Spontaneous formation of heteroligated PtII Complexes with chelating hemilabile ligands

Article abstract of DOI:10.1002/chem.200601837

The spontaneous formation of the heteroligated complex [PtCl(κ ²-Ph₂PCH₂CH₂SMe)(Ph ₂PCH₂CH₂SPh)]-Cl (8a) by a novel ligand rearrangement process has been observed. By using the w

Full text of DOI:10.1002/chem.200601837

FULL PAPER
DOI: 10.1002/chem.200601837
II
Spontaneous Formation of Hetero
Hemilabile Ligands
A
H
R
U
G
[
a]
[a]
[a]
[a]
Pirmin A. Ulmann, Aaron M. Brown, Maxim V. Ovchinnikov, Chad A. Mirkin,*
[
b]
[b]
Antonio G. DiPasquale, and Arnold L. Rheingold
À
À
Abstract: The spontaneous formation
of the heteroligated complex [PtCl(k -
Ph PCH CH SPh)]
opening using halide ions to form semi-
A
H
R
U
G
BF4 (8b; X=Cl ) and (8c; X=I ).
Analogous
2
2
2
4 2
2
procedures
and
using
1,4-
Ph PCH CH SMe)(Ph PCH CH SPh)]-
open
complexes
Ph PCH CH SMe
2
2
2
2
2
2
2
2
2
Cl (8a) by a novel ligand rearrange-
ment process has been observed. By
using the weak-link approach, the rela-
tive arrangement of the alkyl and aryl
groups can be controlled by abstraction
of chloride from 8a to form the closed
Ph PCH CH SMe)(Ph PCH CH SPh)]-
(Ph PCH CH S) C H lead to heteroli-
2 2 2 2 6 4
2
2
2
2
2
2
gated bimetallic complexes 7 and 9, il-
lustrating that this ligand rearrange-
ment process can be used as a tool for
the assembly of complementary metal-
losupramolecular structures.
Keywords: coordination modes
hemilabile ligands platinum
·
·
·
supramolecular chemistry · transi-
tion metals
2
2
complex [Pt(k -Ph PCH CH SMe)(k -
2
2
2
[
2,5]
Introduction
ing metallated and catalytically active salen moieties,
into
[6]
metallosupramolecular structures in a way that could facil-
itate cooperative interactions in the context of tweezer or
“triple-decker” complexes. These molecules are essential for
We recently reported a novel halide-induced ligand rear-
rangement process in bisphosphane–Rh complexes, which
I
results in metal complexes with heteroligated coordination
the development of allosteric regulators with regard to both
[1]
[6f,7]
environments. This process was developed into a stepwise
reaction that allows us to predictably construct square-
catalysis and chemical sensing.
Thus far, the utility of the
I
reaction has been limited to Rh , which generally means
that inert atmosphere conditions have to be used. Therefore,
creating comparable capabilities with other metal centers
that lead to air- and moisture-tolerant complexes could sub-
stantially extend the scope of utility of the allosteric systems
as well as the range of molecules that can be used to initiate
opening and closing of such complexes. Herein, we report a
I
[2]
[3]
planar Rh complexes with tweezer (1) or “triple-decker”
(
(
2) conformations that can be opened and closed reversibly
Scheme 1). A related procedure, also developed by our
group, involving the stepwise addition of two different phos-
phane ligands leads to qualitatively similar heteroligated
I
[4]
Rh macrocycles. This reaction is quite powerful as it
allows us to incorporate sophisticated functionality, includ-
II
synthetic strategy to synthesize heteroligated Pt complexes
bearing hemilabile aryl- and alkylthioether–phosphane li-
gands that are stable under ambient conditions. A large vari-
ety of synthetic methods are available to generate P,S li-
gands with functionalized alkyl and aryl groups, potentially
allowing for the convergent assembly of complex supra-
molecular structures from relatively simple building blocks.
[
a] P. A. Ulmann, A. M. Brown, M. V. Ovchinnikov, Prof. C. A. Mirkin
Department of Chemistry and the
International Institute for Nanotechnology
Northwestern University, 2145 Sheridan Road
Evanston, Illinois 60208-3113 (USA)
Fax : (+1)847-467-5123
E-mail: chadnano@northwestern.edu
[
b] A. G. DiPasquale, Prof. A. L. Rheingold
Department of Chemistry and Biochemistry
University of California, San Diego, 9500 Gilman Drive
La Jolla, California 92093-0358 (USA)
Results and Discussion
Synthesis of heteroligated complexes: Target structures 5
Supporting information for this article is available on the WWW
under http://www.chemeurj.org/ or from the author. The Supporting
Information contains P{ H} NMR spectra that illustrate the forma-
(
Scheme 2) and 7 (Scheme 3) bear the S-alkyl and S-aryl
3
1
1
groups in cis position with respect to each other to allow for
tion of complex 8a via homoligated intermediate complexes.
cooperative effects or blocking of a catalytic site between
Chem. Eur. J. 2007, 13, 4529 – 4534
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4529

3
148 Hz), corresponding to the
2
P atom of the k -P,S-alkyl che-
lating ligand and to the P atom
1
of the unchelated k -P,S-aryl
[9]
ligand, respectively. A single-
crystal X-ray crystallographic
study confirms the solid-state
cis-phosphane semi-open struc-
[
8]
ture of 8a (Figure 2, Table 1).
II
The Pt center exhibits a dis-
torted square-planar geometry
with P1-Pt1-P2, P2-Pt1-Cl1,
and S1-Pt1-Cl1 angles of
9
8
9.46(5),
88.57(5),
and
6.19(5)8, respectively. The
Scheme 1. M=metal; X=S,O; L =ligand; A, B = functional or catalytic groups.
Pt1ÀS1 and Pt1ÀCl1 bond
lengths are 2.3465(15) and
2
.3497(14) Š, respectively. The preferential coordination of
II
the alkylthioether moiety to the Pt center, while the aryl-
AHCTREUNG
Scheme 2.
Scheme 3.
functionalized alkyl and aryl groups, as has been realized
I
[2,3,7a–e]
with Rh structures using P,S and P,O ligands.
They
can be formed in a one-pot procedure, in which the semi-
open precursor complexes 8a (Scheme 4) or 9 (Scheme 5)
are formed in situ, followed by chloride abstraction with
Figure 1. ORTEP diagram of 5·CH Cl ·0.5pentane with thermal ellipsoids
2
2
À
À
drawn at 30% probability. Hydrogen atoms, counterions and solvent mol-
ecules have been omitted for clarity. Selected bond lengths [Š] and
angles [8]: Pt1ÀP1 2.2669(17), Pt1ÀP2 2.2726(16), Pt1ÀS1 2.3597(17),
Pt1ÀS2 2.3536(17), P1-Pt1-P2 97.65(6), P1-Pt1-S1 85.60(6), P2-Pt1-S2
AgBF or NaBArF (BArF : B
A
H
R
U
G
A
H
R
U
G
4
(
88% yield) or 7 (70% yield), respectively. A single-crystal
[
8]
X-ray crystallographic study of 5 (Figure 1, Table 1) shows
that the methyl and phenyl groups of the two ligands are
pointing away from each other and that the five-membered
86.13(6), S1-Pt1-S2 90.85(6), P1-Pt1-S2 175.43(6), P2-Pt1-S1 174.25(6).
II
chelate rings assume a half-chair geometry. The Pt center
exhibits a distorted square-planar geometry with P1-Pt1-P2
and S1-Pt1-S2 angles of 97.65(6) and 90.85(6)8, respectively.
The Pt1ÀS1 and Pt1ÀS2 bond lengths are 2.3597(17) and
nificant influence of the substituent on the thioether group
[10]
on its ability to undergo complexation with a metal. This
is likely due to the electron-withdrawing properties of the
phenyl ring, resulting in a lower electron density on the S
atom of the arylthioether ligand compared to the alkylth-
ioether ligand.
2.3536(17) Š, respectively.
Compound 8a, the semi-open chloride precursor to struc-
ture 5, is synthesized by the addition of one equivalent of
Pt(cod)Cl ] (cod: 1,5-cyclooctadiene) to one equivalent of
Ph PCH CH SMe (3) in CH Cl , followed by the addition of
[
A
C
H
T
R
E
U
N
G
When the bisbidentate phosphane ligand 1,4-
(Ph PCH CH S) C H (6) is used instead of bidentate ligand
2
2
2
2
2
2
2
2
2
2
6
4
one equivalent of Ph PCH CH SPh (4) at 248C in 89%
4, bimetallic complex 9 is formed in 90% yield (Scheme 5).
2
2
2
3
1
1
yield (Scheme 4). Complex 8a exhibits resonances in its
It exhibits resonances in its P{ H} NMR spectrum at d=
3
1
1
2
1
2
1
ACHTREUNG
P{ H} NMR spectrum at d=43.8 (d,
J
A
H
R
N
(P,P)=14 Hz, J-
44.0 (d, J
A
H
R
U
G
2
1
2
1
ACHTREUNG
A
C
H
T
R
E
U
N
G
(Pt,P)=3500 Hz) and 8.5 ppm (d, J
A
H
R
U
G
A
H
R
U
G
(d,
J
A
H
R
U
G
4530
www.chemeurj.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 4529 – 4534

Supramolecular Chemistry
FULL PAPER
Table 1. Crystallographic data.
formula
5
·CH
2
Cl
2
·0.5pentane
8a·CH
2
Cl
2
C
38.5
H
31.5
B
2
Cl PtS
2
F
8
P
2
2
C
36
H38Cl
4
P
2 2
PtS
M
r
1059.81
colorless, plate
0.30”0.30”0.10
C2/c
monoclinic
37.718(3)
12.8281(12)
18.8568(17)
90
115.3160(10)
90
8247.7(13)
8
933.61
color, habit
crystal dimensions [mm]
space group
crystal system
a [Š]
b [Š]
c [Š]
a [8]
b [8]
colorless, needle
0.15”0.10”0.05
¯
P1
triclinic
9.6990(13)
11.4350(15)
16.537(2)
84.367(2)
86.080(2)
85.345(2)
1815.8(4)
2
Scheme 5.
II
coordination geometry around the Pt center is similar to
complex 8a. Furthermore, complex 9 exhibits molecular ion
peaks in its ESIMS spectrum at m/z 1581.6 and 773.2, corre-
g [8]
V [Š ]
Z
3
+
2+
sponding to the [MÀCl] and [MÀ2Cl] ions.
À3
1
calcd [gcm
]
1.707
1.708
Reactivity of closed complex 5: Initial investigations on the
reactivity of condensed complex 5 with small molecules
showed that selective cleavage of the PtÀS aryl bond is pos-
radiation (l [Š])
(000)
MoKa (0.71073)
4148
3.84 to 56.56
3.776
100(2)
34287
MoKa (0.71069)
924
4.16 to 56.18
4.387
100(2)
20752
F
ACHTREUNG
2
q range [8]
À1
m [mm
T [K]
]
sible with halide molecules, giving the semi-open chloride
complex 8b or iodide complex 8c through the addition of
two equivalents of tetramethylammonium chloride or tetra-
methylammonium iodide in MeOH at 248C (Scheme 6, both
reflns measured
independent reflns
9493
8083
[
R
A
H
R
U
G
[R(int)=0.0427]
A
H
R
U
G
2
GOF on F
1.053
1.040
final R indices [I>2s(I)]
R1=0.0517
wR2=0.1361
R1=0.0747
wR2=0.1495
2.424/À1.762
R1=0.0446
wR2=0.1089
R1=0.0581
wR2=0.1152
4.200/À2.467
R indices (all data)
À3
Largest diff. peak/hole [eŠ
]
Scheme 6.
Scheme 4.
À
complexes contain BF4 as a counterion), while no opening
of 5 is observed upon the addition of 20 equivalents of
acetonitrile in CD OD after 24 h at 248C, according to in
A
H
R
U
G
3
3
1
1
situ P{ H} NMR spectroscopy. Therefore, complementary
I
[11]
reactivity with regard to Rh complexes was observed.
Control reactions for ligand rearrangement process: To in-
vestigate whether the observed spontaneous formation of
II
heteroligated Pt complexes is the result of a ligand rear-
rangement process, ligands 3 (2 equiv) and 4 (2 equiv) each
were separately mixed with [Pt
A
H
R
U
G
CD Cl /CH Cl (1:5 v/v). The homoligated intermediates ex-
2
2
2
2
3
1
1
hibit broad resonances in their P{ H} NMR spectra, indi-
cating exchange processes that are fast on the NMR time-
scale at room temperature. This observation is consistent
with literature references on the formation of homoligated
II
[12,13]
Figure 2. ORTEP diagram of 8a·CH
2
Cl
2
with thermal ellipsoids drawn at
Pt complexes with ligands 3 and 4.
Upon mixing of the
3
0% probability. Hydrogen atoms, counterion and solvent molecules
two solutions, the formation of heteroligated complex 8a
and the complete disappearance of the reactants was ob-
served after 15 min, according to in situ P{ H} NMR spec-
troscopy (see Supporting Information). In a separate experi-
have been omitted for clarity. Selected bond lengths [Š] and angles [8]:
Pt1ÀP1 2.2241(14), Pt1ÀP2 2.2698(15), Pt1ÀS1 2.3465(15), Pt1ÀCl1
3
1
1
2
.3497(14), P1-Pt1-P2 99.46(5), P1-Pt1-S1 85.89(5), P2-Pt1-Cl1 88.57(5),
S1-Pt1-Cl1 86.19(5), P1-Pt1-Cl1 171.92(5), P2-Pt1-S1 172.34(5).
Chem. Eur. J. 2007, 13, 4529 – 4534
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
4531

C. A. Mirkin et al.
ment, [Pt
A
C
H
T
R
E
U
N
G
(cod)Cl ] was added to a mixture of ligands 3 and
Micromass Quatro II triple quadrupole mass spectrometer. Electron ioni-
zation mass spectra (EIMS) were recorded on a Fisions VG 70–250 SE
mass spectrometer. Melting points were measured on a Mel-Temp 2
2
4
in CD Cl /CH Cl (1:5 v/v), and complex 8a was observed
2
2
2
2
3
1
1
exclusively after 15 min, according to in situ P{ H} NMR
spectroscopy.
(
Laboratory Devices) apparatus. Elemental analyses were performed by
Quantitative Technologies, Whitehouse, NJ (USA).
Thus, the observed reaction constitutes a ligand rear-
rangement process leading from two different homoligated
complexes to a single heteroligated complex. This example
of spontaneous selective pairing of two P,S ligands A and B
and a metal M in solution to form heteroligated A-M-B
motifs instead of a mixture of A-M-A, B-M-B, and A-M-B
motifs is one of relatively few examples of spontaneous
[22]
(
2-Methylthioethyl)diphenylphosphane (3):
2
KPPh in THF (79 mL,
0.5m, 39.5 mmol, 1 equiv) was added to 2-chloroethylmethyl sulfide
(4.0 mL, 40.5 mmol, 1.03 equiv) over 15 min at 248C. The solution turned
from yellow to red. After stirring for 3 h, the reaction solution was con-
centrated in vacuo and redissolved in CH
O (3”75 mL), dried with Na SO , filtered, and concentrated in vacuo
to give a yellow oil. Recrystallization from MeOH gave 3 as an off-white
2 2
Cl (ca. 100 mL), washed with
H
2
2
4
1
powder (8.580 g, 83%). M.p. 548C; H NMR (300 MHz, CD
d=7.46–7.40 (m, 4H; arom), 7.39–7.33 (m, 6H; arom), 2.59–2.51 (m, 2H;
2 2
Cl , 228C):
[14]
complementary metallosupramolecular complexation that
is more frequently observed in organic supramolecular
-
SCH
2
CH
2
P-), 2.37–2.32 (m, 2H; -SCH
C{ H} NMR (75.5 MHz, CD Cl , 228C): d=138.7 (d,
(C,P)=19.0 Hz; C -P), 129.3 (s; C
(C,P)=21.7 Hz; -SCH
), 15.8 ppm (s; -SCH ); P{ H} NMR
, 228C): d=À16.8 ppm (s); MS (EI): m/z calcd for
17PS [M] : 260.0789; found: 260.0788; elemental analysis calcd (%)
2
CH
2
P-), 2.09 ppm (s, 3H; -SCH
3
);
1
3
1
1
ACHTREUNG
2
2
J
(C,P)=13.2 Hz;
-P), 129.1 (d, J-
[15]
chemistry.
2
ACHTREUNG
3
C
i
-P), 133.2 (d,
J
o
p
2
A
H
R
U
G
m
-P), 31.1 (d,
(C,P)=14.3 Hz; -CH PPh
Cl
J
A
H
R
U
2 2 2
CH PPh ), 28.7
1
31
1
(
(
d,
J
A
H
R
U
G
2
2
3
121.5 MHz, CD
2
2
Conclusion
+
15
C H
for C15
H
17PS: C 69.21, H 6.59; found: C 69.28, H 6.68.
We have presented a novel ligand rearrangement process
that spontaneously leads to heteroligated Pt complexes co-
2
2
[
Pt(k -Ph
2
PCH
2
CH
2
SMe)(k -Ph
2
PCH
2
CH
2
SPh)]
A
H
R
U
G
4
]
2
(5): A solution of
II
[
Pt
A
H
R
U
G
2
] (100.7 mg, 0.269 mmol, 1 equiv) in CH
2
2
(3 mL) was added
ordinating to P,S-aryl and P,S-alkyl ligands. Condensation to
closed complexes and reopening using halide ions illustrate
dropwise to a stirring solution of ligand 3 (70.0 mg, 0.269 mmol, 1 equiv)
in CH Cl (3 mL) at 248C. The solution turned slightly yellow. After
5 min, a solution of 4 (86.7 mg, 0.269 mmol, 1 equiv) in CH Cl (3 mL)
2
2
[
20]
[6e,f,7a–f,10,16,17]
how the weak-link approach
can be used to ma-
2
2
II
was added dropwise to the stirring reaction mixture. After 1 h, AgBF
104.7 mg, 0.538 mmol, 2 equiv) was added to the reaction mixture, which
4
nipulate the coordination environment around Pt centers
to make various heteroligated complexes with different rela-
tive arrangements of the thioether substituents. Because of
the robustness of the Pt complexes with respect to oxygen
and moisture and the high selectivity of the rearrangement
process, the reaction is expected to become a valuable tool
for the “programmed” assembly of complex functional
(
turned cloudy. After 1 h, the reaction mixture was filtered through celite,
followed by recrystallisation from CH Cl /hexanes, resulting in 5 as a
2
2
1
white powder (229.3 mg, 88%). M.p. 1688C; H NMR (300 MHz,
CD Cl , 228C): d=7.84–7.50 (m, 25H; arom), 3.8–2.1 ppm (m, 11H;
aliph); P{ H} NMR (121.5 MHz, CD
2
2
3
1
1
2
ACHTREUNG
2
Cl
(Pt,P)=3085 Hz), 45.8 ppm (d,
130 Hz); MS (ESI): m/z calcd for C35
863.8; elemental analysis
PtS ·0.25C 14: C 45.03, H 4.09; found: C 44.92; H 3.81. A
residual amount of hexane was observed by H NMR spectroscopy after
purification and extended drying in vacuo. Crystals of
·CH Cl ·0.5pentane suitable for single-crystal X-ray crystallography
were obtained by slow diffusion of pentane into a saturated solution of 5
2
, 228C): d=46.4 (d,
J
(P,P)=
1
2
1
ACHTREUNG
1
3
1 Hz,
J
A
H
R
U
G
J
A
H
R
U
J
(Pt,P)=
+
H
36BF
4
P
2
2
4
] : 864.1;
for
[7]
supramolecular structures and allosteric catalysts. The se-
lective reactivity of the complexes with respect to various
small molecules suggests potential applications for the de-
velopment of sensors for small molecules. The interaction of
nucleobases as N-donor ligands with respect to hemilabile,
found:
C
35
H
36
B
2
F
8
P
2
2
6
H
1
5
2
2
II
[18]
homoligated Pt –P,N complexes
indicates that a further
in CH
2
Cl
2
(colorless plates).
2
2
2
2
extension to biologically relevant analyte molecules may be
possible.
A
H
R
U
G
2
{k :m :k -1,4-(Ph
7): A solution of [Pt
2
PCH
(cod)Cl
3 mL) was added dropwise to
.0576 mmol, 2 equiv) in CH Cl
slightly yellow. After 5 min, a solution of 6
1 equiv) in CH Cl (3 mL) was added dropwise to the reaction mixture.
After 30 min, NaBArF (102.2 mg, 0.115 mmol, 4 equiv) was dissolved
in CH Cl (3 mL) and added to the reaction mixture, which turned
cloudy. After 2 h, the reaction mixture was filtered through celite, fol-
lowed by recrystallization from CH Cl /hexanes, resulting in 7 as a white
powder (99.2 mg, 70%). M.p. 1188C; H NMR (300 MHz, CD
2
CH
] (21.6 mg, 0.0577 mmol, 2 equiv) in CH
stirring solution of
(3 mL) at 248C. The solution turned
2
S)
2
C
6
H
4
}(k -Ph
2
PCH
2
CH
2
SMe)
2
]
A
C
H
T
R
E
U
N
G
[BArF]
4
(
(
0
A
T
E
N
2
2
Cl
2
a
3 (15.0 mg,
2
2
[
17]
(16.3 mg, 0.0288 mmol,
Experimental Section
2
2
[
21]
2
2
General methods/instrument details: All reactions were carried out
under an inert atmosphere of nitrogen using standard Schlenk techniques
2
2
or an inert atmosphere glovebox unless otherwise noted. CH
2 2
Cl , acetoni-
1
2
2
Cl , 228C):
trile, and hexanes were dried and purified through activated alumina col-
3
1
1
[
19]
d=7.72–6.95 (m, 92H; arom), 3.1–2.3 ppm (m, 22H; aliph); P{ H}
umns as described by Grubbs et al. prior to use. All solvents were de-
gassed with nitrogen prior to use. Deuterated solvents were purchased
from Cambridge Isotope Laboratories and used as received. All other
chemicals were used as received from Aldrich Chemical Company or
2
1
ACHTREUNG
NMR (121.5 MHz, CD
093 Hz), 46.7 ppm (d,
m/z calcd for C128
2
Cl
2
, 228C): d=47.0 (d, J
A
H
R
U
G
J
(Pt,P)=
2
1
3
J
A
H
E
N
J(Pt,P)=3020 Hz); MS (ESI):
A
H
R
U
G
2
+
H
90
B
2
F
48
P
4
2
S
4
[MÀ2BArF] : 1601.7; found: 1601.7;
[
20]
[17]
[21]
114 4 96 4 2 4
elemental analysis calcd (%) for C192H B F P Pt S : C 46.75, H, 2.33;
prepared according to literature procedures (4,
6,
H NMR and C{ H} NMR spectra were recorded on a Varian Mercury
00 MHz FT-NMR spectrometer at 300 and 75.5 MHz, respectively, and
referenced to residual proton resonances in deuterated solvents.
NaBArF ).
1
13
1
found: C 46.98, H 2.03.
2
3
A
H
E
N
[PtCl(k -Ph
(cod)Cl
2
PCH
] (139.9 mg, 0.374 mmol, 1 equiv) in CH
dropwise to a stirring solution of 3 (97.3 mg, 0.374 mmol, 1 equiv) in
CH Cl (5 mL) at 248C. The solution turned slightly yellow. After 5 min,
a solution of 4 (120.5 mg, 0.374 mmol, 1 equiv) in CH
added dropwise, and the reaction mixture was stirred for 1 h. Recrystalli-
sation from CH Cl /hexanes resulted in 8a as a white powder (310.5 mg,
89%). M.p. 1668C; H NMR (300 MHz, CD
2
CH
2
SMe)(Ph
2
PCH
2
CH
2
SPh)]Cl (8a): A solution of
[Pt
A
H
R
U
G
2
2
Cl (5 mL) was added
2
3
1
1
P{ H} NMR spectra were recorded on a Varian Mercury 300 MHz FT-
NMR spectrometer at 121.5 MHz and referenced relative to an external
2
2
1
9
1
[20]
8
5% H
Mercury 300 MHz FT-NMR spectrometer at 282.5 MHz and referenced
relative to an external CFCl in CDCl standard. All chemical shifts are
reported in ppm. Electrospray mass spectra (ESIMS) were recorded on a
3
PO
4
standard. F{ H} NMR spectra were recorded on a Varian
2 2
Cl (5 mL) was
3
3
2
2
1
2
2
Cl , 228C): d=7.52–7.15 (m,
4532
www.chemeurj.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 4529 – 4534

Supramolecular Chemistry
FULL PAPER
2
2
5H; arom), 3.17–3.11 (m, 3H; -SCH
3
), 2.99–2.92 (m, 4H; -CH
2
-), 2.68–
over 1 min to a stirring solution of 3 (10.0 mg, 0.0384 mmol, 2 equiv) in
3
1
1
.59 ppm (m, 4H; -CH
2
-); P{ H} NMR (121.5 MHz, CD Cl , 228C): d=
2
2
CH
(7.2 mg, 0.0192 mmol, 1 equiv) in CH
over 1 min to a stirring solution of 4 (12.4 mg, 0.0385 mmol, 2 equiv) in
CH Cl (1 mL). CD Cl (0.4 mL) was added to each vial. A 1 mL aliquot
2
Cl
2
(1 mL) at 248C. In a separate vial, a solution of [Pt
A
C
H
T
R
E
U
N
G
2
(cod)Cl ]
2
1
2
4
3.8 (d,
J
A
C
H
T
R
E
U
N
G
(P,P)=14 Hz,
(Pt,P)=3148 Hz); MS (ESI): m/z calcd for C35
12.1; found: 812.4; elemental analysis
PtS ·CH Cl
molecule found in the combustion analysis is also observed in the
crystal structure. Crystals of 8a·CH Cl suitable for single-crystal X-ray
crystallography were obtained by slow evaporation of Et O into a satu-
J
A
H
R
U
G
J
ACHTREUNG
(P,P)=15 Hz,
2
2
Cl (1 mL) was added dropwise
1
+
J
A
C
H
T
R
E
U
N
G
H
36ClP
calcd
2
PtS
2
[MÀCl] :
8
C
(%)
for
2
2
2
2
3
1
1
35
H
36Cl
2
P
2
2
2
2
: C 46.40, H 4.11; found: C 46.08, H 4.00. The
of each solution was transferred into two air-free NMR tubes and P{ H}
NMR spectra were recorded, showing broad resonances that are consis-
tent with those given in reference [12a]. After 1 h, the two aliquots were
recombined with the respective solutions and then the two solutions were
mixed. After 5 min, a 1 mL aliquot was transferred into an air-free NMR
2 2
CH Cl
2
2
2
rated solution of 8a in CH
2
Cl
2
(colorless needles).
3
1
1
2
tube and another P{ H} NMR spectrum was recorded after 10 min,
A
C
H
T
R
E
U
N
G
[PtCl(k -Ph
2
PCH
2
CH
2
SMe)(Ph
2
PCH CH SPh)]BF (8b): A solution of
2
2
4
A
H
R
U
G
showing the clean formation of complex 8a.
4
Me NCl (4.6 mg, 0.042 mmol, 2 equiv) in MeOH (anhydrous, 5 mL) was
added to a stirring solution of complex 5 (20.0 mg, 0.0210 mmol, 1 equiv)
in MeOH (anhydrous, 5 mL) at 248C. The solution was colorless. After
Reaction of [Pt
in heteroligated complex 8a:
0.0385 mmol, 1 equiv) in CH Cl
added dropwise over 1 min to
0.0384 mmol, 1 equiv) and 4 (12.4 mg, 0.0385 mmol, 1 equiv) in CH
(2 mL). A 1 mL aliquot was transferred into an air-free NMR tube after
A
H
R
U
G
2
] with a mixture of P,S ligands 3 and 4, resulting
solution of [Pt(cod)Cl (14.4 mg,
(2 mL) and CD Cl (0.75 mL) was
stirring solution of (10.0 mg,
Cl
A
A
T
U
2
]
3
(
0 min, the solution was concentrated in vacuo. Addition of CH
3 mL) and hexanes (ca. 1 mL), filtration through celite, and concentra-
tion in vacuo gave 8b as a white powder (16.2 mg, 82%). M.p. 1328C;
2
Cl
2
2
2
2
2
a
3
2
2
1
H NMR (300 MHz, CD
.09 (m, 3H; -SCH ), 2.99–2.91 (m, 4H; -CH
-); P{ H} NMR (121.5 MHz, CD Cl , 228C): d=43.7 (d,
(Pt,P)=3505 Hz), 8.4 ppm (d,
2
Cl
2
, 228C): d=7.54–7.15 (m, 25H; arom.), 3.14–
3
1
3
-
1
3
2
-), 2.68–2.59 ppm (m, 4H;
5 min and a P{ H} NMR spectrum was recorded after 10 min, showing
the clean formation of complex 8a.
3
1
1
2
ACHTREUNG
CH
2
2
2
J
1
2
1
ACHTREUNG
[
8]
5 Hz,
J
A
C
H
T
R
E
U
N
G
J
A
H
R
U
G
J
X-ray crystallography: Crystallographic data are collected in Table 1.
Colorless crystals of 5 and 8a were mounted on fiber loops and cooled to
100 K. In both cases the centrosymmetric space group option was select-
ed based on the results of the refinement. The structures were solved by
1
9
1
3
118 Hz); F{ H} NMR (282.5 MHz, CD
2
Cl
2
1
0
11
BF
4
), À152.99 ppm (s; BF
4
H
36
P
2
2
+
[
C
MÀBF
4
] : 812.1; found: 812.5; elemental analysis calcd (%) for
2
35
H
36BClF
4
P
2
PtS
2
·0.5C
6
H
14: C 48.40, H 4.60; found: C 48.05, H, 4.42. A
direct methods, and refined by full-matrix least-squares methods on F
1
residual amount of hexane was observed by H NMR spectroscopy after
with anisotropic thermal parameters, and contained idealized hydrogen
atoms, except for the fractional and disordered pentane molecule in 5.
The asymmetric units contained cocrystallized solvent molecules in both
purification and extended drying in vacuo.
2
A
C
H
T
R
E
U
N
G
[PtI(k -Ph
2
PCH
2
CH
2
SMe)(Ph
2
PCH
2
CH
2
SPh)]BF
4
(8c): A solution of
A
H
R
U
G
Me
4
NI (8.4 mg, 0.042 mmol, 2 equiv) in MeOH (anhydrous, 5 mL) was
cases: for 5, CH
2 2
Cl and 0.5pentane located on an inversion center, and
added to a stirring solution of complex 5 (20.0 mg, 0.0210 mmol, 1 equiv)
in MeOH (anhydrous, 5 mL) at 248C. The solution was yellow. After
for 8a CH Cl . All software is contained in the SMART, SAINT and
SHELXTL software libraries of the Bruker XRD corporation.
2
2
3
0 min, the solution was concentrated in vacuo. Addition of CH
2 2
Cl
(
3 mL), filtration through celite, and concentration in vacuo gave 8c as a
1
yellow-orange powder (19.7 mg, 95%). M.p. 1228C; H NMR (300 MHz,
CD Cl , 228C): d=7.57–7.14 (m, 25H; arom), 3.2–3.02 (m, 3H; -SCH ),
.90–2.63 ppm (m, 8H; -CH
Acknowledgements
2
2
3
3
1
1
2
2
-); P{ H} NMR (121.5 MHz, CD
2
Cl
Cl
2
,
,
2
1
ACHTREUNG
2
28C): d=49.2 (d,
(P,P)=12 Hz,
28C): d=À152.97 (s; BF
J
A
C
H
T
R
E
U
N
G
(P,P)=11 Hz,
(Pt,P)=3073 Hz); F{ H} NMR (282.5 MHz, CD
J
(Pt,P)=3343 Hz), 2.7 ppm (d,
We acknowledge the NSF, ARO, AFOSR and DDRE (MURI) for finan-
cial support of this research. C.A.M. is grateful for a NIH Directorꢁs Pio-
neer Award.
2
1
19
1
A
C
H
T
R
E
U
N
G
J
A
C
H
T
R
E
U
N
G
J
A
C
H
T
R
E
U
N
G
2
2
1
0
11
2
4
), À153.02 ppm (s; BF
4
); MS (ESI): m/z
] : 904.0; found: 904.2; elemental analy-
+
calcd for C35
sis calcd (%) for C35
.55.
[Pt Cl
solution of [Pt
2 mL) was added dropwise to
.0907 mmol, 2 equiv) in CH Cl
slightly yellow. After 5 min, a solution of 6
equiv) in CH Cl (2 mL) was added dropwise and the reaction mixture
was stirred for 1 h at 248C. Recrystallisation from CH Cl /hexanes result-
ed in 9 as an off-white powder (65.8 mg, 90%). M.p. 1868C; H NMR
300 MHz, CD Cl , 228C): d=7.51–7.19 (m, 44H; arom), 3.18–3.05 (m,
H; -SCH ), 2.85–2.60 (m, 8H; -CH -), 2.48–2.28 ppm (m, 8H; -CH -);
P{ H} NMR (121.5 MHz, CD Cl , 228C): d=44.0 (d, (P,P)=12 Hz,
(Pt,P)=3146 Hz); MS
[MÀCl] : 1581.1; found: 1581.6;
[MÀ2Cl] : 773.1; found: 773.2; elemental
Pt : C 47.52, H 4.12; found: C 47.92,
H
36IP
2
PtS
2
[MÀBF
4
H
36BF
4
IP
2
PtS
2
: C 42.38, H 3.66; found: C 42.10, H
3
[1] A. M. Brown, M. V. Ovchinnikov, C. L. Stern, C. A. Mirkin, J. Am.
Chem. Soc. 2004, 126, 14316–14317.
2
2
A
C
H
T
R
E
U
N
G
2
2
A
C
H
T
R
E
U
N
G
{m -1,4-(Ph
2
PCH
2
CH
2
S)
2
C
6
H
4
}(k -Ph
2
PCH
2
CH
2
SMe)
2
]Cl
2
(9): A
[
[
[
2] A. M. Brown, M. V. Ovchinnikov, C. A. Mirkin, Angew. Chem. 2005,
17, 4279–4281; Angew. Chem. Int. Ed. 2005, 44, 4207–4209.
3] Y.-M. Jeon, J. Heo, A. M. Brown, C. A. Mirkin, Organometallics
2006, 25, 2729–2732.
4] M. V. Ovchinnikov, A. M. Brown, X. Liu, C. A. Mirkin, L. N. Za-
kharov, A. L. Rheingold, Inorg. Chem. 2004, 43, 8233–8235.
A
C
H
T
R
E
U
N
G
(cod)Cl
2
]
(33.9 mg, 0.0906 mmol, 2 equiv) in CH
stirring solution of (23.6 mg,
at 248C (2 mL). The solution turned
2 2
Cl
1
(
0
a
3
2
2
[
17]
(25.7 mg, 0.0454 mmol,
1
2
2
2
2
1
[5] A. M. Brown, M. V. Ovchinnikov, C. L. Stern, C. A. Mirkin, Chem.
Commun. 2006, 4386–4388.
(
2
2
[
6] a) S. Leininger, B. Olenyuk, P. J. Stang, Chem. Rev. 2000, 100, 853–
907; b) S. R. Seidel, P. J. Stang, Acc. Chem. Res. 2002, 35, 972–983;
c) M. Fujita, Acc. Chem. Res. 1999, 32, 53–61; d) P. Thanasekaran,
R.-T. Liao, Y.-H. Liu, T. Rajendran, S. Rajagopal, K.-L. Lu, Coord.
Chem. Rev. 2005, 249, 1085–1110; e) B. J. Holliday, C. A. Mirkin,
Angew. Chem. 2001, 113, 2076–2097; Angew. Chem. Int. Ed. 2001,
6
3
2
2
3
1
1
2
ACHTREUNG
2
2
J
1
2
1
ACHTREUNG
A
C
H
T
R
E
U
N
G
J
A
C
H
T
R
E
U
N
G
(Pt,P)=3514 Hz), 8.9 ppm (d,
ESI): m/z calcd for C64
m/z calcd for C64 Pt
J
A
H
R
N
(P,P)=13 Hz,
H66Cl P Pt S
3 4 2 4
J
+
(
2
+
H
66Cl
2
P
4
2 4
S
analysis calcd (%) for C64
H
66Cl
4
P
4
2 4
S
4
0, 2022–2043; f) N. C. Gianneschi, M. S. Masar, C. A. Mirkin, Acc.
H 4.42.
Chem. Res. 2005, 38, 825–837; g) D. Fiedler, D. H. Leung, R. G.
Bergman, K. N. Raymond, Acc. Chem. Res. 2005, 38, 349–358; h) B.
Kesanli, W. Lin, Coord. Chem. Rev. 2003, 246, 305–326; i) C. H. M.
Amijs, G. P. M. van Klink, G. van Koten, Dalton Trans. 2006, 308–
Control reactions
Reaction of acetonitrile with complex 5: Acetonitrile (5 mL, 0.1 mmol,
2
1
0 equiv) was added to a solution of complex 5 (5.0 mg, 0.0053 mmol,
equiv) in CD OD (0.75 mL) in a vial at 248C and transferred into an
3
3
27; j) F. A. Cotton, C. Lin, C. A. Murillo, Acc. Chem. Res. 2001, 34,
3
1
1
air-free NMR tube. After 24 h, a P{ H} NMR spectrum was recorded,
which showed no resonance upfield to 30 ppm, indicating the absence of
unchelated phosphorus ligand.
7
59–771; k) R. V. Slone, K. D. Benkstein, S. BØlanger, J. T. Hupp,
I. A. Guzei, A. L. Rheingold, Coord. Chem. Rev. 1998, 171, 221–
43; l) E. Lindner, S. Pautz, M. Haustein, Coord. Chem. Rev. 1996,
2
Separate reaction of P,S ligands 3 and 4 with [Pt
mixing to give heteroligated complex 8a: A solution of [Pt
7.2 mg, 0.0192 mmol, 1 equiv) in CH Cl (1 mL) was added dropwise
A
H
R
U
G
2
], followed by
155, 145–162; m) J. W. Lee, S. Samal, N. Selvapalam, H.-J. Kim, K.
Kim, Acc. Chem. Res. 2003, 36, 621–630; n) G. F. Swiegers, T. J.
Malefetse, Chem. Rev. 2000, 100, 3483–3537.
A
H
R
U
G
2
(
2
2
Chem. Eur. J. 2007, 13, 4529 – 4534
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
4533

C. A. Mirkin et al.
[
7] a) C. G. Oliveri, N. C. Gianneschi, S. T. Nguyen, C. A. Mirkin, C. L.
Stern, Z. Wawrzak, M. Pink, J. Am. Chem. Soc. 2006, 128, 16286–
C. Lin, T.-Y. Hsieh, M.-C. Cheng, S.-M. Peng, S.-T. Liu, Phosphorus
Sulfur Silicon Relat. Elem. 1996, 108, 61–73; f) G. K. Anderson,
G. J. Lumetta, Organometallics 1985, 4, 1542–1545; g) K. Issleib, W.
Gans, Z. Anorg. Allg. Chem. 1981, 475, 116–130; h) A. Benefiel,
D. M. Roundhill, Inorg. Chem. 1986, 25, 4027–4031; i) P. V. Rao, S.
Bhaduri, J. Jiang, D. Hong, R. H. Holm, J. Am. Chem. Soc. 2005,
127, 1933–1945; for more examples see reference [18].
1
6296; b) J. Heo, C. A. Mirkin, Angew. Chem. 2006, 118, 955–958;
Angew. Chem. Int. Ed. 2006, 45, 941–944; c) N. C. Gianneschi, S. T.
Nguyen, C. A. Mirkin, J. Am. Chem. Soc. 2005, 127, 1644–1645;
d) N. C. Gianneschi, S.-H. Cho, S. T. Nguyen, C. A. Mirkin, Angew.
Chem. 2004, 116, 5619–5623; Angew. Chem. Int. Ed. 2004, 43, 5503–
5
507; e) N. C. Gianneschi, P. A. Bertin, S. T. Nguyen, C. A. Mirkin,
L. N. Zakharov, A. L. Rheingold, J. Am. Chem. Soc. 2003, 125,
0508–10509; f) B. J. Holliday, J. R. Farrell, C. A. Mirkin, K.-C.
[14] a) M. Schmittel, V. Kalsani, Top. Curr. Chem. 2005, 245, 1–53; b) M.
Yoshizawa, M. Nagao, K. Kumazawa, M. Fujita, J. Organomet.
Chem. 2005, 690, 5383–5388; c) P. Baxter, J.-M. Lehn, A. DeCian, J.
Fischer, Angew. Chem. 1993, 105, 92–95; Angew. Chem. Int. Ed.
Engl. 1993, 32, 69–72; d) P. N. W. Baxter, J.-M. Lehn, B. O. Kneisel,
G. Baum, D. Fenske, Chem. Eur. J. 1999, 5, 113–120; e) M. Kuil,
P. E. Goudriaan, P. W. N. M. van Leeuwen, J. N. H. Reek, Chem.
Commun. 2006, 4679–4681.
1
Lam, A. L. Rheingold, J. Am. Chem. Soc. 1999, 121, 6316–6317;
g) L. Zhu, E. V. Anslyn, Angew. Chem. 2006, 118, 1208–1215;
Angew. Chem. Int. Ed. 2006, 45, 1190–1196; h) L. Kovbasyuk, R.
Krämer, Chem. Rev. 2004, 104, 3161–3187.
[
8] CCDC-631442
(5·CH
2
Cl
2
·0.5pentane)
and
CCDC-631443
(
8a·CH Cl ) contain the supplementary crystallographic data for this
2
2
[15] L. J. Prins, D. N. Reinhoudt, P. Timmerman, Angew. Chem. 2001,
113, 2446–2492; Angew. Chem. Int. Ed. 2001, 40, 2382–2426.
[16] J. R. Farrell, C. A. Mirkin, I. A. Guzei, L. M. Liable-Sands, A. L.
Rheingold, Angew. Chem. 1998, 110, 484–487; Angew. Chem. Int.
Ed. 1998, 37, 465–467.
paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre at www.ccdc.cam.ac.uk/data_
request/cif.
[
9] P. E. Garrou, Chem. Rev. 1981, 81, 229–266.
[
[
10] a) M. S. Masar, M. V. Ovchinnikov, C. A. Mirkin, L. N. Zakharov,
A. L. Rheingold, Inorg. Chem. 2003, 42, 6851–6858; b) M. S. Masar,
C. A. Mirkin, C. L. Stern, L. N. Zakharov, A. L. Rheingold, Inorg.
Chem. 2004, 43, 4693–4701.
[17] F. M. Dixon, A. H. Eisenberg, J. R. Farrell, C. A. Mirkin, L. M.
Liable-Sands, A. L. Rheingold, Inorg. Chem. 2000, 39, 3432–3433.
[18] a) N. Margiotta, A. Habtemariam, P. J. Sadler, Angew. Chem. 1997,
109, 1233–1236; Angew. Chem. Int. Ed. Engl. 1997, 36, 1185–1187;
b) A. Habtemariam, J. A. Parkinson, N. Margiotta, T. W. Hambley,
S. Parsons, P. J. Sadler, J. Chem. Soc. Dalton Trans. 2001, 362–372;
c) A. Habtemariam, B. Watchman, B. S. Potter, R. Palmer, S. Par-
sons, A. Parkin, P. J. Sadler, J. Chem. Soc. Dalton Trans. 2001, 1306–
1318; d) A. Habtemariam, P. J. Sadler, Chem. Commun. 1996, 1785–
1786; e) K. Neplechova, J. Kasparkova, O. Vrana, O. Novakova, A.
Habtemariam, B. Watchman, P. J. Sadler, V. Brabec, Mol. Pharma-
col. 1999, 56, 20–30.
I
11] Heteroligated Rh -P,S-P,O complexes can be opened quantitatively
by nitrile groups and chloride (references [1–3,5,6f]), whereas ho-
I
moligated Rh -P,S-P,S complexes can be opened by the combination
of CO and chloride, but not by chloride anions alone (references
A
C
H
T
R
E
U
N
G
[6f,7a,c–e] and F. M. Dixon, A. H. Eisenberg, J. R. Farrell, C. A.
Mirkin, L. M. Liable-Sands, A. L. Rheingold, Inorg. Chem. 2000, 39,
432–3433).
3
[
[
12] a) A. Del Zotto, A. Mezzetti, P. Rigo, M. Bressan, F. Morandini, A.
Morvillo, Inorg. Chim. Acta 1989, 158, 151–158; b) A. R. Sanger,
Can. J. Chem. 1983, 61, 2214–2219; c) G. K. Anderson, R. Kumar,
Inorg. Chem. 1984, 23, 4064–4068.
[19] A. B. Pangborn, M. A. Giardello, R. H. Grubbs, R. K. Rosen, F. J.
Timmers, Organometallics 1996, 15, 1518–1520.
[20] D. L. DuBois, W. H. Myers, D. W. Meek, J. Chem. Soc. Dalton
Trans. 1975, 1011–1015.
II
13] Further examples of Pt -P,X (X=S, N, O) bidentate complexes:
a) T. B. Rauchfuss, F. T. Patino, D. M. Roundhill, Inorg. Chem. 1975,
[21] N. A. Yakelis, R. G. Bergman, Organometallics 2005, 24, 3579–3581.
[22] K. Noda, T. Sasaki, S. Iwatsuki, K. Kashiwabara, T. Suzuki, H. D.
Takagi, Inorg. Chim. Acta 2004, 357, 526–532.
1
4, 652–656; b) D. A. Wrobleski, T. B. Rauchfuss, J. Am. Chem.
Soc. 1982, 104, 2314–2316; c) G. K. Anderson, R. Kumar, J. Chem.
Res. Synop. 1988, 48; J. Chem. Res. Miniprint 1988, 0432–0443;
d) R. Romeo, L. M. Scolaro, M. R. Plutino, A. Romeo, F. Nicolo’,
A. Del Zotto, Eur. J. Inorg. Chem. 2002, 629–638; e) D.-R. Hou, T.-
Received: December 20, 2006
Published online: March 29, 2007
4534
www.chemeurj.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 4529 – 4534