Synthesis and spectroscopy of cis-configured mononuclear palladium(II) and platinum(II) complexes of chalcogeno o-carboranes and structures of [Pt(SCb oPh)2(dppm)], [Pt(SeCboPh)2(dppm)], [Pt(SCboS)(PM

Article abstract of DOI:10.1016/j.jorganchem.2011.09.021

The reactions of [MCl₂(P^∩P)] and [MCl ₂(PR₃)₂)] with 1-mercapto-2-phenyl-o-carborane/ NaSeCb^oPh and 1,2-dimercapto-o-carborane yield mononuclear complexes of composition, [M(SCb^o

Full text of DOI:10.1016/j.jorganchem.2011.09.021

Journal of Organometallic Chemistry 696 (2012) 4257e4263
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Synthesis and spectroscopy of cis-configured mononuclear palladium(II) and
platinum(II) complexes of chalcogeno o-carboranes and structures of
[Pt(SCboPh)2(dppm)], [Pt(SeCboPh)2(dppm)], [Pt(SCboS)(PMe2Ph)2] and
[Pt(SCboS)(PMePh2)2]
,
a
b
b
Manoj K. Pal a, Vimal K. Jain a , Amey P. Wadawale , Sergey A. Glazun , Zoya A. Starikova ,
*
,
Vladimir I. Bregadze b
**
a Chemistry Division, Bhabha Atomic Research Center, Mumbai 400085, India
b A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., 119991 Moscow, Russia
a r t i c l e i n f o
a b s t r a c t
The reactions of [MCl2(PXP)] and [MCl2(PR3)2)] with 1-mercapto-2-phenyl-o-carborane/NaSeCboPh and
1,2-dimercapto-o-carborane yield mononuclear complexes of composition, [M(SCboPh)2(PXP)],
[M(SeCboPh)2(PXP)] (M ¼ Pd or Pt; PXP ¼ dppm (bis(diphenylphosphino)methane), dppe (1,2-
bis(diphenylphosphino)ethane) or dppp (1,3-bis(diphenylphosphino)propane)) and [M(SCboS)(PR3)2]
(2PR3 ¼ dppm, dppe, 2PEt3, 2PMe2Ph, 2PMePh2 or 2PPh3). These complexes have been characterized by
elemental analysis and NMR (1H, 31P, 77Se and 195Pt) spectroscopy. The 1J(PteP) values and 195Pt NMR
chemical shifts are influenced by the nature of phosphine as well as thiolate ligand. Molecular structures
of [Pt(SCboPh)2(dppm)], [Pt(SeCboPh)2(dppm)], [Pt(SCboS)(PMe2Ph)2] and [Pt(SCboS)(PMePh2)2] have
been established by single crystal X-ray structural analyses. The platinum atom in all these complexes
acquires a distorted square planar configuration defined by two cis-bound phosphine ligands and two
chalcogenolate groups. The carborane rings are mutually anti in [Pt(SCboPh)2(dppm)] and
[Pt(SeCboPh)2(dppm)].
Article history:
Received 9 August 2011
Received in revised form
26 September 2011
Accepted 28 September 2011
Keywords:
Palladium
Platinum
1-Mercapto-2-phenyl-o-carborane
1,2-Dimercapto-o-carborane
NMR
X-ray structure
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
thiolate ligands (S-R-S)2ꢀ [17,18], (iii) bulky chalcogenolate ligands
[19,20] and internally functionalized chalcogenolate ligands
The synthesis and characterization of platinum group metal
chalcogenolate complexes continue to be an active area of research.
There are several obvious reasons for this sustained interest as these
complexes display novel structures [1e4] and have relevance in
catalysis [5e10]. More recently they have shown potential as single
source precursors for the synthesis of metal chalcogenides [11e13]
and anti-cancer agents, e.g. both cis- and trans-PtP2S2 core
(P2 ¼ mono or chelating phosphines) exhibit promising anti-
proliverative properties [14,15]. The high propensity of organo-
chalcogenolate ligand, in general, leads to M-ER-M bridges as
a consequence the resulting complexes are isolated as oligomeric,
insoluble or sparingly soluble, non-volatile species. Several strategies
have been adopted to stabilize monomeric frameworks. These
include (i) use of chelating phosphine ligands [16], (ii) chelating
[5,21e23]. Monomeric complexes, [M(SR)2(PR3)2] have been studied
with reference to cis- and trans-isomerizationprocess [24] and in fact
the cis isomer is readily isomerized to trans form in solution [24e28].
The DFT calculations on model complexes, [Pt(SeR)2(PH3)2] revealed
that the cis isomers lie at higher energy than that of the trans isomer
[25]. Mononuclear chalcogenolate complexes with cis configuration
have been used as molecular tactons for the preparation of bi- and
high-nuclearity complexes [29e34]. The cis-[M(ER)2(PR3)2] have
been shown to be catalytically active and catalytic activity degrades
with time due to isomerization into trans form [8].
The chemistry of functionalized icosahedral-closo-carboranes
has attracted considerable attention due to their use in organic
synthesis [35,36] and potential applications in medicine [37e42]
and materials science [43,44]. The unique rigidity and gross steric
bulk, which is comparable to rotating benzene, of carborane offer
several possibilities and can aid in the formation and stabilization
of novel structures. For instance, steric congestion of 1,2-dicarba-
closo-dodecaborane-1,2-dichalcogenolate (E2C2B10H10; E ¼ S or Se)
* Corresponding author. Tel.: þ912225595095; fax: þ91 22 25505151.
** Corresponding author. Tel.: þ7 495 135 7405; fax: þ7 499 135 5085.
E-mail addresses: jainvk@barc.gov.in (V.K. Jain), bre@ineos.ac.ru (V.I. Bregadze).
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.09.021

4258
M.K. Pal et al. / Journal of Organometallic Chemistry 696 (2012) 4257e4263
ligands assists in stabilizing coordinatively unsaturated 16-electron
half-sandwich mononuclear complexes, [Cp#M(E2C2B10H10)]
(Cp# ¼ Cp or Cp*; M ¼ Co, Rh, Ir) and [(p-cymene) M(E2C2B10H10)]
(M ¼ Ru or Os) complexes which exhibit rich reaction chemistry
[45e52].
With the above perspective and in pursuance of our interest in
platinum metal chalcogenolate chemistry we have isolated several
mononuclear Pd and Pt complexes derived from carborane chal-
cogenolate ligands and characterized them by NMR spectroscopy
and some by X-ray crystallography.
These complexes were isolated as yellow (in case of palladium) or
white (in case of platinum) crystalline solids and could be crystal-
lized from appropriate solvent mixtures in 51e85% yield.
The 1H NMR spectra of these complexes showed expected
resonances and peak multiplicities. The 77Se{1H} NMR spectra
showed a doublet due to coupling with a 31P nucleus of the phos-
phine trans to the selenolate ligand. The magnitude of 2J(77See31P)
is typical of palladium and platinum complexes bearing phosphine
ligands [18,53,54]. The 31P NMR spectra of palladium complexes
displayed single resonances while the resonances for platinum
complexes were flanked by 195Pt satellites. The magnitude of
1J(195Pte31P) is reduced significantly from the corresponding
dichlorides owing to strong trans influence of the chalcogen ligand.
2. Results and discussions
The 195Pt{1H} NMR spectra exhibited a triplet in the region
d
ꢀ3892
2.1. Synthesis and spectroscopy
to ꢀ4949 ppm due to coupling with two equivalent 31P nuclei. The
following salient trends are evident from the 31P and 195Pt NMR
spectra of platinum complexes (Table 1):
The reactions of [MCl2(PXP)] with 1-mercapto-2-phenyl-o-car-
borane in the presence of pyridine as HCl scavenger yield mono-
nuclear thiolate complexes of composition, [M(SCboPh)2(PXP)]
(Scheme 1). Analogous selenolate complexes, [M(SeCboPh)2(PXP)]
(M ¼ Pd or Pt; PXP ¼ dppm, dppe or dppp), have been isolated by
treatment of [MCl2(PXP)] with NaSeCboPh, prepared by reductive
cleavage of SeeSe bond of (PhCboSe)2 by methanolic NaBH4. The
reactions of [MCl2(PXP)] and [MCl2(PR3)2] with one equivalent of
1,2-dimercapto-o-carborane in the presence of pyridine afforded
mononuclear complexes containing chelating dithiolate ligand.
ꢁ The magnitude of 1J(PteP) in selenolate complexes is slightly
larger than the corresponding thiolate derivatives. Similarly
the 195Pt NMR resonances of selenolate complexes are more
shielded than the corresponding thiolate derivative [e.g.,
[Pt(ECboPh)2(dppm)]; 195Pt NMR
d
¼ ꢀ4063 (E ¼ S) and ꢀ4289
(E ¼ Se)]. This may be attributed to greater nucleophilicity of
selenolate ligand.
P
P
M
S
S
Ph
Ph
SH
Ph
...(1)
P
P
MCl2
2
M
P
P
dppm (1)
Pd
Pd dppe (2)
Pt
dppm (3)
P
P
M
Se
Se
SeNa
Ph
Se
Se
Ph
Ph
Ph
Ph
P
P
MCl2
NaBH4
...(2)
2
M
P
P
dppe (4)
dppm (5)
dppe (6)
Pd
Pt
Pt
Pt dppp (7)
P
PR3
P
R3P
M
M
SH
S
S
HS
S
S
MCl2(PR3)2
P
P
MCl2
...(3)
M
PR3
PEt3
M
P
P
(12)
Pd
dppm (8)
Pd
Pd PMePh2 (13)
Pd dppe (9)
Pt
Pt dppe (11)
Pd
Pt
Pt
Pt
PPh3
PEt3
PMe2Ph (16)
PMePh2 (17)
(14)
dppm (10)
(15)
Scheme 1.

M.K. Pal et al. / Journal of Organometallic Chemistry 696 (2012) 4257e4263
4259
Table 1
31P{1H} and 195Pt{1H} NMR spectral data for platinum chalcogenolate complexes in
CDCl3.
Complex
31P NMR Data
in ppm
195Pt NMR
d in ppm
d
1J(PteP) in Hz
[Pt(SCbꢂPh)2(dppm)] (3)
[Pt(SeCbꢂPh)2(dppm)] (5)
[Pt(SeCbꢂPh)2(dppe)] (6)
[Pt(SeCbꢂPh)2(dppp)] (7)
[Pt(SCbꢂS)(dppm)] (10)
[Pt(SCbꢂS)(dppe)] (11)
ꢀ52.6
ꢀ55.7
41.4
ꢀ11.5
ꢀ46.4
44.6
2605
2649
2994
2840
2382
2796
2775
2784
2848
3031
3022
3054
ꢀ4063
ꢀ4289
ꢀ4949
e
ꢀ3892
ꢀ4460
ꢀ4437
ꢀ4358
ꢀ4381
ꢀ4572
e
[Pt(SCbꢂS)(PEt3)2] (15)
7.6
[Pt(SCbꢂS)(PMe2Ph)2] (16)
[Pt(SCbꢂS)(PMePh2)2] (17)
[Pt(SCbꢂPh)2(PMe2Ph)2] (18)
[Pt(SeCbꢂPh)2(PMe2Ph)2]a
[Pt(SeCbꢂPh)2(PMePh2)2]a
ꢀ17.6
-1.5
ꢀ16.3
ꢀ19.5
-7.8
e
a
From reference [55].
ꢁ The 1J(PteP) values and 195Pt NMR chemical shifts are influ-
enced by the nature of phosphine as well as thiolate ligand. The
magnitude of 1J(PteP) and shielding of the 195Pt NMR reso-
nance increased in the following order: chelating phosphine
and chelating dithio ligand > chelating phosphine and mono-
dentate thio ligand > monodentate phosphine and chelating
dithio ligand > monodentate phosphine and monodentate thio
ligand.
Fig. 2. Structure of [Pt(SeCboPh)2(dppm)] (5).
PteP distances (w2.27 Å) in all these complexes are similar and are
in accord with the literature values [29,55]. The PteS (2.32e2.38 Å)
and PteSe distances are well within the range reported for plat-
inum chalcogenolate complexes [29,55]. These distances are,
however, slightly longer than those complexes containing chalco-
genolate ligand trans to halide as in [PtCl(SCH2CHMeNMe2)
(PMe2Ph)] (PteS ¼ 2.235 (2) Å) [33] and [Pt3Cl4(SeCH2CH2N-
Me2)2(PEt3)2] (PteSe ¼ 2.3775 (8) Å) [56] owing to the strong trans
influence of the phosphine ligand which is trans to chalcogenolate
ligand in the present complexes. The PteSe distances can, however,
be compared with those complexes containing selenolate ligand
trans to strong trans influencing ligand as in [Pt3
(SeCH2CH2NH2)2Cl3(PPr3)3]Cl (Pt2eSe ¼ 2.4211 (15) and 2.4630
(16) Å) [57]. The CeS (av. 1.77 Å) and CeSe (av. 1.93 Å) in these
complexes can be compared with the corresponding distances re-
ported in mercapto- and seleno-carborane complexes [55,58].
2.2. Molecular structures
Molecular structures of [Pt(SCboPh)2(dppm)] (3), [Pt(SeC-
boPh)2(dppm)] (5), [Pt(SCboS)(PMe2Ph)2] (16) and [Pt(SCboS)(P-
MePh2)2] (17) have been established by single crystal X-ray
diffraction analyses. ORTEP drawings with crystallographic
numbering scheme are given in Figs. 1e4 while selected bond
lengths and angles are summarized in Tables 2e5. The platinum
atoms in all these complexes acquire a distorted square planar
configuration defined by cis-“E2P2” (E ¼ S or Se) donor atoms. The
Fig. 1. Structure of [Pt(SCboPh)2(dppm)] (3).
Fig. 3. Structure of [Pt (SCboS)(PMe2Ph)2 ] (16).

4260
M.K. Pal et al. / Journal of Organometallic Chemistry 696 (2012) 4257e4263
Table 3
The selected bond lengths (Å) and angles (ꢂ) for [Pt(SeCboPh)2(dppm)] (5).a
Pt1eSe1
Pt1eSe2
Pt1eP1
Pt1eP2
2.4980 (17)
2.4244 (17)
2.266 (3)
Se1eC2
Se2eC10
P1eC1
1.930 (10)
1.924 (12)
1.812 (10)
1.866 (11)
2.273 (3)
P2eC1
Se1ePt1eSe2
P1ePt1eP2
Se1e-Pt1eP1
Se1ePt1eP2
Se2ePt1eP1
80.24 (4)
72.51 (11)
96.77 (8)
168.99 (8)
172.02 (8)
Se2ePt1eP2
Pt1eP1eC1
Pt1eP2eC1
P1eC1eP2
Pt1eSe1eC2
Pt1eSe2eC10
110.05 (8)
94.2 (4)
92.5 (3)
93.7 (5)
105.7 (3)
119.8 (3)
a
CeB distances lie between 1.663 (16) and 1.773 (16) Å.
Chemical shifts are relative to internal chloroform peak (7.26 ppm)
for 1H and external 85% H3PO4 (for 31P), Me2Se (Ph2Se2 in CDCl3,
463 ppm relative to Me2Se for 77Se) and Na2PtCl6 in D2O (for 195Pt).
3.1. Preparation of [Pd(SCboPh)2(dppm)] (1)
To a stirred dichloromethane solution (20 ml) of [HSCboPh]
(105 mg, 0.418 mmol), [PdCl2dppm] (117 mg, 0.208 mmol) and
pyridine (34 mg, 0.418 mmol) were added and the whole was
stirred for 4 h. The solvent was removed under vacuum and the
residue was washed with methanol (2 ꢃ 5 ml). Product was
recrystallized from CH2Cl2/hexane mixture to give a yellow crys-
talline powder (115 mg, 56% yield); m.p. 198 ꢂC. Anal. Calcd. for
C41H52B20P2PdS2: C, 49.56; H, 5.28%. Found: C, 49.50; H, 5.27%. 1H
Fig. 4. Structure of [Pt(SCboS)(PMePh2)2] (17).
The complexes, [Pt(SCboPh)2(dppm)] (3) and [Pt(SeC-
boPh)2(dppm)] (5) have isomorphous structures. The PePteP and
EePteE (E ¼ S or Se) angles in two complexes are similar. To avoid
steric crowding, the carborane rings are mutually anti, one lying
above and another below the platinum square plane. A similar
configuration has been reported for [Pt(SeCboPh)2(PMe2Ph)2] [55].
One of the PteE bonds is significantly longer (0.056 (for E ¼ S) and
0.074 (for E ¼ Se) Å) than the other. The two PteSe distances in
complexes containing monodentate phosphine, like [Pt(SeC-
boPh)2(PMe2Ph)2] [55], differ only slightly (0.015 Å).
NMR (CDCl3)
d
: 4.13 (t, 2J(PeH) ¼ 10 Hz, PCH2P); 7.35e7.56 (m, Ph).
31P{1H} NMR (CDCl3)
d: ꢀ42.6 ppm.
3.2. Preparation of [Pd(SCboPh)2(dppe)] (2)
The dithio-o-carborane in [Pt(SCboS)(PMe2Ph)2] (16) and
[Pt(SCboS)(PMePh2)2] (17) forms a five membered chelate ring.
Various angles in two molecules are similar. The complex
[Pt(SCboS)(PMe2Ph)2] (16) has a mirror plane bisecting the mole-
cule through palladium and “CeC” bond of carborane.
Prepared similar to 1 using HSCboPh (107 mg, 0.42 mmol),
[PdCl2dppe] (122 mg, 0.21 mmol) and pyridine (35 mg, 0.44 mmol)
in dichloromethane and isolated as an orange crystalline solid in
85% (181 mg)
C42H54B20P2PdS2.0.5 (CH2Cl2): C, 48.61; H, 5.28%. Found: C, 48.11; H,
5.46%; 1H NMR (CDCl3)
: 2.24e2.37(m, CH2CH2); 7.36e7.61 (m,
Ph). 31P{1H} NMR (CDCl3)
: 54.0 ppm.
yield,
m.p. 160 ꢂC.
Anal.
Calcd.
For
d
3. Experimental
d
The compounds, 1-mercapto-2-phenyl-o-carborane (PhCboSH)
[59,60], bis(2-phenyl-o-carborane)diselenide, (PhCboSe)2 [61,62],
1,2-dimercapto-o-carborane (HSCboSH) [63], [MCl2(PR3)2] [64]
were prepared according to literature methods. All reactions were
carried out in anhydrous conditions under a nitrogen atmosphere.
Melting points were determined in capillary tubes and are uncor-
rected. Elemental analyses were carried out on a Thermo Fisher
Flash EA-1112 CHNS instrument. 1H, 31P{1H}, 77Se{1H} and 195Pt{1H}
NMR spectra were recorded on a Bruker Avance-II 300 MHz spec-
trometer operating at 300,121.5, 57.24 and 64.29 MHz, respectively.
3.3. Preparation of [Pt(SCboPh)2(dppm)] (3)
Prepared similar to 1 using HSCboPh (94 mg, 0.37 mmol),
[PtCl2dppm] (121 mg, 0.18 mmol) and pyridine (30 mg, 0.38 mmol)
in dichloromethane and isolated as a yellow crystalline solid in 52%
(105 mg) yield, m.p. 250 ꢂC (single crystals for X-ray analysis were
grown from CH2Cl2/MeOH/hexane solution). Anal. Calcd. for
C41H52B20P2PtS2.CH2Cl2: C, 43.22; H, 4.66%. Found: C, 44.11; H,
4.86%. 1H NMR (C6D6)
d
:
3.78 (t, 2J(PeH) ¼ 10 Hz; PCH2P);
6.99e7.09; 7.42e7.47; 7.82e7.85 (m, Ph). 31P{1H} NMR (C6D6)
d
: ꢀ52.6 (1J(PteP) ¼ 2605 Hz). 195Pt{1H} NMR (CDCl3)
: ꢀ4063 (t,
d
1J(PteP) ¼ 2640 Hz) ppm.
Table 2
The selected bond lengths (Å) and angles (ꢂ) for [Pt (SCboPh)2(dppm)] (3).a
Pt1eS1
Pt1eS2
Pt1eP1
Pt1eP2
2.3243 (9)
2.3799 (9)
2.2768 (9)
2.2639 (9)
S1eC1
S2eC9
P1eC17
P2eC17
1.776 (4)
1.767 (4)
1.858 (4)
1.834 (4)
Table 4
The selected bond lengths (Å) and angles (ꢂ) for [Pt (SCboS)(PMe2Ph)2] (16).a
Pt1eS1
Pt1eP1
S1eC1
C1eC1
2.3182 (4)
2.2741 (4)
1.7828 (15)
1.633 (3)
P1eC3
P1eC4
P1eC2
1.8195 (17)
1.8169 (16)
1.8160 (16)
S1ePt1eS2
P1ePt1eP2
S1ePt1eP1
S1ePt1eP2
S2ePt1eP1
80.92 (3)
72.20 (3)
111.33 (3)
172.89 (3)
166.60 (3)
S2ePt1eP2
Pt1eP1eC17
Pt1eP2eC17
P1eC17eP2
Pt1eS1eC1
Pt1eS2eC9
95.03 (3)
92.94 (11)
94.02 (11)
92.88 (15)
121.07 (12)
108.97 (12)
S1ePt1eS2
P1ePt1eP2
S1ePt1eP1
91.807 (19)
92.55 (2)
S1AePt1eP2
Pt1eS1eC1
179.354 (14)
105.68 (5)
87.824 (15)
a
a
CeB distances lie between 1.693 (6) and 1.737 (6) Å.
CeB distances lie between 1.711 (2) and 1.733 (2) Å.

M.K. Pal et al. / Journal of Organometallic Chemistry 696 (2012) 4257e4263
4261
3.8. Preparation of [Pd(SCboS)(dppm)] (8)
Table 5
The selected bond lengths (Å) and angles (ꢂ) for [Pt(SCboS)(PMePh2)2] (17).a
To a stirred dichloromethane solution (20 ml) of [HSCboSH]
(51 mg, 0.245 mmol), [PdCl2dppm] (137 mg, 0.244 mmol) and
pyridine (42 mg, 0.531 mmol) were added and the whole was
stirred for 4 h. The solvent was removed through vacuum, residue
was washed with methanol (2 ꢃ 5 ml) and recrystallized from
CH2Cl2/hexane mixture to give a yellow crystalline powder (91 mg,
53% yield); m.p. 256 ꢂC. Anal. Calcd. for C27H32B10P2PdS2: C, 46.52;
Pt1eS1
Pt1eS2
Pt1eP1
Pt1eP2
2.3311 (6)
2.3388 (6)
2.2735 (6)
2.2753 (6)
S1eC1
S2eC2
C1eC2
1.783 (2)
1.782 (2)
1.646 (3)
S1ePt1eS2
P1ePt1eP2
S1ePt1eP1
S1ePt1eP2
91.55 (2)
94.93 (2)
168.61 (2)
88.58 (2)
S2ePt1eP1
S2ePt1eP2
Pt1eS1eC1
Pt1eS2eC2
86.60 (2)
171.34 (2)
104.37 (8)
104.46 (8)
H, 4.63%. Found: C, 46.58; H, 4.43%. 1H NMR (CDCl3)
d: 4.15 (t,
a
CeB distances lie between 1.717 (4) and 1.736 (4) Å.
J(PeH) ¼ 10 Hz, PCH2P); 7.40e7.52; 7.62e7.68 (m, PPh2). 31P{1H}
NMR (CDCl3)
d: ꢀ38.7 ppm.
3.4. Preparation of [Pd(SeCboPh)2(dppe)] (4)
3.9. Preparation of [Pd(SCboS)(dppe)] (9)
To a dichloromethane solution (15 ml) of [PdCl2dppe] (108 mg,
0.188 mmol), a methanolic solution of NaSeCboPh (prepared from
reduction of (PhCboSe)2 (112 mg 0.188 mmol) in 5 ml benzene by
methanolic solution of NaBH4 (16 mg, 0.42 mmol)) was added with
vigorous stirring which continued for 4 h. The solvents were evap-
orated under vacuum and the residue was extracted with dichloro-
methane and filtered through a G-3 filtration unit. The filtrate was
concentrated under vacuum and the residue was recrystallized from
chloroform as a red crystalline solid (155 mg, 75% yield); m.p. 174 ꢂC.
Anal. Calcd. for C42H54B20P2PdSe2: C, 45.80; H, 4.94%. Found: C,
Prepared similar to 8 using HSCboSH (58 mg, 0.28 mmol) and
[PdCl2dppe] (160 mg, 0.28 mmol) and pyridine (50 mg, 0.63 mmol)
and recrystallized from CH2Cl2/hexane mixture to yield a yellow
crystalline solid (113 mg, 57%), m.p. >300 ꢂC. Anal. Calcd. for
C28H34B10P2PdS2: C, 47.29; H, 4.82%. Found: C, 47.44; H, 4.83%. 1H
NMR (CDCl3)
d
: 2.36 (d, CH2eCH2); 7.46e7.54 (m, PPh2); 7.62e7.67
(m, PPh2). 31P{1H} NMR (CDCl3)
d
: 53.2 ppm.
3.10. Preparation of [Pt(SCboS)(dppm)] (10)
46.79; H, 4.91%. 1H NMR (CDCl3)
(m, Ph). 31P{1H} NMR (CDCl3)
NMR (CDCl3)
d: 2.23e2.28 (m, CH2P); 7.33e7.82
Prepared similar to 8 using HSCboSH (53 mg, 0.25 mmol) and
[PtCl2dppm] (165 mg, 0.25 mmol) and pyridine (48 mg, 0.61 mmol)
and recrystallized from CH2Cl2/hexane mixture to yield a white
crystalline solid (123 mg, 62%), m.p. >300 ꢂC. Anal. Calcd. for
C27H32B10P2PtS2: C, 41.27; H, 4.10; S, 8.16%. Found: C, 41.59; H, 4.14;
d
: 51.8 (2J (SeeP) ¼ 85 Hz); 77Se{1H}
d
: 254 (d, J(SeeP) ¼ 85 Hz) ppm.
3.5. Preparation of [Pt(SeCboPh)2(dppm)] (5)
S, 8.56%. 1H NMR (CDCl3)
d
: 4.44 (t, 2J(PeH) ¼ 10.8 Hz; PCH2P);
Prepared similar to 4 by a reaction between [PtCl2dppm] (143 mg,
0.22 mmol) and NaSeCboPh generated in situ from (PhCboSe)2
(131 mg, 0.22 mmol) and methanolic NaBH4 (18 mg, 0.47 mmol) and
isolated as a yellowcrystalline solid in 62% (159 mg) yield, m.p.192 ꢂC.
Anal. Calcd. for C41H52B20P2PtSe2$CH2Cl2: C, 40.00; H, 4.32%. Found: C,
7.42e7.51; 7.62e7.68 (m, PPh2). 31P{1H} NMR (CDCl3)
d
: ꢀ46.4
(1J(PteP) ¼ 2382 Hz). 195Pt{1H} NMR (C6D6)
d
: ꢀ3892 (t, 1J(PteP) ¼
2382 Hz) ppm.
3.11. Preparation of [Pt(SCboS)(dppe)] (11)
40.36; H, 4.29%. 1H NMR (C6D6)
d
: 3.89 (t, 2J(PeH) ¼ 10 Hz, PCH2P);
4.35(s,CH2Cl2); 7.05e7.06;7.47e7.52;7.72e7.75 (m, Ph). 31P{1H} NMR
Prepared similar to 8 using HSCboSH (40 mg, 0.19 mmol) and
[PtCl2dppe] (128 mg, 0.19 mmol) and pyridine (35 mg, 0.44 mmol)
and recrystallized from CH2Cl2/hexane mixture to yield a white
crystalline solid (86 mg, 56%), m.p. >300 ꢂC. Anal. Calcd. for
C28H34B10P2PtS2: C, 42.05; H, 4.28%. Found: C, 42.38; H, 4.30%. 1H
(C6D6)
d
: ꢀ55.7 (1J(PteP) ¼ 2649 Hz). 77Se{1H} NMR (C6D6)
d: 431(br)
ppm. 195Pt{1H} NMR (C6D6)
d
: ꢀ4289 (1J(PteP) ¼ 2676 Hz) ppm.
3.6. Preparation of [Pt(SeCboPh)2(dppe)] (6)
NMR (CDCl3) d: 2.25e2.37 (m, CH2); 7.46e7.51; 7.63e7.67 (m, PPh2).
31P{1H} NMR (CDCl3)
d
: 44.6 (1J(PteP) ¼ 2796 Hz). 195Pt{1H} NMR
Prepared similar to 4 by a reaction between [PtCl2dppe]
(127 mg, 0.19 mmol) and NaSeCboPh generated in situ from
(PhCboSe)2 (114 mg, 0.22 mmol) and methanolic NaBH4 (17 mg,
0.45 mmol) and isolated as a yellow crystalline solid in 56%
(126 mg) yield, m.p. 210 ꢂC. Anal. Calcd. for C42H54B20P2PtSe2: C,
(C6D6)
d
: ꢀ4460 (1J(PteP) ¼ 2801 Hz) ppm.
3.12. Preparation of [Pd(SCboS)(PEt3)2] (12)
42.39; H, 4.57%. Found: C, 42.70; H, 4.56%. 1H NMR (C6D6)
d:
Prepared similar to 8 using HSCboSH (65 mg, 0.31 mmol) and
[PdCl2(PEt3)2] (129 mg, 0.31 mmol) and pyridine (55 mg,
0.69 mmol) and recrystallized from CH2Cl2/hexane mixture to yield
a yellow crystalline solid (89 mg, 52%), m.p. 212 ꢂC. Anal. Calcd. for
C14H40B10P2PdS2: C, 30.62; H, 7.34%. Found: C, 30.81; H, 7.39%. 1H
2.12e2.25 (m, CH2); 7.32e7.58 (m, Ph). 31P{1H} NMR (C6D6)
d: 41.4
(1J(PteP) ¼ 2994 Hz). 77Se{1H} NMR (C6D6)
d
: 266 (d, 2J(SeeP) ¼
65 Hz). 195Pt{1H} NMR (C6D6)
d
: ꢀ4949 (1J(PteP) ¼ 3004 Hz) ppm.
3.7. Preparation of [Pt(SeCboPh)2(dppp)] (7)
NMR (CDCl3)
d
: 1.10e1.18 (m, PCH2Me); 1.75e1.83 (m, PCH2). 31P
: 19.0 ppm.
{1H} NMR (CDCl3)
d
Prepared similar to 4 by a reaction between [PtCl2dppp]
(118 mg, 0.17 mmol) and NaSeCboPh generated in situ from
(PhCboSe)2 (104 mg, 0.17 mmol) and methanolic NaBH4 (15 mg,
0.40 mmol) and isolated as a yellow powder in 53% (111 mg) yield,
m.p. 160 ꢂC. Anal. Calcd. for C43H56B20P2PtSe2.CH2Cl2: C, 41.00; H,
3.13. Preparation of [Pd(SCboS)(PMePh2)2] (13)
Prepared similar to 8 using HSCboSH (44 mg, 0.21 mmol) and
[PdCl2(PMePh2)2] (123 mg, 0.21 mmol) and pyridine (36 mg,
0.45 mmol) and recrystallized from CH2Cl2/hexane mixture to yield
a yellow crystalline solid (85 mg, 56%), m.p. 252 ꢂC. Anal. Calcd. for
C28H36B10P2PdS2: C, 47.15; H, 5.09%. Found: C, 46.35; H, 5.02%. 1H
4.54%. Found: C, 41.13; H, 4.49%. 1H NMR (C6D6)
d: 3.64 (m), 3.87 (m)
(CH2); 6.98e7.16 (m); 7.38 (br), 7.45(br), 7.62 (d, 8 Hz) (Ph). 31P{1H}
NMR (C6D6)
d
: ꢀ11.5 (1J(PteP) ¼ 2840 Hz) ppm. Because of poor
solubility of the complex 77Se and 195Pt NMR spectra could not be
obtained.
NMR (CDCl3)
NMR (CDCl3)
d
: 1.59 (d, 8.4 Hz, PMe); 7.29e7.45 (m, Ph). 31P{1H}
: 7.6 ppm.
d

4262
M.K. Pal et al. / Journal of Organometallic Chemistry 696 (2012) 4257e4263
3.14. Preparation of [Pd(SCboS)(PPh3)2] (14)
(1J(PteP) ¼ 2784 Hz). 195Pt{1H} NMR (C6D6)
d
: ꢀ4358 (1J(PteP) ¼
2803 Hz) ppm.
Prepared similar to 8 using HSCboSH (36 mg, 0.17 mmol) and
[PdCl2(PPh3)2] (120 mg, 0.17 mmol) and pyridine (30 mg,
0.38 mmol) and recrystallized from CH2Cl2/hexane mixture to yield
a yellow crystalline solid (81 mg, 56%), m.p. 260 ꢂC. Anal. Calcd. for
C38H40B10P2PdS2: C, 54.51; H, 4.82%. Found: C, 54.27; H, 4.74%. 1H
3.17. Preparation of [Pt(SCboS)(PMePh2)2] (17)
Prepared similar to 8 using HSCboSH (31 mg, 0.15 mmol) and
[PtCl2(PMePh2)2] (99 mg, 0.15 mmol) and pyridine (28 mg,
0.35 mmol) and recrystallized from CH2Cl2/hexane mixture to yield
an off-white crystalline solid (71 mg, 60%), m.p. 250 ꢂC. Anal. Calcd.
for C28H36B10P2PtS2: C, 41.94; H, 4.52%. Found: C, 41.23; H, 4.46%. 1H
NMR (CDCl3)
26.0 ppm.
d d:
: 7.18 (t, Ph); 7.34 (m, Ph). 31P{1H} NMR (CDCl3)
NMR (CDCl3)
d
: 1.73 (d, J(PeH) ¼ 9.5 Hz; J(PteH) ¼ 36 Hz, PMe);
3.15. Preparation of [Pt(SCboS)(PEt3)2] (15)
7.27e7.31; 7.37e7.42 (m, Ph). 31P{1H} NMR (CDCl3)
d:
ꢀ1.5
(1J(PteP) ¼ 2848 Hz). 195Pt{1H} NMR (C6D6)
d
: ꢀ4381 (1J(PteP) ¼
Prepared similar to 8 using HSCboSH (63 mg, 0.30 mmol) and
[PtCl2(PEt3)2] (153 mg, 0.30 mmol) and pyridine (52 mg,
0.66 mmol) and recrystallized from CH2Cl2/hexane mixture to yield
a white crystalline solid (121 mg, 62%), m.p. 213 ꢂC. Anal. Calcd. for
2859 Hz) ppm.
3.18. Preparation of [Pt(SCboPh)2(PMe2Ph)2] (18)
C14H40B10P2PtS2: C, 26.37; H, 6.32%. Found: C, 26.26; H, 6.32%. 1
H
Prepared similar to 1 using HSCbꢂPh (83 mg, 0.33 mmol),
[PtCl2(PMe2Ph)2] (89 mg, 0.16 mmol) and pyridine (30 mg,
0.38 mmol) in dichloromethane and isolated as an off-white crys-
talline solid in 62% (99 mg) yield, m.p. 215 ꢂC. Anal. Calcd. for
C32H52B20P2PtS2: C, 39.46; H, 5.38%. Found: C, 39.73; H, 5.40%. 1H
NMR (CDCl3) d
: 1.06e1.17 (m, PCH2Me); 1.84e1.97 (m, PCH2). 31P
{1H} NMR (CDCl3)
d
: 7.6 (1J(PteP) ¼ 2775 Hz). 195Pt{1H} NMR
(CDCl3)
d
: ꢀ4437 (1J(PteP) ¼ 2777 Hz) ppm.
3.16. Preparation of [Pt(SCboS)(PMe2Ph)2] (16)
NMR (CDCl3) d: 1.14, 1.27 (br, each singlet, PMe2) 7.09e7.76 (m, Ph).
31P{1H} NMR (CDCl3)
d
: ꢀ16.3 (1J (PteP) ¼ 3031 Hz). 195Pt{1H} NMR
: ꢀ4572 (1J(PteP) ¼ 3033 Hz) ppm.
Prepared similar to 8 using HSCboSH (53 mg, 0.25 mmol) and
[PtCl2(PMe2Ph)2] (103 mg, 0.25 mmol) and pyridine (45 mg,
0.57 mmol) and recrystallized from CH2Cl2/hexane mixture to yield
a white crystalline solid (88 mg, 51%), m.p. 275 ꢂC. Anal. Calcd. for
C18H32B10P2PtS2: C, 31.90; H, 4.76%. Found: C, 31.91; H, 4.72%. 1H
(CDCl3)
d
3.19. Crystallographic experiments
Single crystal X-ray diffraction data for [Pt(SCboPh)2(dppm)],
[Pt(SeCboPh)2(dppm)], [Pt(SCboS)(PMe2Ph)2] and [Pt(SCboS)(P-
MePh2)2] were collected on a Bruker APEX 2 CCD diffractometer
NMR (CDCl3)
d
: 1.53 (d, 2J(PeH) ¼ 10 Hz, J(PteH) ¼ 27 Hz; PMe2);
7.32e7.35; 7.40e7.45 (m, Ph). 31P{1H} NMR (CDCl3)
d: e17.6
Table 6
Crystallographic and structure refinement data for [Pt (SCboPh)2(dppm)] (3), [Pt(SeCboPh)2(dppm)] (5), [Pt (SCboS)(PMe2Ph)2] (16) and [Pt(SCboS)(PMePh2)2] (17).
[Pt (SCb0Ph)2(dppm)] (3)
[Pt(SeCb0Ph)2(dppm)] (5)
41H52B20P2PtSe2.CH2Cl2
[Pt (SCboS)(PMe2Ph)2 ] (16)
[Pt(SCboS)(PMePh2)2] (17)
Chemical formula
C41H52B20P2PtS2.CH2Cl2,
C
C18H32B10P2PtS2
C28H36B10P2PtS2.0.5(CH2Cl2)
0.75(CH3OH), 0.25(C6H14
)
Formula weight
T/K
1212.68
100 (2)
1260.90
120 (2)
677.69
100 (2)
844.28
100 (2)
Size/color
0.25 ꢃ 0.13 ꢃ 0.10/
colourless-plate
Monoclinic
P21/c
12.1658 (6)
23.2493 (11)
19.8148 (9)
90.00
104.2720 (10)
90.00
5431.6 (4)
4
0.35 ꢃ 0.25 ꢃ 0.20/
colourless-needle
Triclinic
0.42 ꢃ 0.23 ꢃ 0.20/
colourless-needle
Monoclinic
C 2/c
17.0781 (5)
12.7838 (4)
12.2130 (4)
90.00
97.3730 (10)
90.00
2644.33 (14)
4
0.45 ꢃ 0.30 ꢃ 0.25/
colourless-plate
Monoclinic
P 21/n
11.9632 (5)
20.4256 (8)
15.2455 (6)
90.00
110.4120 (10)
90.00
3491.4 (2)
4
Crystal system
Space group
a/Å
b/Å
c/Å
P-1
12.018 (6)
13.868 (7)
17.965 (11)
67.441(13)
83.248 (18)
70.569 (12)
2607 (2)
ꢂ
ꢂ
a
/
b
/
ꢂ
/
g
V/Å3
Z
2
dcalc/g cmꢀ3
1.483
1.606
1.702
1.606
m
(mmꢀ1)/F(000)
2.853/2424
1.94e29.00
ꢀ16 ꢄ h ꢄ 16
ꢀ31 ꢄ k ꢄ 31
ꢀ26 ꢄ l ꢄ 27
14,386
4.283/1232
2.05e26.00
ꢀ14 ꢄ h ꢄ 14
ꢀ17 ꢄ k ꢄ 17
ꢀ22 ꢄ l ꢄ 22
10,121
5.593/1320
2.41e29.99
ꢀ24 ꢄ h ꢄ 24
ꢀ17 ꢄ k ꢄ 17
ꢀ17 ꢄ l ꢄ 17
16,520
4.328/1660
2.45e29.00
ꢀ16 ꢄ h ꢄ 16
ꢀ27 ꢄ k ꢄ 27
ꢀ20 ꢄ l ꢄ 16
28,142
q
for data collection
Limiting indices
No. of reflections
collected
No. of observed
reflections with I > 2
10,692
5219
3721
8030
s(I)
Data/restraints/parameters
Final R1, R2 indices
(R_factor_gt/ R_factor_gt)
R1, R2 (all data)
(R_factor_all/
GOF
Largest difference peak
and hole (e Åꢀ3
14,386/5/660
0.0436/0.0835
10,121/0/626
0.0687/0.1069
3833/0/152
0.0143/0.0348
9227/0/415
0.0226/0.0516
u
u
u
0.0700/0.0939
0.1454/0.1284
0.0151/0.0351
0.0301/0.0516
u
R_Factor_ref)
1.004
2.481 and ꢀ1.169
1.028
2.113 and ꢀ0.978
1.007
1.141 and ꢀ0.670
1.015
1.209 and ꢀ0.926
)

M.K. Pal et al. / Journal of Organometallic Chemistry 696 (2012) 4257e4263
4263
[23] S. Dey, L.B. Kumbhare, V.K. Jain, T. Schurr, W. Kaim, A. Klein, F. Belaj, Eur. J.
Inorg. Chem. (2004) 4510e4520.
using graphite monochromated Mo K
a
radiation (
l
¼ 0.71703 Å).
Low temperature of the crystals was maintained with a cryostream
(Oxford Cryo-system) open-flow N2 gas cryostat. Reflection inten-
sities were integrated using SAINT software and semi-empirical
method SADABS [65,66]. The structures were solved by direct
methods [67] and refinement was on F2 using data that had been
corrected for Lorentz and polarization effects with an empirical
procedure [68]. The non-hydrogen atoms were refined anisotrop-
ically. All carborane hydrogen atoms were located from difference
Fourier synthesis, the H(C) atoms were placed in geometrically
calculated positions. All hydrogen atom positions were refined in
isotropic approximation in riding model with the Uiso(H) param-
eters equal to 1.2 Ueq(Xi) or Ueq(Ci) where U(Xi) are the equivalent
thermal parameters of the boron and methylene carbon. Molecular
structures were drawn using ORTEP [69]. Crystallographic data,
together with the data collection and refinement details are given
in Table 6.
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We thank Drs. T. Mukherjee and D. Das for encouragement of
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Moscow for financial support under ILTP project No. B-5.22. This
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833860 (for 17) contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge at www.
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