands of the type
[R2PXY]− (R=alkyl, aryl, alkoxy; X, Y=O, S) often
affords the isolation of inorganic and organometallic
derivatives of antimony(III) exhibiting a large variety of
structures [1]. Two factors often considered to be of
importance in contributing to distortion of the metal
coordination core are the small bite of the ligand
and/or the stereochemical activity of the antimony lone
pair of electrons. For most organoantimony(III) deriva-
tives of phosphorus ligands, the primary bonds to the
metal center form the usual trigonal pyramidal geome-
try. However, if the secondary Sb···chalcogen interac-
tions and the possible stereochemical activity of the
* Corresponding author. Fax: +40-64-190818.
E-mail address: cristi@chem.ubbcluj.ro (C. Silvestru).
0022-328X/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01198-6

114
I. Ghesner et al. / Journal of Organometallic Chemistry 642 (2002) 113–119
Tetraorganodichalcogenoimidodiphosphinato anions,
spectroscopy and X-ray diffraction. The crystal and
[(XPR2)(YPR%)N]− are versatile chelating ligands able
molecular structures of PhSb[(SPPh2)2N]2 and PhSb-
[(OPPh2)(SPPh2)N]2 were determined by single crystal
X-ray diffraction.
2
to adjust to various coordination geometries required
by metal centers because of the flexibility of the XP-
NPY skeleton [4–7]. Therefore, they are good candi-
dates for investigation of the ligand bite influence on
the distortion degree of the coordination polyhedron
around a metal center. The use of such ligands in
organometallic chemistry of main group metals has
been mainly limited to Sn [8–12] and Te compounds
[13–19]. Only two inorganic antimony(III) compounds,
i.e. Sb[(SePPh2)2N]3 [20] and (m-S)(m-I)2[Sb(SPPh2)2N]2
[21], and few diphenylantimony(V) derivatives,
Ph2SbCl2[(OPPh2)(XPPh2)N] (X=O, S) and Ph2SbCl2-
[(OPMe2)(OPPh2)N] [22], have been reported so far.
Here we report on the synthesis and spectroscopic
characterization of some phenylantimony(III) com-
pounds, PhSbCl[(XPPh2)(YPPh2)N] and PhSb[(XPPh2)-
(YPPh2)N]2 (X=O, S), as well as the crystal and
molecular structures of PhSb[(SPPh2)2N]2 and PhSb-
[(OPPh2)(SPPh2)N]2.
2.2. IR spectra
The absence of strong absorptions around 2700–
2600 [w(NH)] and 950–900 cm−1 [assigned to
was(P2NH)], which are characteristic of the free
(XPPh2)(SPPh2)NH acids, along with the presence of
strong absorptions in the regions 1240–1200 cm−1
,
assigned to the was(P2N) stretching vibrations, indicate
that the phosphorus ligands are coordinated to the
metal center in the deprotonated form.
2.3. NMR spectra
The 1H-NMR spectra of the PhSbCl[(XPPh2)-
(YPPh2)N] (1–3) and PhSb[(XPPh2)(YPPh2)N]2 (4–6)
derivatives show the expected resonances for the phenyl
groups bonded to antimony and phosphorus atoms.
For the complexes containing symmetric ligand units,
only one broad 31P resonance was observed at room
temperature. This could be indicative of fluxional be-
havior of molecules of type (a) and (b) (X=Y), respec-
tively, with imidodiphosphinato ligands asymmetrically
coordinated through both chalcogen atoms to anti-
mony. However, an attempt to record the low-tempera-
ture 31P-NMR spectrum for a freshly prepared PhSbCl-
[(SPPh2)2N]2 (1) sample resulted only in a broader
resonance at −40 °C (the quality of the spectrum
prevented us from recording it at lower temperature).
The 31P-NMR spectrum of PhSbCl[(OPPh2)-
(SPPh2)N] (2) exhibits two singlet resonances (phospho-
rus–phosphorus coupling was not resolved). The mag-
nitude of the chemical shifts [l (ppm) 27.6 (Ph2PO),
33.4 (Ph2PS)] indicates O, S-chelate coordination of the
asymmetric imidodiphosphinato ligand moiety, with the
oxygen trans to the chlorine atom (structure a) [cf.
Ph2SbCl2[(OPPh2)(SPPh2)N] [22]: l 26.5 (Ph2PO), 32.1
(Ph2PS)]. For the disubstituted complex PhSb[(OPPh2)-
(SPPh2)N]2 (5) the 31P spectrum exhibits four broad
resonances of 1:1:2 intensity ratio (signals at l 21.8 and
23.5 ppm are partially overlapped), a pattern consistent
with a structure of type (c) in solution, with non-equiv-
alent PS and PO atoms, as established in the solid state
by X-ray diffraction.
2. Results and discussion
2.1. Preparation
The title compounds were prepared according to Eqs.
(1) and (2), by reacting stoichiometric amounts of
phenylantimony chlorides and the alkali salt of the
appropriate organophosphorus ligand:
PhSbCl2+M[(XPPh2)(YPPh2)N]
“PhSbCl[(XPPh2)(YPPh2)N]+MCl
X=Y=S
(1)
1
2
3
X=O, Y=S
X=Y=O
PhSbCl2+2M[(XPPh2)(YPPh2)N]
“PhSb[(XPPh2)(YPPh2)N]2+2MCl
(2)
4
5
6
X=Y=S
X=O, Y=S
X=Y=O
All compounds were isolated as air-stable crystalline
products. The dithio derivative 1 and 4 are yellow,
while the other compounds are white solids. They were
characterized by IR and NMR (1H, 31P) spectroscopy.
During attempts to grow crystals of the chloro deriva-
tive PhSbCl[(SPPh2)2N] from a chloroform–hexane sol-
vent mixture, a rearrangement process occurred leading
to the isolation of yellow crystals of the disubstituted
derivative PhSb[(SPPh2)2N]2 as was shown by NMR

I. Ghesner et al. / Journal of Organometallic Chemistry 642 (2002) 113–119
115
S(2)ꢀSb(1)ꢀS(4) 169.5(1)° for 4, and O(1)ꢀSb(1)ꢀO(2)
169.1(7)°, S(1)ꢀSb(1)ꢀS(2) 172.5(1)° for 5]. In com-
,
pound 4 the antimony atom is displaced −0.107 A
from the best basal plane formed by the sulfur atoms
(sulfur atom deviations ranging from −0.136 to 0.144
,
A) in the opposite direction with respect to the apical
carbon of the CSbS4 core [CꢀSb(1)ꢀS range 83.8(1)–
96.2(1)°]. A quite similar geometry was observed for
the CSbO2S2 core in 5, where the chalcogen atoms
are basically coplanar and the metal atom lies about
,
−0.161 A under the basal plane [CꢀSb(1)ꢀchalcogen
range 83.8(3)–88.2(3)°].
The ligand moieties are coordinated through both
sulfur atoms in compound 4 with a cis arrangement of
,
the short Sb(1)ꢀS [2.666(1), 2.690(1) A, S(2)ꢀSb(1)ꢀS(3)
,
80.73(3)°] and long Sb(1)ꢀS bonds [2.778(1), 2.810(1) A,
Fig. 1. ORTEP plot of the molecule PhSb[(SPPh2)2N]2 (4). The atoms
are drawn with 20% probability ellipsoids except for the hydrogen
atoms.
S(1)ꢀSb(1)ꢀS(4) 93.76(4)°], respectively. The aniso-
bidentate coordination of the ligand moieties in the
molecule of 4 is not dramatically reflected in the magni-
tude of the PꢀS [range 2.011(1)–2.030(1) A] and PꢀN
[range 1.587(3)–1.596(3) A] bonds which are equal,
,
2.4. Crystal and molecular structure of PhSb-
[(SPPh2)2N]2 (4) and PhSb[(OPPh2)(SPPh2)N]2 (5)
,
within the experimental errors, and intermediate be-
tween single and double phosphorusꢀsulfur and phos-
phorusꢀnitrogen bonds [cf. the free acid (SꢁPPh2)2NH
The molecular structures of compounds 4 and 5 with
the atom numbering scheme are shown in Figs. 1 and 2,
respectively, and selected interatomic distances and an-
gles are listed in Table 1. The crystal structures of both
compounds consist of discrete monomeric molecular
units separated by normal van der Waals distances.
The structures of compounds 4 (Fig. 1) and 5 (Fig. 2)
reveal some common trends. Thus, the coordination
geometry around the antimony atom is distorted square
pyramidal with an apical phenyl group and asymmetric
monometallic biconnective dichalcogenoimidodiphos-
phinato ligands [trans S(1)ꢀSb(1)ꢀS(3) 170.2(1)°,
,
[23]: PꢁS 1.937(1), 1.950(1), PꢀN 1.683(2), 1.672(2) A;
[2-(Me2NCH2)C6H4]TeꢀSꢀPPh2ꢁNꢀPPh2ꢁS [19]: PꢀS
,
2.057(1), PꢁS 1.945(1), PꢀN 1.612(3), PꢁN 1.557(3) A].
The conformation of both inorganic SbS2P2N rings is
distorted boat, but with different atom types in the
apices; the metal and N(1) atoms in one and P(3) and
S(4) atoms in the other, in both cases bringing the
nitrogen atoms below the basal plane. A significant
difference in the magnitude of the SbꢀSꢀP angles within
the two rings, i.e. 97.52(5), 93.80(5) versus 107.87(5),
101.62(5)°, should be also noted.
Fig. 2. ORTEP plot of the molecule PhSb[(OPPh2)(SPPh2)N]2 (5). The atoms are drawn with 20% probability ellipsoids except for the hydrogen
atoms.

116
I. Ghesner et al. / Journal of Organometallic Chemistry 642 (2002) 113–119
Table 1
,
Selected interatomic distances (A) and angles (°) in PhSb[(SPPh2)2N]2 (4) and PhSb[(OPPh2)(SPPh2)N]2 (5)
PhSb[(SPPh2)2N]2 (4)
PhSb[(OPPh2)(SPPh2)N]2 (5)
Sb(1)ꢀC(1)
Sb(1)ꢀS(1)
Sb(1)ꢀS(2)
2.192(3)
2.7778(11)
2.6659(12)
Sb(1)ꢀC(1)
Sb(1)ꢀO(1)
Sb(1)ꢀS(1)
2.162(7)
2.169(5)
2.902(2)
Sb(1)ꢀS(3)
Sb(1)ꢀS(4)
2.6901(11)
2.8097(12)
Sb(1)ꢀO(2)
Sb(1)ꢀS(2)
2.329(5)
2.661(2)
S(1)ꢀP(1)
P(1)ꢀN(1)
P(2)ꢀN(1)
S(2)ꢀP(2)
2.0111(15)
1.596(3)
1.587(3)
S(3)ꢀP(3)
P(3)ꢀN(2)
P(4)ꢀN(2)
S(4)ꢀP(4)
2.0169(15)
1.590(3)
1.596(3)
P(1)ꢀO(1)
P(1)ꢀN(1)
P(2)ꢀN(1)
P(2)ꢀS(1)
1.532(5)
1.572(6)
1.597(6)
2.004(3)
P(3)ꢀO(2)
P(3)ꢀN(2)
P(4)ꢀN(2)
P(4)ꢀS(2)
1.515(5)
1.606(6)
1.577(6)
2.036(3)
2.0304(14)
2.0114(13)
C(1)ꢀSb(1)ꢀS(1)
C(1)ꢀSb(1)ꢀS(2)
85.04(10)
86.61(10)
C(1)ꢀSb(1)ꢀS(3)
C(1)ꢀSb(1)ꢀS(4)
96.22(10)
83.84(10)
C(1)ꢀSb(1)ꢀO(1)
C(1)ꢀSb(1)ꢀS(1)
88.2(3)
85.5(2)
C(1)ꢀSb(1)ꢀO(2)
C(1)ꢀSb(1)ꢀS(2)
83.8(3)
88.0(2)
S(1)ꢀSb(1)ꢀS(2)
S(1)ꢀSb(1)ꢀS(4)
S(1)ꢀSb(1)ꢀS(3)
89.63(4)
93.76(4)
170.17(3)
S(3)ꢀSb(1)ꢀS(4)
S(2)ꢀSb(1)ꢀS(3)
S(2)ꢀSb(1)ꢀS(4)
96.06(3)
80.73(3)
169.55(3)
O(1)ꢀSb(1)ꢀS(1)
O(1)ꢀSb(1)ꢀS(2)
O(1)ꢀSb(1)ꢀO(2)
88.66(14)
87.35(14)
169.15(17)
O(2)ꢀSb(1)ꢀS(2)
O(2)ꢀSb(1)ꢀS(1)
S(1)ꢀSb(1)ꢀS(2)
85.11(13)
97.92(13)
172.46(7)
Sb(1)ꢀS(1)ꢀP(1)
Sb(1)ꢀS(2)ꢀP(2)
97.52(5)
93.80(5)
Sb(1)ꢀS(3)ꢀP(3)
Sb(1)ꢀS(4)ꢀP(4)
107.87(5)
101.62(5)
Sb(1)ꢀO(1)ꢀP(1)
Sb(1)ꢀS(1)ꢀP(2)
130.3(3)
96.12(11)
Sb(1)ꢀO(2)ꢀP(3)
Sb(1)ꢀS(2)ꢀP(4)
118.0(3)
94.79(10)
S(1)ꢀP(1)ꢀN(1)
P(1)ꢀN(1)ꢀP(2)
S(2)ꢀP(2)ꢀN(1)
118.37(13)
135.6(2)
117.14(12)
S(3)ꢀP(3)ꢀN(2)
P(3)ꢀN(2)ꢀP(4)
S(4)ꢀP(4)ꢀN(2)
119.41(13)
134.3(2)
118.07(12)
O(1)ꢀP(1)ꢀN(1)
P(1)ꢀN(1)ꢀP(2)
S(1)ꢀP(2)ꢀN(1)
118.1(3)
134.6(4)
117.4(2)
O(2)ꢀP(3)ꢀN(2)
P(4)ꢀN(2)ꢀP(3)
S(2)ꢀP(4)ꢀN(2)
116.9(3)
131.5(4)
117.3(3)
In the case of 5 the ligand units are again coordinated
asymmetrically through both chalcogens to the metal.
Surprisingly the primary coordination is established by
different atoms for the two ligand moieties of a molecule
as suggested by the Sb(1)ꢀO versus Sb(1)ꢀS bond
lengths for a SbOSP2N ring [Sb(1)ꢀO(1) 2.169(5),
occupying the apex positions [P(1)/S(1) and Sb(1)/N(2)
atoms, respectively] and both nitrogen atoms below the
basal plane. It should also be noted that there is signifi-
cant opening up of the SbꢀOꢀP bond angle [130.3(3)°] in
comparison with the Sb’OꢁP angle [118.0(3)°],
whereas the corresponding Sb’SꢁP [96.1(1)°] and
SbꢀSꢀP [94.8(1)°] bond angles are of same magnitude.
,
Sb(1)ꢀS(1) 2.902(2) A, and Sb(1)ꢀO(2) 2.329(5),
,
Sb(1)ꢀS(2) 2.661(2) A, respectively], with the shorter
SbꢀO and SbꢀS bonds in cis positions [O(1)ꢀSb(1)ꢀS(2)
87.3(1)°]. This unexpected asymmetric coordination be-
havior seems to be preserved in solution too and might
explain the non-equivalence of the phosphorus atoms
bearing the same chalcogen atom in PhSb[(OPPh2)-
(SPPh2)N]2 (see Section 2.3.). The O- versus S-primary
coordinations of the asymmetric bidentate ligand units
in the molecule of 5 resulted in different bond lengths
within the OPNPS skeletons (scheme d) which is consis-
tent with a slightly higher degree of double bonding in
the P(2)ꢀS(1), P(3)ꢀO(2), P(1)ꢀN(1) and P(4)ꢀN(2)
bonds than in the others [cf. the free acid (OꢁPPh2)-
(SꢁPPh2)NH [24]: PꢁS 1.935(2), (S)PꢀN 1.694(4),
3. Conclusions
New PhSbCl[(XPPh2)(YPPh2)N] and PhSb[(XPPh2)-
(YPPh2)N]2 derivatives were prepared and characterized
using IR and NMR (1H, 31P) spectroscopy. The molecu-
lar structures of PhSb[(XPPh2)(SPPh2)N]2 [X=S(4),
O(5)] were investigated by X-ray diffraction. Both com-
pounds are monomeric, with asymmetric chelating lig-
and fragments, thus resulting in square pyramidal
CSbX2S2 cores. For the monothio derivative, the
molecule displays different ligand behaviour, i.e. O- and
S-primary coordinations, respectively. The displace-
ment of the antimony atom from the best basal plane of
the four chalcogens in the opposite direction with re-
spect to the apical carbon atom suggests that the anti-
mony lone pair of electrons is stereochemically active
and located trans to the phenyl group.
,
(O)PꢀN 1.668(5), PꢁO 1.491(4) A]:
4. Experimental
4.1. Materials and procedures
The conformation of the inorganic SbOSP2N rings is
similar to that observed for the molecule of the dithio
derivative 4, i.e. distorted boat with different atom types
All manipulations were carried out under Ar by
Schlenk techniques. Solvents were dried and freshly

I. Ghesner et al. / Journal of Organometallic Chemistry 642 (2002) 113–119
117
distilled prior to use. Phenylantimony(III) dichloride
was prepared from Ph3Sb and SbCl3 (molar ratio 1:2, in
the absence of a solvent) [25]. The starting materials
were prepared according to literature methods:
Na[(OPPh2)2N] [26], K[(SPPh2)2N] [8] and K[(OPPh2)-
(SPPh2)N] [11]. Infrared spectra were recorded in the
range 4000–250 cm−1 as KBr pellets on a Jasco FT/
(cm−1): 1215s [was(P2N)]. 1H-NMR: l 7.41m (15H,
PꢀC6H5+SbꢀC6H5, meta+para), 7.72ddd [4H, P(S)-
3
3
4
C6H5-ortho, JPH 12.9, JHH 6.9, JHH 1.5 Hz], 7.85dd
3
3
[4H, P(O)ꢀC6H5-ortho, JPH 14.4, JHH 7.5 Hz], 8.10dd
(2H, SbꢀC6H5-ortho, JHH 7.8, JHH 1.5 Hz); 31P-NMR:
l 27.6s (Ph2PO), 33.4s (Ph2PS).
3
4
1
IR-615 instrument. The H- and 31P-NMR spectra were
4.2.3. PhSbCl[(OPPh2)2N] (3)
recorded on a Varian Gemini 300S instrument operat-
ing at 299.5 and 121.4 MHz, respectively, using solu-
tions in dried CDCl3. The chemical shifts are reported
in ppm relative to TMS and H3PO4 85%, respectively.
Anal. Found: C, 55.51; H, 3.73; N, 2.03. Calc. for
C30H25ClNO2P2Sb: C, 55.38; H, 3.87; N, 2.15%. IR
(cm−1): 1230s [was(P2N)]. 1H-NMR: l 7.27m (11H,
PꢀC6H5-meta, SbꢀC6H5-meta+para), 7.40t (4H,
3
PꢀC6H5-para, JHH 7.2 Hz), 7.67dd (8H, PꢀC6H5-ortho,
3
4.2. Preparation of the title compounds,
PhSbCl[(XPPh2)(YPPh2)N] and
3JPH 12.6, JHH 7.8 Hz), 7.94m (2H, SbꢀC6H5-ortho);
31P-NMR: l 24.9s,br.
PhSb[(XPPh2)(YPPh2)N]2 (Table 2)
4.2.4. PhSb[(SPPh2)2N]2 (4)
Mixtures of PhSbCl2 and alkali salt, M[(XPPh2)-
(YPPh2)N] (1:1 and 1:2 molar ratios) in 30 ml anhy-
drous CHCl3 were stirred for 6 h, then filtered under Ar
atmosphere to remove the resulting MCl. The filtrate
was evaporated under reduced pressure and a solid was
obtained. Details of the preparations and the melting
points are given in Table 2. Microanalyzes (C, H, N)
and NMR spectra are consistent with the given compo-
sition of the isolated products.
Anal. Found: C, 59.37; H, 3.98; N, 2.45. Calc. for
C54H45N2P4S4Sb: C, 59.19; H, 4.14; N, 2.56%. IR
(cm−1): 1210vs [was(P2N)]. 1H-NMR: l 7.22m (27H,
PꢀC6H5+SbꢀC6H5, meta+para), 7.70s,br (16H,
PꢀC6H5-ortho), 8.24m (2H, SbꢀC6H5-ortho); 31P-NMR:
l 38.2s,br.
4.2.5. PhSb[(OPPh2)(SPPh2)N]2 (5)
Anal. Found: C, 60.75; H, 4.03; N, 2.57. Calc. for
C54H45N2O2P4S2Sb: C, 60.97; H, 4.26; N, 2.63%. IR
(cm−1): 1240vs [was(P2N)]. 1H-NMR: l 7.30m (27H,
4.2.1. PhSbCl[(SPPh2)2N] (1)
Anal. Found: C, 52.70; H, 3.89; N, 1.97. Calc. for
C30H25ClNP2S2Sb: C, 52.77; H, 3.69; N, 2.05%. IR
(cm−1): 1200s [was(P2N)]. 1H-NMR: l 7.40m (15H,
PꢀC6H5+SbꢀC6H5, meta+para), 7.83s,br (8H,
PꢀC6H5+SbꢀC6H5,
meta+para),
7.63m
[10H,
P(S)ꢀC6H5+SbꢀC6H5, ortho], 7.87m [8H, P(O)ꢀC6H5-
ortho]; 31P-NMR: l 21.8s, 23.5s,br (Ph2PO), 35.1s,
57.5s,br (Ph2PS).
3
PꢀC6H5-ortho), 8.09dd (2H, SbꢀC6H5-ortho, JHH 8.1,
4JHH 1.2 Hz); 31P-NMR: l 37.3s,br.
4.2.6. PhSb[(OPPh2)2N]2 (6)
Anal. Found: C, 62.98; H, 4.26; N, 2.93. Calc. for
C54H45N2O4P4Sb: C, 62.87; H, 4.40; N, 2.71%. IR
(cm−1): 1240vs [was(P2N)]. 1H-NMR: l 7.15m (19H,
PꢀC6H5-meta, SbꢀC6H5-meta+para), 7.35t (8H,
4.2.2. PhSbCl[(OPPh2)(SPPh2)N] (2)
Anal. Found: C, 53.90; H, 3.94; N, 2.07. Calc. for
C30H25ClNOP2SSb: C, 54.04; H, 3.78; N, 2.10%. IR
Table 2
Preparation and IR data for PhSbCln[(XPPh2)(YPPh2)N]2−n derivatives
Starting materials
Product [yield: g (%)]
m.p. (°C)
PhSbCl2 (g mmol−1
)
M[(XPPh2)(YPPh2)] (g mmol−1
)
K[(SPPh2)2N]
0.487/1.00
K[(OPPh2)(SPPh2)N]
0.447/0.9
Na[(OPPh2)2N]
0.439/1.00
K[(SPPh2)2N]
0.974/2.00
K[(OPPh2)(SPPh2)N]
0.942/2.00
Na[(OPPh2)2N]
0.729/1.66
PhSbCl[(SPPh2)2N] (1)
0.62 (91)
PhSbCl[(OPPh2)(SPPh2)N] (2)
0.54 (86)
PhSbCl[(OPPh2)2N] (3)
0.65 (100)
PhSb[(SPPh2)2N]2 (4)
0.92 (86)
PhSb[(OPPh2)(SPPh2)N]2 (5)
0.83 (78)
PhSb[(OPPh2)2N]2 (6)
0.44 (51)
92
0.270/1.00
0.256/0.9
160–162
68–84
0.270/1.00
0.270/1.00
0.270/1.00
0.224/0.83
199–200
185–188
219–221

118
I. Ghesner et al. / Journal of Organometallic Chemistry 642 (2002) 113–119
Table 3
that of the carbon atom to which they were attached.
The final cycle of full-matrix least-squares refinement
[28] converged (largest parameter shift was 0.001 times
its estimated S.D.).
X-ray crystal data and structure refinement for 4 and 5
4
5
Empirical formula
Formula weight
Temperature (K)
C54H45N2P4S4Sb
1095.88
173(2)
0.71073
Triclinic
C
54H45N2O2P4S2Sb
1063.67
299(2)
0.71073
Triclinic
5. Supplementary material
,
Wavelength (A)
Crystal system
Space group
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre CCDC no. 161031 for compound (4), and
160918 for compound (5). Copies of the information
may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(Fax: +44-1223-336033; e-mail: deposit@ccdc.cam.
ac.uk or www: http://www.ccdc.cam.ac.uk).
(
(
P1
P1
Unit cell dimension
,
a (A)
11.330(2)
11.678(1)
21.070(6)
74.98(1)
77.97(2)
68.40(1)
2483.6(9)
2
11.157(2)
11.634(2)
20.864(4)
77.82(3)
79.57(3)
68.60(3)
2448.5(8)
2
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
V (A )
Z
Dcalc (g cm−3
)
1.465
1.443
Absorption coefficient
(mm−1
F (000)
Crystal size (mm)
q range for data collection 2.23–27.50
(°)
0.892
0.823
Acknowledgements
)
1116
0.7×0.5×0.4
1084
0.22×0.20×0.20
1.01–23.25
This work was supported by the Romanian National
University Research Council (CNCSIS) through re-
search project No. 312/2000. The financial support of
the Deutscher Akademischer Austauschdienst (C.S.—
DAAD grant/2000) and the Natural Sciences and Engi-
neering Research Council of Canada (J.E.D.) is
gratefully acknowledged.
Reflections collected
Independent reflections
12257
10616
[Rint=0.0308]
17509
6924 [Rint=0.1070]
Data/restraints/parameters 10616/0/588
6924/0/586
1.081
Goodness-of-fit on F2
Final R indices
0.990
R1=0.0437;
wR2=0.0937
R1=0.0699;
wR2=0.1050
0.605 and
−0.769
R1=0.0853;
wR2=0.0899
R1=0.1518;
wR2=0.1050
0.452 and −0.494
[F2\2|(F2)]
R indices (all data)
References
Largest difference peak
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,
and hole (e A
)
3
PꢀC6H5-para, JHH 7.2 Hz), 7.70dd (16H, PꢀC6H5-or-
3
3
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tions with isotropic thermal parameters set at 1.2 times

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