Preparation of the first complexes of bidentate sulfimides; the X-ray crystal structures of [PdBr2{1,4-(PhS{NH})2C6H4}] 2, [PdCl2{1,2-(PhS{NH})(PhS)C6H4}] and trans-[PdCl2{1,2-(PhS{NH})(PhS)C6H4} PPh3]

Article abstract of DOI:10.1002/ejic.200390012

Reaction of [PPh₄]₂[Pd₂X₆] (where X = Cl, Br or I) with 1,4-(PhS{NH})₂C₆H₄ (1) in dichloromethane results in the formation of [Pd{1,4-(PhS{NH})₂C₆H₄}X₂] ₂ (2). X-ray crystallography (performed using a synchrotron source) confirms that in the case where X = Br (2a) both the bis-sulfimides act as bridging ligands through N-Pd bonds producing an 18-membered ring system linking the four sulfur atoms into an almost perfect square. Changing the reaction solvent to methanol/dichloromethane results in the formation of a polymeric material. Reaction of [PdCl₂(PhCN)₂] with 1,2-(PhS{NH})-(PhS)C₆H₄ (3) results in the formation of [PdCl₂{1,2-(PhS{NH})(PhS)C₆H₄}] (4) in which 3 acts as a bidentate ligand, bound by N-Pd and S-Pd bonds to form a unique MSCCSN metallacycle. The Pd-S bond is broken upon reaction with one equivalent of PPh₃, generating trans-[PdCl₂{1,2-(PhS{NH})(PhS)C₆H₄} PPh₃] (5); further reaction with PPh₃ results in complete removal of 3 from the system and formation of trans-[PdCl₂(PPh₃)₂]. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejic.200390012

FULL PAPER
Preparation of the First Complexes of Bidentate Sulfimides; the X-ray Crystal
Structures of [PdBr2{1,4-(PhS{NH})2C6H4}]2, [PdCl2{1,2-
(PhS{NH})(PhS)C6H4}] and trans-[PdCl2{1,2-(PhS{NH})(PhS)C6H4}PPh3]
Mark R. J. Elsegood,[a] Kathryn E. Holmes,[a] Paul F. Kelly,*[a] Elizabeth J. MacLean,[b]
Jonathon Parr,[c] and Julia M. Stonehouse[a]
Keywords: S ligands / N ligands / Palladium / Bridging ligands
Reaction of [PPh4]2[Pd2X6] (where X = Cl, Br or I) with 1,4-
(PhS)C6H4 (3) results in the formation of [PdCl2{1,2-
(PhS{NH})2C6H4 (1) in dichloromethane results in the forma- (PhS{NH})(PhS)C6H4}] (4) in which 3 acts as a bidentate li-
tion of [Pd{1,4-(PhS{NH})2C6H4}X2]2 (2). X-ray crystallo-
graphy (performed using a synchrotron source) confirms that
in the case where X = Br (2a) both the bis-sulfimides act as
gand, bound by N−Pd and S−Pd bonds to form a unique
MSCCSN metallacycle. The Pd−S bond is broken upon reac-
tion with one equivalent of PPh3, generating trans-
bridging ligands through N−Pd bonds producing an 18-mem- [PdCl2{1,2-(PhS{NH})(PhS)C6H4}PPh3] (5); further reaction
bered ring system linking the four sulfur atoms into an almost
perfect square. Changing the reaction solvent to methanol/
dichloromethane results in the formation of a polymeric
material. Reaction of [PdCl2(PhCN)2] with 1,2-(PhS{NH})-
with PPh3 results in complete removal of 3 from the system
and formation of trans-[PdCl2(PPh3)2].
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
ation. They both also have clear potential as new ligands.
Ligand 1 has the obvious potential to act as a bidentate
bridge between two metal centres. Examples of such ligands
are, of course, well-known and they can often act as the
lynchpin for much important chemistry. By way of example,
Godfrey et al. recently demonstrated the ability of 1,3-
bis(diphenylphosphinoyl)propane to bridge manganese
centres in binuclear complexes.[5] In this particular case the
ligand is crucial to the product’s ability to reversibly take
up SO2. Such properties highlight the need to investigate
new ligand systems of this type, and here we demonstrate
for the first time that 1 can act in this way and in doing so
highlight the potential of an entirely new class of bidentate
ligand. In the case of 3 the presence of both nitrogen and
sulfur atoms capable of binding to metal centres provides
the potential for the system to act as a bidentate chelating
ligand. The use of ligands containing coordination sites of
different binding strengths continues to be of importance
(for example with the use of hemilabile ligands within cata-
lytically important systems)[6] and here we show that 3 can
indeed act as a bidentate ligand.
Recent work within our group has demonstrated that the
mononuclear sulfimide Ph2SNH is an excellent ligand inso-
far as it readily forms N-bound complexes with a range of
transition metal centres.[1] In addition, its importance as a
ligand is enhanced by the fact that it is capable of stabilising
unusual coordination geometries[2] and that significant hy-
drogen-bonding effects can be observed between the ligand
and counterions.[3] In order to build upon these results, we
have recently reported the preparation of a range of
new sulfimide systems based upon polysulfide starting
materials.[4] These include the bis-sulfimide 1,4-
(PhS{NH})2C6H4 (1) and the mixed sulfide/sulfimide 1,2-
(PhS{NH})(PhS)C6H4 (3), both of which prove to have an
interesting structure in their own right thanks to the ap-
pearance of hydrogen-bonding arrays generated by interac-
tions between the sulfimide units and waters of crystallis-
[a]
Department of Chemistry, Loughborough University
Loughborough LE11 3TU, UK
Fax: (internat.) ϩ44-(0)1509/223-925
E-mail: p.f.kelly@lboro.ac.uk
[b]
CLRC Daresbury Laboratory,
Daresbury, Warrington, WA4 4AD, UK
Fax: (internat.) ϩ44-(0)1025/603-193
E-mail: e.j.maclean@dl.ac.uk
Results and Discussion
[c]
Department of Chemistry, Yale University,
225 Prospect Street, New Haven
CT 06520-8107, USA.
Fax: (internat.) ϩ1-203/423-9990
E-mail: parr@jaxindy.chem.yale.edu
We have recently demonstrated that reaction of 1,4-
(PhS)2C6H4 with MSH (O-mesitylsulfonylhydroxylamine)
results in the formation of a salt of the protonated bis-sulf-
120
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/03/0101Ϫ0120 $ 20.00ϩ.50/0 Eur. J. Inorg. Chem. 2003, 120Ϫ127

The First Complexes of Bidentate Sulfimides
FULL PAPER
˚
Figure 1. The X-ray crystal structure of one of the two unique molecules in the unit cell of 2a; selected bond lengths (A) and angles (°):
Pd(1)ϪN(1) 2.020(5), Pd(1)ϪN(2) 2.025(5), Pd(1)ϪBr(1) 2.4411(9), Pd(1)ϪBr(2) 2.4227(9), N(1)ϪS(1) 1.622(5), N(2)ϪS(2) 1.618(5);
Pd(1)ϪN(2)ϪS(2) 122.4(3), Pd(1)ϪN(1)ϪS(1) 122.2(3), Br(2)ϪPd(1)ϪBr(1) 170.91(3), N(1)ϪPd(1)ϪN(2) 174.7(2)
imide [1,4-(PhS{NH2})2C6H4]2ϩ from which the free bis- side on view shown in Figure 2 (this illustrates the structure
sulfimide 1 may be generated by treatment with the base of one of the two independent molecules in the unit cell Ϫ
DBU. Compound 1 is an air-stable, colourless material see X-ray text below). The PdϪBr bonds are almost perpen-
which may be crystallised in hydrated or water-free forms, dicular to the Pd2N4 plane [N(2)ϪPd(1)ϪBr(2) ϭ 85.7°]
both of which have structures containing extended hydro- while the SϪN bonds of each of the ligands also project on
gen-bonding arrays. In the light of the high affinity of the either side of this plane (in what has been referred to as a
related monosulfimide Ph2SNH for metal centres one might ‘‘sofa-bed’’ arrangement).[7] The linking phenyl units of
expect 1 to readily react with transition metal complexes each ligand are parallel to each other and inclined at an
and we have now found this to indeed be the case.
Reaction of a stirred suspension of 1 with [PPh4]2[Pd2Br6] guing thing about the structure is that the positions of the
angle of 52.8° to the Pd2N4 plane. Perhaps the most intri-
in CH2Cl2 results in the formation of an insoluble orange/ sulfur atoms are such that they define an almost perfect
˚
˚
red product 2a. The IR spectrum of 2a clearly indicates the square, with S(2)ϪS(1) ϭ 6.325 A, S(2)ϪS(1A) ϭ 6.326 A
presence of 1 as a ligand. We have previously shown that in and S(1)ϪS(2)ϪS(1A) ϭ 91.5°. As Figure 2 shows, the fact
complexes of Ph2SNH the two key features which vary in that the bridging phenyls are offset relative to each other
the IR spectra are the SN and NH stretches, and in this precludes any π-π interactions. Unlike many of the com-
case they are shifted from 928 and 3111 cmϪ1 respectively plexes of Ph2SNH we have previously investigated there ap-
in the free ligand to 880 and 3260 cmϪ1 upon coordination. pear to be no significant interactions between the NϪH
In addition, microanalysis confirms the formulation groups of the ligands and halide ligands of adjacent molec-
‘‘[PdBr2{1,4-(PhS{NH})2C6H4}]n’’, although, of course, it ules.
provides no information as to the value of n. Standard crys-
tallisation techniques cannot be used upon 2a as, once
formed, it appears to be totally insoluble in a range of solv-
ents. Small microcrystals of the product can, however, be
obtained by changing the reaction conditions. If CH2Cl2 is
added to a solid mixture of the two reagents without stir-
ring, then a slow reaction occurs and 2a forms as crystals
large enough to be investigated by X-ray crystallography
using a synchrotron source.
X-ray crystallography performed in this manner reveals
that the structure of 2a consists of two PdBr2 units linked
Figure 2. The X-ray crystal structure of 2a viewed side-on, illustrat-
ing the relative disposition of the sulfimide groups and the
bridging phenyls
by two bis-sulfimide ligands, resulting in an overall binuc-
Complex 2a appears to be the only isolable material from
lear 18-membered ring arrangement (Figure 1).
this reaction. The initial yield equates to 67% based upon
The resulting relative dispositions of the PdϪBr, PϪN, palladium and more of the same material is obtained when
SϪN and bridging phenyl units are best illustrated by the the reaction filtrate is treated with Et2O. The latter proced-
Eur. J. Inorg. Chem. 2003, 120Ϫ127
121

P. F. Kelly et al.
FULL PAPER
ure generates 2a as an orange solid which does not then than the bright orange red colour of 2a the product is a
redissolve back into the CH2Cl2. From this observation we pale brown colour. IR spectroscopy reveals the presence of
can conclude that a small amount of another, soluble, com- bands due to 1 but the key stretches, ν[NϪH] and ν[NϪS],
plex of 1 is present in the initial filtrate; however, all at- are both stronger and broader than those in 2a and are
tempts to isolate this result in formation of 2a and so it is shifted to 3220 and 897 cmϪ1, respectively. Microanalysis
difficult to speculate as to its nature. The reaction of supports the formulation [PdBr2{1,4-(PhS{NH})2C6H4}]
[PPh4]2[Pd2I6] with 1 appears to proceed in an identical but unlike 2a (which shows the peaks which may be pre-
manner to that of its bromo counterpart (Scheme 1). Again, dicted from the aforementioned single crystal data) the X-
the product is an insoluble orange/red material whose IR ray powder pattern of this product shows no discernible
spectrum is extremely similar to that of 2a. Taken together peaks. This leads us to believe that this product is an
with microanalysis this allows us to formulate it as amorphous polymeric material rather than the binuclear
[PdI2{1,4-(PhS{NH})2C6H4}]2 (2b) with confidence. Al- structure of 2a. Interestingly, it forms even when only one
though we have yet to produce crystals suitable for X-ray equivalent of 1 is used in the reaction. In this case the ex-
crystallographic confirmation, we have every reason to be- pected [PPh4]2[(PdBr3)2{1,4-(PhS{NH})2C6H4}] (in which
lieve that 2b has the same kind of binuclear structure as 2a. the bis-sulfimide would link two [PdBr3]Ϫ units) does not
Likewise [PdCl2{1,4-(PhS{NH})2C6H4}]2 (2c) forms in the form. Rather, the polymeric material is generated, while the
analogous reaction with [PPh4]2[Pd2Cl6]; in this case mic- reaction filtrate contains just [PPh4]Br and unchanged
roanalysis results indicate that the dichloromethane solvate [PPh4]2[Pd2Br6] (as shown by IR spectroscopy). Given that
forms. The IR spectrum of this material is, however, very it is reasonable to assume this reaction proceeds via a tran-
similar to that of 2a and 2b and in this case PdϪCl stretches sient intermediate of the form [PdBr31]Ϫ in which one of
at 346 and 304 cmϪ1 consistent with the trans-halides are the nitrogen atoms of the ligand is bound to palladium, it
observed.
would appear that the halide trans to N in this case is activ-
The reaction time needed for the formation of com- ated towards displacement by another nitrogen. Similar re-
pounds 2 is long (typically three days), a fact dictated by sults are observed for reactions involving [Pd2Cl2]2Ϫ and
the insolubility of 1 in CH2Cl2. Although this would appear [Pd2I2]2Ϫ, generating insoluble polymeric products which
inefficient, in fact it is key to the formation of the binuclear are very pale brown and dark brown, respectively. The IR
product; changing the solvent system has a dramatic effect spectra of both products are analogous to that of the brom-
upon the course of the reaction (Scheme 1). Compound 1 ide product with broad ν[NϪH] (3211 and 3217 cmϪ1 for
is actually soluble in methanol and so addition of a solution chloride and iodide, respectively) and very broad ν[NϪS]
of the ligand in this solvent to a solution of [PPh4]2[Pd2Br6] peaks (centred on 897 cmϪ1 in both cases).
in CH2Cl2 results in an immediate reaction. Again, an in-
It would appear, therefore, that only when the reaction of
soluble product is generated (with just [PPh4]Br left in solu- 1 with [Pd2X6]2Ϫ is slowed down by the use of CH2Cl2 as
tion, as shown by IR spectroscopy) but in this case rather solvent is a molecular product seen; the use of methanol
Scheme 1
122
Eur. J. Inorg. Chem. 2003, 120Ϫ127

The First Complexes of Bidentate Sulfimides
FULL PAPER
encourages the fast formation of a polymeric material. It and we have yet to obtain crystalline samples. Once formed
should be noted, though, that in some solvents the reaction the material is totally insoluble in all solvents and tech-
does not proceed at all. For example, if the reactions are niques used to obtain single crystals of 2a are not amenable
attempted in MeCN then after three days of stirring the in this case due to the fast reaction time.
mixture simply consists of a suspension of unchanged 1 in
Reaction of [PdCl2(PhCN)2] with 1,2-(PhS{NH})-
the solution of the palladium starting material. As for the (PhS)C6H4 (3; molar ratio 1:1) in CH2Cl2 results in the
structure of the polymeric complexes we can only speculate formation of an orange solution from which a mass of dark
that they possess a linear polymeric arrangement made up orange/red crystals appears upon standing overnight. X-ray
of alternating PdX21 units. Of course other structural mo- crystallography reveals that this product is [PdCl2{1,2-
tifs could be envisaged and it may even be that the material (PhS{NH})(PhS)C6H4}] (4) in which 3 acts as a bidentate
contains a mixture of different oligomers (although we can ligand bound to the palladium through the sulfimide nitro-
be sure that none of the binuclear complex is present thanks gen and the thioether sulfur (Figure 3) (Scheme 2).
to the IR and powder X-ray results); only single crystal X-
The resulting metallacycle, which shows significant devi-
ray crystallography would provide an unequivocal answer ation from planarity (thus, for example, the two sulfurs ap-
˚
Figure 3. The X-ray crystal structure of 4; selected bond lengths (A) and angles (°): Pd(1)ϪN(1) 2.0203(19), N(1)ϪS(1) 1.5971(19),
S(1)ϪC(7) 1.7969(2), C(7)ϪC(8) 1.396(3), C(8)ϪS(2) 1.791(2), S(2)ϪPd(1) 2.2771(6), Pd(1)ϪCl(1) 2.3056(6), Pd(1)ϪCl(2) 2.3271(6);
Pd(1)ϪN(1)ϪS(1) 128.28(11), N(1)ϪS(1)ϪC(7) 113.75(10), S(1)ϪC(7)ϪC(8)125.82(17), C(7)ϪC(8)ϪS(2) 126.45(17), C(8)ϪS(2)ϪPd(1)
114.14(8), Cl(1)ϪPd(1)ϪN(1) 85.58(6), Cl(2)ϪPd(1)ϪS(2) 84.25(2)
Scheme 2
Eur. J. Inorg. Chem. 2003, 120Ϫ127
123

P. F. Kelly et al.
FULL PAPER
pear 0.2821 A (S1) and 0.2162 A (S2) above the mean plane a sulfur and to an NϪH unit on an SϪN bond.[11] In that
of the six atoms in the metallacycle), constitutes a rare ex- case a 1-D structure was formed by an infinite array of the
ample of an XNSCCS ring. A search of the Cambridge cations; in the case of 4 this cannot take place as the ori-
Structural Database[8] reveals only eight examples within entation of the non-bridging phenyl groups — both to one
which such an arrangement is observed. As Figure 4 shows, side of the plane of each metallacycle — precludes the close
the only examples (a and b) in which atom X is a metal approach of further molecules.
˚
˚
contain a tridentate ligand.[9] The rest consist of the two
That the thioether group of 3 should coordinate to a
examples shown wherein X is a nitrogen atom (c and d)
together with four examples in which this atom is carbon
(including the one shown, e).[10aϪ10f]
metal centre is of no great surprise given that the coordina-
tion chemistry of such units is extensive. In general, how-
ever, such ligands are relatively weakly bound and, indeed,
can often act as easily substituted leaving groups. Of the
two coordination sites in 4 one would thus expect the PdϪS
bond to be broken by an incoming ligand and this can be
demonstrated by the reaction of 4 with triphenylphosphane.
Slow addition of the solid phosphane to a stirred solution
of 4 in CH2Cl2 results in lightening of the colour of the
solution; removal of the solvent in vacuo followed by trit-
uration with petroleum ether results in a yellow solid 5
(Scheme 2) The 31P NMR spectrum of this solid (CDCl3)
consists of a singlet at δ ϭ 27.7 ppm while the IR spectrum
confirms the presence of bands typically associated with
both sulfimide units (911 cmϪ1) and with phosphanes (1096
cmϪ1). Slow diffusion of diethyl ether into a CH2Cl2 solu-
tion of the product results in the formation of orange crys-
tals for which X-ray crystallography reveals the structure
shown in Figure 6. As Figure 6 shows, 5 consists of a palla-
dium centre coordinated to a PPh3 ligand and to 3 (acting
in this case as a monodentate N-bound ligand) bound in a
trans fashion. Two trans-chloride ligands make up the rest
of the coordination sphere.
Figure 4. Previous examples of species exhibiting the XSCCSN
cyclic unit observed in 4
Perhaps the most intriguing feature of the structure of 4
is the fact that the molecules arrange themselves into dimers
(Figure 5). These units are held together by hydrogen bond-
The course of the reaction of 4 with PPh3 thus involves
ing between the NϪH groups and chlorides of opposite mo- two steps: substitution of the PdϪS bond by the phos-
lecules. The contact between molecules is close, with a phane, followed by isomerisation to the observed trans ar-
˚
PdϪPd distance of 3.512 A. Interestingly, this value is al- rangement. Presumably the latter effect is brought about
most exactly the same as the closest PdϪPd interactions in by the significant steric interactions that would be present
[Pd(S2N2H)(PMe2Ph)2][BF4] which also has Pd attached to between the six phenyl groups in the initially formed cis
˚
Figure 5. The formation of dimers within the overall structure of 4; intra-dimer distances (A) and angles (°): Pd(1)ϪPd(1A) 3.512,
S(2)ϪCl(1A) 3.428, N(1)ϪCl(2A) 3.469(2), N(1)ϪH(1)ϪCl(2A) 165(3)
124
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The First Complexes of Bidentate Sulfimides
FULL PAPER
˚
Figure 6. The X-ray crystal structure of 5; selected bond lengths (A) and angles (°): Pd(1)ϪN(1) 2.094(6), N(1)ϪS(1) 1.603(6), S(1)ϪC(7)
1.823(7), C(7)ϪC(12) 1.382(9), C(12)ϪS(2) 1.798(8), S(2)ϪC(13) 1.773(7), Pd(1)ϪCl(1) 2.2873(18), Pd(1)ϪCl(2) 2.3010(17), Pd(1)ϪP(1)
2.2331(14); Pd(1)ϪN(1)ϪS(1) 121.6(3), N(1)ϪS(1)ϪC(7) 106.0(3), S(1)ϪC(7)ϪC(12)115.9(6), C(12)ϪS(2)ϪC(13) 102.8(3),
Cl(1)ϪPd(1)ϪN(1) 94.79(18), Cl(2)ϪPd(1)ϪN(1) 84.47(18)
intermediate. The 31P chemical shift of the phosphane isolation of 5 also confirms that the PdϪS bond within this
group is consistent with it being trans to an NϪH unit.
Addition of the phosphane to 4 has to be very slow in
order to obtain pure 5. If this is not carefully observed then
variable amounts of a yellow, far less soluble product are
obtained. Microanalysis indicates that this product is
[PdCl2(PPh3)2] and in such cases it appears in the 31P NMR
spectrum of the product as a peak at δ ϭ 23.4 ppm. The
ability of PPh3 to break the PdϪN bond as well as the
PdϪS bond of the starting material can be confirmed by
addition of one molar equivalent of the phosphane to 5.
This results in the immediate precipitation of the sparingly
soluble [PdCl2(PPh3)2].
molecule is significantly weaker than the PdϪN bond.
Experimental Section
Compounds 1 and 3 were prepared by the reaction of MSH with
appropriate thioether starting materials.[4] Salts of the type
[PPh4]2[Pd2X6] were prepared from PdCl2 (X ϭ Cl or Br) as re-
ported previously[12] or, in the case of X ϭ I, by addition of a hot
solution of NaI (20 mmol) and PdI2 (2.2 mmol) in EtOH (100 mL)
to a hot solution of [PPh4]I (2.2 mmol) in the same solvent (100
mL) followed by filtration. [PdCl2(PhCN)2] was prepared by the
dissolution of PdCl2 into hot benzonitrile followed by precipitation
with 60:80 petroleum ether. Microanalysis was performed by the
Loughborough Departmental service. 31P NMR spectra were re-
corded on a Jeol FX90Q spectrometer operating at 36.21 MHz. IR
spectra were run on a Perkin Elmer PE2000 spectrometer.
Conclusion
The isolation and full characterisation of 2a (together
with 2b and 2c) constitutes the first successful use of a bis-
sulfimide system as a ligand. It is, therefore, the first ex-
ample of the use of an entirely new class of bidentate ligand
and this observation strongly suggests that many more ex-
amples of complexes of 1 should be isolable (although the
observed polymer formation upon using methanol as solv-
ent does highlight a problem which may need to be resolved
in other systems). Such results also indicate that the coor-
dination chemistry of other examples of bis-sulfimides
should be extensive. Although (as shown in previous work)
the ortho-isomer 1,2-(PhS{NH})2C6H4 cannot be formed in
the same manner as 1, the mixed sulfimide/sulfide 1,2-
(PhS{NH})(PhS)C6H4 (3) is known and the isolation of
[PdBr2{1,4-(PhS{NH})2C6H4}]2 (2a): A solution of [PPh4]2[Pd2Br6]
(0.102 g, 0.074 mmol) in CH2Cl2 (20 mL) was treated with 1
(0.05 g, 0.15 mmol) added in one portion with stirring. The re-
sulting mixture was then stirred for three days during which time
a red/orange precipitate formed. The latter was filtered from the
solution, washed with CH2Cl2 (50 mL), Et2O (20 mL) and then
dried in vacuo yielding 60 mg of red/orange solid. A further 10 mg
was obtained when the filtrate was treated with Et2O. Total yield
70 mg, 79%. C36H32Br4N4S4Pd2 (1181.3): calcd. C 36.8, H 2.7, N
4.8; found C 36.3, H 2.6, N 4.4. IR (KBr): ν˜ ϭ 3260 cmϪ1
(ν NϪH), 880 (ν NϪS).
Microcrystalline material of sufficient size for use in synchrotron
X-ray crystallography was generated by a variation on the above
procedure wherein the starting materials were mixed (in the same
complex 4 confirms its potential as a chelating ligand. The amounts as above) as solids and then the CH2Cl2 added without
Eur. J. Inorg. Chem. 2003, 120Ϫ127 125

P. F. Kelly et al.
FULL PAPER
stirring. After one week the solution was decanted from the re-
was added. The resulting solid was then recrystallised from di-
sulting crystalline mass which was then washed with CH2Cl2. The chloromethane/Et2O giving orange crystals. Yield: 0.036 g (61%).
IR spectrum of the material prepared this way was identical to that
prepared above.
C36H30Cl2NPPdS2 (749.0): calcd. C 57.2, H 3.9, N 1.7; found C
57.7, H 4.0, N 1.9. 31P NMR (CDCl3): δ ϭ 27.7 ppm. IR (KBr):
ν˜ ϭ 3294, 3048, 1096, 911 cmϪ1
.
[PdI2{1,4-(PhS{NH})2C6H4}]2 (2b): This was prepared as a red/or-
ange solid by reaction of [PPh4]2[Pd2I6] (0.202 g, 0.122 mmol) with
1 (0.079 g, 0.244 mmol) in exactly the same way as for 3. Yield
105 mg, 63%. C36H32I4N4Pd2S4 (1369.3): calcd. C 31.6, H 2.4,
N 4.1; found C 31.9, H 2.4, N 4.1. IR (KBr): ν˜ ϭ 3260 cmϪ1
(ν NϪH), 880 (ν NϪS).
X-ray Crystallographic Study: Data (Table 1) for 2a were collected
at 150 K on a Bruker AXS SMART 1 K CCD area-detector dif-
˚
fractometer using synchrotron radiation (λ ϭ 0.6879 A) at Dares-
bury SRS Station 9.8.[13,14] Absorption correction was applied
semi-empirically from equivalent and repeated data. The structure
was solved by direct methods and refined by full-matrix least-
squares on F2. The asymmetric unit comprises two half molecules
on centres of symmetry. Some disorder is present within one of the
molecules with alternative positions for the sulfimide SNH unit
with 90.4:9.6 (4)% refined occupancies. Hydrogen atoms were
placed in geometrical positions and allowed to ride on their at-
tached atom with Uiso(H) set to be 1.2 times Ueq of the carrier
atom.
[PdCl2{1,4-(PhS{NH})2C6H4}]2·CH2Cl2 (2c): This was prepared as
a
red/orange solid by reaction of [PPh4]2[Pd2Cl6] (0.082 g,
0.077 mmol) with 1 (0.050 g, 0.154 mmol) in exactly the same way
as for 3. Yield 45 mg, 61%. C37H34Cl6N4Pd2S4 (1088.5): calcd. C
40.8, H 3.1, N 5.1; found C 40.3, H 3.1, N 4.8. IR (KBr): ν˜ ϭ 3260
cmϪ1 (ν NϪH), 898 (ν NϪS).
[PdCl2{1,2-(PhS{NH})(PhS)C6H4}]
(4):
A
solution
of
Data for 4 and 5 were collected at 150 K with a Bruker AXS
SMART 1000 CCD diffractometer using Mo-Kα radiation (λ ϭ
[PdCl2(PhCN)2] (0.176 g, 0.460 mmol) in dichloromethane (10 mL)
was treated with a solution of 1,2-(PhS{NH})(PhS)C6H4 (0.142 g,
0.460 mmol) in an equal volume of the same solvent added drop-
wise with stirring. After addition of the ligand a precipitate was
present which then redissolved after a minute of stirring. The solu-
tion was then left to stand for 48 hours and the resulting orange/
red or brown crystals were collected. Yield: 0.165 g (86%).
C18H15Cl2NPdS2 (486.7): calcd. C 44.4, H 3.1, N 2.9; found C 44.4,
˚
0.71073 A). Both structures were solved by Patterson synthesis and
refined by full-matrix least-squares methods on F2. NH hydrogens
were located from the difference map and their coordinates were
freely refined. All other hydrogens were placed in geometrical posi-
tions using a riding model as described above. Some disorder is
present in 5 with alternative positions for the sulfur and nitrogen
atoms with refined occupancies of 84.0:16.0 (5)%.
H 3.0, N 2.8. IR (KBr): ν˜ ϭ 3215, 3053, 944 cmϪ1
.
The programs used were Bruker SMART,[15a] SAINT,[15a]
SHELXTL[15b] and local programs.
trans-[PdCl2{1,2-(PhS{NH})(PhS)C6H4}PPh3] (5): A solution of 4
(0.039 g, 0.08 mmol) in dichloromethane (10 mL) was treated with
solid PPh3 (21 mg, 0.08 mmol) added slowly in small portions with CCDC-176115 (2a), -186575 (4) and -186576 (5) contain the sup-
vigorous stirring. After complete addition of the PPh3 the clear
solution was reduced in volume and petroleum ether 40:60 (50 mL)
plementary crystallographic data for this paper. These data can be
obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html
Table 1. Crystallographic data of 2a, 4, 5
Compound
2a
4
5
Formula
Mol. wt.
C36H32Br4N4Pd2S4
1181.34
C18H15Cl2NPdS2
486.73
C36H30Cl2NPPdS2
749.00
Crystal dimensions
Crystal system
Space group
0.070 ϫ 0.020 ϫ 0.005
Triclinic
P1
0.19 ϫ 0.11 ϫ 0.08
Triclinic
P1
0.33 ϫ 0.15 ϫ 0.05
Triclinic
P1
¯
¯
¯
˚
a (A)
8.4402(15)
11.044(2)
22.519(4)
94.962(3)
98.383(3)
101.418(2)
2021.2(6)
2
9.5236(8)
10.7767(9)
11.1578(9)
61.497(2)
66.767(2)
67.985(2)
899.72(13)
2
9.5178(7)
9.9441(7)
17.7459(13)
90.768(2)
99.786(2)
96.508(2)
1643.6(2)
2
˚
b (A)
˚
c (A)
α (°)
β (°)
γ (°)
3
˚
V (A )
Z
Absorption coefficient, µ (mmϪ1
Min. and max. transmission
θ range (°)
)
5.082
1.560
0.930
0.717 and 0.975
1.83 to 25.46
0.6877
0.756 and 0.885
2.15 to 28.89
0.71073
0%
0.749 and 0.955
2.06 to 25.00
0.71073
0%
˚
Wavelength (A)
Decay
20%
Measured reflections
Independent reflections
16679
8215
5244
0.0430
0.0453
0.0991
0.942 and Ϫ1.144
7941
4144
3678
0.0142
0.0236
0.0622
0.953 and Ϫ0.698
12081
5772
4576
0.0276
0.0553
0.1313
2.943 and Ϫ1.503
Observed reflections [F2 Ͼ 2σ(F2)]
Rint
R [F2 Ͼ 2σ(F2)][a]
wR2 [all data][b]
Ϫ3
˚
Largest difference map features (e·A
)
[a]
[b]
2
2 2
2 2
R ϭ ||Fo| Ϫ |Fc||//Fo|. wR2 ϭ {[w(Fo Ϫ Fc ) ]/[w(Fo ) ]}1/2
.
126
Eur. J. Inorg. Chem. 2003, 120Ϫ127

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127