Platinum(II) alkynyl complexes containing N- and S-propargylated ligands: Synthesis, structures and formation of PtII/AgI coordination compounds

Article abstract of DOI:10.1002/ejic.200700157

Alkylation of 2-hydroxypyridine, 2-pyridinethiol, 2-hydroxy-4- methylquinoline, phthalimide and pyrazole with propargyl bromide gave a series of alkynes in high yield. These alkynes were reacted with the chloroplatinum(II) compounds trans-[PtCl₂(PPh₃)₂] and cis-[PtCl₂(dppe)] to afford the respective trans- and cis-bis(alkynyl)platinum(II) complexes, which were characterised by spectroscopic analysis and by X-ray diffraction. The platinum(II) complexes containing the thiopyridyl- and pyrazolyl-substituted alkynes react with 1 or 2 equiv. of [Ag(NO₃)(PPh₃)] to give dimetallic Pt ^II/Ag^I complexes. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Full text of DOI:10.1002/ejic.200700157

FULL PAPER
DOI: 10.1002/ejic.200700157
Platinum(II) Alkynyl Complexes Containing N- and S-Propargylated Ligands:
Synthesis, Structures and Formation of PtII/AgI Coordination Compounds
Fabian Mohr,*[a,b] Aránzazu Mendía,*[b] and Mariano Laguna[c]
Keywords: Platinum / Alkynes / Silver / Dimetallic / Coordination complexes
Alkylation of 2-hydroxypyridine, 2-pyridinethiol, 2-hydroxy-
diffraction. The platinum(II) complexes containing the thio-
4-methylquinoline, phthalimide and pyrazole with propargyl pyridyl- and pyrazolyl-substituted alkynes react with 1 or
bromide gave a series of alkynes in high yield. These alkynes
were reacted with the chloroplatinum(II) compounds trans-
[PtCl2(PPh3)2] and cis-[PtCl2(dppe)] to afford the respective
trans- and cis-bis(alkynyl)platinum(II) complexes, which
were characterised by spectroscopic analysis and by X-ray
2 equiv. of [Ag(NO3)(PPh3)] to give dimetallic PtII/AgI com-
plexes.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
of mercury containing N-propargylated acridone are
strongly fluorescent and have been used as sensitive sensors
for the detection of organomercury compounds in water or
biological systems.[21,22] S-Propargylated compounds are
even less well-studied; their preparation and some organic
chemistry of only a small number of compounds has been
reported.[23,24] The only known example of a metal-contain-
ing derivative of an S-propargylated compound is the tin
complex of propargylthiotriazole, which was patented as a
fungicide.[25] In light of this lack of organometallic chemis-
try of N- and S-propargylated compounds, we wished to
pursue our interest in metal alkynyl complexes[26–28] and the
chemistry of platinum complexes with N,S-donor ligands[29]
by preparing and structurally characterising some plati-
num(II) alkynyl complexes of various N- and S-propar-
gylated compounds.
Introduction
Platinum(II) alkynyl complexes have been known for
many years, but since the discovery of their luminescence
and nonlinear optical (NLO) properties the field has experi-
enced rapid growth.[1–5] Numerous platinum(II) alkynyl
complexes have been synthesised by a variety of different
routes and some complexes have been structurally charac-
terised.[6,7] O-Propargylated compounds, in particular those
derived from bisphenols, have been extensively used as C-
donor ligands in the supramolecular assembly of gold(I)
polymers, macrocycles and catenanes;[8–13] however, no ex-
amples of their use as ligands in other transition-metal
complexes have been reported. Whereas the preparation,
some organic transformations and applications of selected
N-propargylated compounds have been published,[14–17] the
organometallic chemistry of these species acting as C-donor
ligands is a relatively unexplored field. Silver alkynyl com-
plexes of various propargylamines have been used as alkyne
transfer reagents in the synthesis of analogues of the opium
derivative cotarnine.[18] Similarly, gold(I) phosphane com-
plexes containing N-propargylphthalimide have been used
to transfer the Au-phosphane moiety to tetra- and penta-
iron clusters.[19] A series of alkynyl tin and silicon com-
plexes containing C-coordinated N-propargylpyrazole have
been prepared from the lithium salt.[20] Alkynyl complexes
Results and Discussion
The tautomerism of 2-hydroxypyridine has been studied
both experimentally and computationally in great detail by
various groups. Spectroscopic data indicates that the hy-
droxy form is the major tautomer in the gas phase.[30–32] In
the solid state, however, the formation of hydrogen bonded
dimers seems to favour the 2-pyridone tautomers.[33] Simi-
1
larly, we found, by H and 13C NMR spectroscopy in ace-
[a] Fachbereich C – Anorganische Chemie, Bergische Universität
Wuppertal,
tone, that 2-hydroxypyridine and 2-pyridinethiol exist exclu-
sively as the 2-pyridone and 2-pyridinethione tautomers,
respectively. Upon reaction of these compounds with pro-
pargyl bromide in the presence of base in acetone, these two
starting materials gave two different propargylated prod-
ucts. In the case of 2-hydroxypyridine, the N-propargylated
product (R1CH2CϵCH) was obtained, whereas from 2-pyr-
idinethiol the S-propargylated compound (R2CH2CϵCH)
42119 Wuppertal, Germany
Fax: +49-202-439-3053
E-mail: fmohr@uni-wuppertal.de
[b] Departamento de Química, Facultad de Ciencias, Universidad
de Burgos,
09001 Burgos, Spain
[c] Departamento de Química Inorgánica, Instituto de Ciencia de
Materiales de Aragón, Universidad de Zaragoza-C.S.I.C,
50009 Zaragoza, Spain
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F. Mohr, A. Mendía, M. Laguna
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was isolated (Scheme 1). We calculated the relative energies
of each of the four possible propargylated isomers using
density functional theory (DFT) methods. In the case of 2-
hydroxypyridine, the N-propargylated compound is
8.8 kcal/mol more stable than the O-propargylated tauto-
mer. In contrast, for 2-pyridinethione the S-propargylated
species is 2.5 kcal/mol more stable than the N-propar-
gylated tautomer (Figure 1). These computational results
are in agreement with our, and previously reported, experi-
mental observations.[16,23] In addition to the two alkynes
discussed above, the previously reported N-propargylated
compounds derived from 2-hydroxy-4-methylquinoline,[14]
phthalimide[17]
and
=
pyrazole[15]
3–5) were prepared similarly
(designated
as
RnCH2CϵCH;
n
(Scheme 2). In our hands, the procedure using K2CO3 in
acetone was much simpler in terms of work up (filtration
and evaporation of acetone) than the previously described
methods. N-Alkylation in R1CH2CCH and R3CH2CCH is
evident from their NMR- (particularly 13C) and IR spectra.
The methylene carbon signal in the 13C NMR spectra of
these two compounds is shifted by ca. 17 ppm downfield
relative to that of the S-propargyl derivative R2CH2CCH.
Similarly, although less pronounced, the NCH2 proton sig-
nals of R1CH2CCH and R3CH2CCH are shifted ca. 2 ppm
downfield relative to the SCH2 resonance of R2CH2CCH,
which is consistent with the difference in electronegativity
of sulfur and nitrogen. Further evidence for N-propar-
gylation is seen in the IR spectra of R1CH2CCH and
R3CH2CCH, which show strong C=O absorption bands.
Figure 1. DFT optimised structures of the propargylated tautomers
of 2-propargyloxypyridine and 2-propargylthiopyridine showing
the energy differences between the two forms.
Scheme 2.
Scheme 1.
NMR spectrum of complex 2 in CDCl3 at room tempera-
ture shows only one set of signals (doublets and triplets) for
the R substituents, which indicates that rotation about the
C–N bond is rapid in solution on the NMR timescale. Low-
ering the temperature to –80 °C has no effect on the appear-
These alkynes react with the dichloroplatinum(II) com-
plexes trans-[PtCl2(PPh3)2] and cis-[PtCl2(dppe)] [dppe =
Ph2P(CH2)2PPh2] in the presence of Et2NH and a catalytic
amount of [CuI][34–36] to afford the air- and water-stable
alkynyl platinum(II) complexes trans-[Pt(CϵCCH2R)2-
(PPh3)2] (R1 = 1, R2 = 3, R3 = 5, R4 = 7, R5 = 9) and cis-
[Pt(CϵCCH2R)2(dppe)] (R1 = 2, R2 = 4, R3 = 6, R4 = 8,
R5 = 10), respectively, in high yields (Scheme 3). Complexes
1
ance of the H NMR spectrum, which suggests that any of
the possible conformations rapidly interconvert in solution.
In the solid-state structures, however, the endo–exo configu-
ration is found. It is worth mentioning here that some of
1
1–10 were characterised spectroscopically including H and
31P{1H} NMR spectroscopy, mass spectrometry, IR spec-
troscopy and elemental analysis. The 31P{1H} NMR spec-
tra of complexes 1–10 show sharp singlet resonances with
Pt satellites having JPt–P values of ca. 2600 and 2300 Hz for
the trans and cis isomers, respectively, which indicates the
presence of a single species in solution. In principle, there
are two possible configurations of the R groups for all but
complexes 7 and 8, namely the exo–exo and endo–exo con-
figurations as illustrated for complex 2 in Figure 2. The H substituents in complex 2.
Figure 2. Illustration of the isomeric configurations of the pyridone
1
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Platinum(II) Alkynyl Complexes Containing N- and S-Propargylated Ligands
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Scheme 3.
these complexes hold water tenaciously, as is evident from in other trans-bis(triphenylphosphane)platinum(II) ace-
1
H2O signals in the H NMR spectra and confirmed by ele- tylide complexes such as trans-[Pt(CϵCC6H4-4-NH2)2-
mental analysis. Even prolonged drying under high vacuum (PPh3)2] [Pt–P = 2.310(1), Pt–C = 2.005(4) and CϵC =
does not seem to remove this solvated water. The LSIMS 1.206(6) Å][37]
or
trans-[Pt{CϵCC6H4-4-SC(O)Me}2-
mass spectra of all ten complexes show molecular ion peaks (PPh3)2] [Pt–P = 2.3177(15), Pt–C = 2.027(6) and CϵC =
whose isotopic distributions match the expected patterns. 1.179(9) Å].[38] A unique feature of the solid-state structure
The solid-state structures of the complexes trans- of complex 1 is the presence of a hydrogen-bonding interac-
[Pt(CϵCCH2R1)2(PPh3)2] (1), cis-[Pt(CϵCCH2R1)2(dppe)] tion between the alkyne ligand carbonyl group oxygen atom
(2), trans-[Pt(CϵCCH2R3)2(PPh3)2] (5), trans-[Pt(Cϵ and a meta hydrogen of one of the Ph3P phenyl rings with
CCH2R5)2(PPh3)2] (9) and cis-[Pt(CϵCCH2R5)2(dppe)] a H···O=C distance of ca. 2.7 Å, a distance typically found
(10) were determined by single-crystal X-ray diffraction. in weak hydrogen-bonding interactions.[39] The molecular
The molecular structure of 1 (Figure 3) consists of a plati- structure of cis complexes 2 (Figure 4) and 10 (Figure 5)
num atom coordinated by two triphenylphosphane ligands consist of a distorted [P–Pt–C angle ca. 173°] square planar
and two acetylide molecules in a trans geometry. The coor- platinum centre to which one dppe unit and two C-bonded
dination about the platinum atom is square planar, and the alkyne molecules are coordinated in a mutually cis arrange-
angle subtended at the Pt centre is 92.90(14)°. The Pt–C, ment. The Pt–C and Pt–P bond lengths (see Table 1) are
Pt–P and CϵC bond lengths [1.998(5), 2.3163(12) and similar to those of the trans derivative (see above) and also
1.201(7) Å, respectively] are very similar to those observed similar to other cis platinum alkynyl complexes including
cis-[Pt(CϵCH)2(dppe)] [Pt–C = 2.025(5), Pt–P = 2.2851(12)
and CϵC = 1.164(8) Å][40] and cis-[Pt(CϵCCϵCH)2(dppe)]
[Pt–C = 2.20(1), Pt–P = 2.269(3) and CϵC = 1.218(6) Å].[41]
Figure 3. Molecular structure of trans-[Pt(CϵCCH2R1)2(PPh3)2]
(1). Thermal ellipsoids show 50% probability levels. Hydrogen
atoms (except those involved in H-bonding interactions) omitted
for clarity.
Figure 4. Molecular structure of cis-[Pt(CϵCCH2R1)2(dppe)] (2).
Thermal ellipsoids show 50% probability levels. Hydrogen atoms
have been omitted for clarity and only the ipso carbon atoms of
the phenyl groups are shown.
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Table 1. Selected structural parameters for complexes 1, 2, 5, 9 and 10.
1
2
5
9
10
P–Pt–C angle [°]
Pt–C [Å]
Pt–P [Å]
92.90(14)
1.998(5)
2.3163(14)
1.201(7)
173.96(14)
2.018(5)
2.2823(13)
1.168(7)
88.39(12)
2.013(4)
2.2872(13)
1.190(6)
93.12(17)
2.006(6)
2.2896(15)
1.191(9)
173.64(18), 174.7(2)
2.046(8), 2.060(7)
2.2802(18), 2.2807(17)
1.135(10), 1.114(9)
CϵC [Å]
As a consequence of the trans effect, the CϵC bond lengths
in cis complexes 2 [1.1687(7) Å] and 10 [1.135(10) and
1.114(9) Å] are slightly shorter than those of the trans com-
plexes. The other two trans complexes 5 (Figure 6) and 9
(Figure 7) are structurally very similar to complex 1, al-
though with slightly longer Pt–P distances. For comparison,
important structural data for the trans and cis complexes is
summarised in Table 1.
The platinum(II) complexes containing the alkynes
R2CH2CϵCH and R5CH2CϵCH (3, 4, 9 and 10) possess
an uncoordinated nitrogen atom which could allow theses
compounds to act as organometallic ligands to give hetero-
dimetallic species upon coordination to other metals. In-
deed, trans complexes 3 and 9 react with 2 equiv. of [Ag-
Figure 5. Molecular structure of cis-[Pt(CϵCCH2R5)2(dppe)] (10).
Thermal ellipsoids show 50% probability levels. Hydrogen atoms
have been omitted for clarity and only the ipso carbon atoms of
the phenyl groups are shown.
Figure 7. Molecular structure of trans-[Pt(CϵCCH2R5)2(PPh3)2]·
2CHCl3 (9). Thermal ellipsoids show 50% probability levels. Hy-
drogen atoms and CHCl3 of solvation have been omitted for clarity.
Figure 6. Molecular structure of trans-[Pt(CϵCCH2R3)2(PPh3)2]
(5). Thermal ellipsoids show 50% probability levels. Hydrogen
atoms have been omitted for clarity.
Scheme 4.
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Platinum(II) Alkynyl Complexes Containing N- and S-Propargylated Ligands
FULL PAPER
(NO3)(PPh3)] to give the cationic platinum(II)/silver(I) com- (dppe)(AgPPh3)2](NO3)2 (n = 2, 15; n = 5, 16), respectively
plexes trans-[Pt(CϵCCH2Rn)2(PPh3)2(AgPPh3)2](NO3)2 (n (Scheme 5). Complexes 11–16 were characterised spectro-
= 2, 11; n = 5, 12) (Scheme 4). The reaction of complexes scopically; attempts to grow X-ray quality crystals so far
3 and 9 with only 1 equiv. of [Ag(NO3)PPh3] gave mixtures have failed as the stability of these compounds in solution
of products which were not analysed further. NMR spectro- is limited. The 31P{1H} NMR spectra of complexes 11–16
scopic data of these mixtures seems to indicate the presence consist of a singlet resonance with 195Pt satellites due to the
of both starting material (i.e. complex 3 or 9) as well as Pt–phosphane unit and, at room temperature, a very broad
dimetallic complexes 11 or 13. Clearly, the trans geometry (almost invisible) signal for the Ag–PPh3 moiety. At –80 °C,
does not allow the system to bend in such a manner that a this broad signal is resolved into a pair of doublets arising
macrocyclic complex incorporating only one silver ion can from coupling of the phosphorus nucleus to both the 109Ag
be formed. Similarly, cis complexes 4 and 10 react with and 107Ag isotopomers (Figure 8). The 195Pt–31P coupling
either 1 or 2 equiv. of the silver compound to give the heter- constants of dimetallic Pt/Ag macrocycles 13–14 are ca.
odimetallic
compounds
cis-[Pt(CϵCCH2Rn)2(dppe)- 100 Hz larger than those of the “free-ligand” Pt complexes,
(AgPPh3)]NO3 (n = 2, 13; n = 5, 14) or cis-[Pt(CϵCCH2Rn)2- consistent with a change of angle about the platinum centre
Scheme 5.
Figure 8. 31P{1H} NMR (162 MHz) spectrum of cis-[Pt(CϵCCH2R5)2(dppe)(AgPPh3)]NO3 (14) in CD2Cl2 at –80 °C.
Eur. J. Inorg. Chem. 2007, 3115–3123
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F. Mohr, A. Mendía, M. Laguna
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Et2NH (5 mL) and EtOH (5 mL) was heated at reflux for ca. 1 h.
The solid products were isolated by filtration, washed with H2O,
EtOH and Et2O and dried in vacuo.
consistent with the expected “tweezer-motion” of the al-
kyne substituents to coordinate to the silver atom. The pos-
sibility that the silver ions are coordinated to the triple
bond rather than the N atom can be disproved from the IR
data; the CϵC stretching frequency of both the “free” and
“coordinated” Pt complexes are almost identical. Com-
plexes 11–16 represent examples of complexes in which an
organometallic compound acts as metalloligand. Some ex-
amples of such metalloligands include the alkynyl gold(I)
macrocycles and [2]catenanes containing pyridyl and bipyr-
idyl backbones that are coordinated to a PtIV centre,[42] the
pyrazolyl- and pyridyl-substituted ferrocenes that are N-co-
ordinated to various Au and Ag species,[43,44] the alkynyl-
functionalised bis(pyrazolyl)methane derivatives containing
Au/Pd and Pt/Pd[45] and various supramolecular assemblies
N-Propargyl-2-pyridone (R1CH2CϵCH): Yield: 2.10 g (75%), dark
1
orange oil. H NMR (400 MHz, CDCl3): δ = 2.27 (t, J = 2.5 Hz,
1 H, ϵCH), 4.74 (d, J = 2.5 Hz, 2 H, NCH2), 6.22 (dt, J = 6.6,
1.3 Hz, 1 H, H5), 6.55 (dd, J = 9.1, 0.8 Hz, 2 H, H3), 7.33 (m, 1
H, H4), 6.61 (ddd, J = 6.8, 2.0, 0.5 Hz, 1 H, H6) ppm. 13C NMR
(100 MHz, CDCl3): δ = 37.45 (NCH2), 75.21 (CϵCH), 76.73
(CϵCH), 106.24 (C5), 120.32 (C3), 135.74 (C4), 139.68 (C6),
161.80 (C2) ppm.
trans-[Pt(CϵCR1)2(PPh3)2] (1): Yield: 0.258 g (83%), pale brown
1
solid. H NMR (400 MHz, CDCl3): δ = 4.01 (t, J = 1.8 Hz, 4 H,
NCH2), 5.61 (dt, J = 6.8, 1.5 Hz, 2 H, H5), 6.33 (ddd, J = 8.8, 2.0,
0.5 Hz, 2 H, H3), 6.88 (dd, J = 6.8, 2.0 Hz, 2 H, H6), 7.12 (dt, J =
6.6, 2.0 Hz, 2 H, H4), 7.31–7.44 (m, 18 H, p-, m-Ph3P), 7.70–7.77
(m, 12 H, o-Ph3P) ppm. 31P{1H} NMR (162 MHz, CDCl3): δ =
based on the M–CϵC (4-C6H4N) (M
= Pt, Ru)
unit.[40,46–48]
18.89 (JPt,P = 2619 Hz) ppm. IR (KBr disk): ν = 2135 (CϵC), 1657
˜
(C=O) cm–1. FAB MS: m/z = 984 [M + H]+. C52H42N2O2P2Pt
(983.9): calcd. C 63.48, H 4.30, N 2.85; found C 63.03, H 4.32, N
3.02. X-ray quality crystals were grown by slow diffusion of Et2O
into a CH2Cl2 solution of the complex.
Conclusion
We have shown that various N- and S-propargylated
compounds form platinum(II) alkynyl complexes in high
yields and that these compounds can act as N-donor li-
gands to AgI ions. In the case of cis-Pt complexes, dimet-
allic macrocycles are formed. Further work on the use of
these organometallic ligands is currently in progress.
cis-[Pt(CϵCR1)2(dppe)] (2): Yield: 0.242 g (75%), colourless solid.
1H NMR (400 MHz, CDCl3): δ = 2.30–2.48 (m, 4 H, PCH2CH2P),
4.76 (t, J = 6.6 Hz, 4 H, NCH2), 5.81 (dt, J = 6.6, 1.2 Hz, 2 H,
H5), 6.42 (d, J = 8.6 Hz, 2 H, H3), 7.19 (m, 2 H, H4), 7.38–7.51
(m, 12 H, p-, m-Ph2P), 7.80–7.88 (m, 8 H, o-Ph2P), 7.89 (dd, J =
7.0, 1.9 Hz, 2 H, H6) ppm. 31P{1H} NMR (162 MHz, CDCl3): δ =
43.23 (JPt,P = 2316 Hz) ppm. IR (KBr disk): ν = 2137 (CϵC), 1652
˜
(C=O) cm–1. FAB MS: m/z = 858 [M + H]+. C42H36N2O2P2Pt
(857.8): calcd. C 58.81, H 4.23, N 3.27; found C 58.88, H 4.24, N
3.35. X-ray quality crystals were grown by slow diffusion of Et2O
into a CH2Cl2 solution of the complex.
Experimental Section
General: NMR spectra were recorded with a 400 MHz Varian In-
ova spectrometer. Chemical shifts are quoted relative to external
TMS (1H, 13C) or 85% H3PO4 (31P). LSIMS mass spectra were
measured with a Micromass Autospec spectrometer in positive ion
mode by using NBA as matrix. IR spectra were recorded with a
Nicolet Impact 410 instrument. Elemental analyses were obtained
in-house by using a LECO CHNS-932 microanalyser. N-Propargyl-
2-pyridone, 2-propargylthiopyridine, N-propargyl-4-methyl-2-quin-
olidone, N-propargylphthalimide and 2-propargylpyrazole were
prepared by modified literature procedures.[14–17,23] Spectroscopic
data of these alkynes is given here since only very few details have
been previously reported. The PtII phosphane complexes trans-
[PtCl2(PPh3)2] and cis-[PtCl2(dppe)] were prepared by the reaction
of [PtCl2(NCMe)2] with appropriate amounts of the phosphanes.
The silver(I) complex [Ag(NO3)(PPh3)] was prepared by a literature
procedure.[49] All other reagents and solvents were obtained com-
mercially and used as received. DFT calculations were carried out
with the PRIRODA software package incorporating relativistic Ste-
vens, Basch, Krauss basis sets.[50,51] Geometries were fully op-
timised and the located minima were confirmed by the absence of
imaginary frequencies.
2-Propargylthiopyridine (R2CH2CϵCH): Yield: 2.01 g (75%), yel-
low oil. 1H NMR (400 MHz, CDCl3): δ = 2.18 (t, J = 2.7 Hz, 1 H,
ϵCH), 3.94 (d, J = 2.7 Hz, 2 H, SCH2), 7.00 (ddd, J = 7.4, 4.7,
0.8 Hz, 1 H, H5), 7.20 (d, J = 8.2 Hz, 1 H, H3), 7.49 (ddd, J = 9.4,
7.4, 1.9 Hz, 1 H, H4), 8.44 (ddd, J = 5.1, 1.9, 1.1 Hz, 1 H, H6)
ppm. 13C NMR (100 MHz, CDCl3): δ = 18.11 (SCH2), 70.40
(CϵCH), 80.01 (CϵCH), 119.80 (C5), 121.93 (C3), 136.05 (C4),
149.44 (C6), 156.96 (C26) ppm. Caution: On several occasions this
alkyne decomposed spontaneously producing large amounts of ex-
tremely malodorous fumes and black soot.
trans-[Pt(CϵCR2)2(PPh3)2] (3): Yield: 0.260 g (81%), pale yellow
1
solid. H NMR (400 MHz, CDCl3): δ = 3.19 (s, 4 H, SCH2), 6.74
(d, J = 8.6 Hz, 2 H, H3), 6.80 (t, J = 5.8 Hz, 2 H, H5), 7.11 (dt, J
= 7.8, 1.6 Hz, 2 H, H4), 7.28–7.40 (m, 18 H, p-, m-Ph3P), 7.66–7.77
(m, 12 H, o-Ph3P), 8.25 (d, J = 4.7 Hz, 2 H, H6) ppm. 31P{1H}
NMR (162 MHz, CDCl3): δ = 19.47 (JPt,P = 2662 Hz) ppm. IR
(KBr disk): ν = 2125 (CϵC) cm–1. FAB MS: m/z = 1016 [M +
˜
H]+. C52H42N2O2P2PtS2·H2O (1033.2): calcd. C 60.39, H 4.29, N
2.71; found C 59.94, H 4.28, N 3.02.
Preparation of the Alkynes: A mixture of the appropriate NH or SH
derivatives (2-pyridone, 2-hydroxy-4-methylquinoline, phthalimide
and 2-pyridinethiol), K2CO3 (excess) and propargyl bromide
(1.6 equiv.) was heated at reflux in acetone for ca. 8 h. The cooled
mixture was filtered, and the filtrate was evaporated to dryness.
The resulting crude products were purified by chromatography on
silica gel using CH2Cl2 as eluent.
cis-[Pt(CϵCR2)2(dppe)] (4): Yield: 0.134 g (40%), pale yellow solid.
1H NMR (400 MHz, CDCl3): δ = 2.31 (m, 4 H, PCH2CH2P), 3.99
(t, J = 7.0 Hz, 4 H, SCH2), 6.75 (dt, J = 5.1, 1.6 Hz, 2 H, H5),
7.06–7.15 (m, 4 H, H3, H4), 7.28–7.41 (m, 12 H, p-, m-Ph2P), 7.79–
7.89 (m, 8 H, o-Ph2P), 8.24 (ddd, J = 5.1, 2.7, 12 Hz, 2 H, H6)
ppm. 31P{1H} NMR (162 MHz, CDCl3): δ = 41.43 (JPt,P
=
2305 Hz) ppm. IR (KBr disk): ν = 2128 (CϵC) cm–1. FAB MS:
˜
Preparation of the [Pt(CϵCR)2(P)] Complexes: A mixture of the
m/z = 890 [M + H]+. C42H36N2O2P2PtS2·1/2H2O (898.1): calcd. C
alkyne (0.228 mmol), [PtCl2(P)] (0.098 mmol), [CuI] (5 mg) in
56.12, H 4.15 N 3.12; found C 55.83, H 4.11, N 3.34.
3120
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 3115–3123

Platinum(II) Alkynyl Complexes Containing N- and S-Propargylated Ligands
FULL PAPER
N-Propargyl-4-methyl-2-quinolidone (R3CH2CϵCH): Yield: 1.36 g
(55%), brown solid. H NMR (400 MHz, CDCl3): δ = 2.33 (t, J =
ppm. 31P{1H} NMR (162 MHz, CDCl3): δ = 20.12 (JPt,P
=
1
2641 Hz) ppm. IR (KBr disk): ν = 2138 (CϵC) cm–1. FAB MS:
˜
2.6 Hz, 1 H, ϵCH), 2.47 (s, 3 H, Me), 5.11 (d, J = 2.6 Hz, 2 H,
m/z = 853 [M + H]+. C48H40N4P2Pt (929.9): calcd. C 61.99, H 4.34,
NCH2), 6.60 (s, 1 H, H3), 7.29 (t, J = 7.7 Hz, 1 H, H6), 7.53 (d, J N 6.03; found C 61.56, H 4.35, N 5.82. X-ray quality crystals were
= 8.1 Hz, 1 H, H5), 7.61 (dt, J = 7.3, 1.3 Hz, 1 H, H7), 7.72 (dd, J
= 8.1, 1.3 Hz, 1 H, H8) ppm. 13C NMR (100 MHz, CDCl3): δ =
19.01 (Me), 31.28 (NCH2), 72.22 (CϵCH), 78.16 (CϵCH), 114.86
(C3), 120.68 (C8), 121.63 (C10), 122.29 (C6), 125.33 (C5), 130.53
(C7), 138.35 (C9), 147.23 (C4), 161.02 (C2) ppm.
grown by slow diffusion of Et2O into a CHCl3 solution of the com-
plex.
cis-[Pt(CϵCR5)2(dppe)] (10): Yield: 0.137 g (71%), tan solid. 1H
NMR (400 MHz, CDCl3): δ = 2.30–2.48 (m, 4 H, PCH2CH2P),
5.01 (t, J = 7.0 Hz, 4 H, NCH2), 5.90 (br. s, J = 1.2 Hz, 2 H, Pz-
1
trans-[Pt(CϵCR3)2(PPh3)2] (5): Yield: 0.225 g (64%), tan solid. H H4), 7.22 (br. s, 2 H, Pz-H5), 7.34 (br. s, 2 H, Pz-H3), 7.36–7.50 (m,
NMR (400 MHz, CDCl3): δ = 2.40 (s, 6 H, Me), 4.36 (s, 4 H,
12 H, p-, m-Ph2P), 7.79–7.90 (m, 8 H, o-Ph2P) ppm. 31P{1H} NMR
NCH2), 6.40 (s, 2 H, H3), 6.82 (d, J = 8.2 Hz, 2 H, H5), 6.94 (t, J (162 MHz, CDCl3): δ = 43.00 (JPt,P = 2315 Hz) ppm. IR (KBr
= 8.2 Hz, 2 H, H6), 7.02 (t, J = 7.4 Hz, 2 H, H7), 7.13–7.24 (m, 18
H, p-, m-Ph3P), 7.51 (dd, J = 7.8, 0.8 Hz, 2 H, H8), 7.54–7.62 (m,
12 H, o-Ph3P) ppm. 31P{1H} NMR (162 MHz, CDCl3): δ = 19.79
disk): ν = 2140 (CϵC) cm–1. FAB MS: m/z = 804 [M + H]+.
˜
C38H34N4P2Pt (803.7): calcd. C 56.79, H 4.26, N 6.97; found C
56.63, H 4.27, N 7.04.
(JPt,P = 2663 Hz) ppm. IR (KBr disk): ν = 2128 (CϵC), 1652
˜
Preparation of Heterodimetallic PtII/AgI Complexes: To a solution
of the Pt complex in CH2Cl2 (7 mL) was added either 1 or 2 equiv.
of solid [Ag(NO3)(PPh3)]. After stirring for ca. 1 h, the solution
was passed through Celite and concentrated in vacuo. Addition of
Et2O precipitated the complexes, which were isolated by filtration
(C=O) cm–1. FAB MS: m/z
=
1112 [M
+
H]+.
C62H50N2O2P2Pt·2H2O (1147.3): calcd. C 64.84, H 4.74, N 2.44;
found C 64.56, H 4.70, N 2.84.
cis-[Pt(CϵCR3)2(dppe)] (6): Yield: 0.245 g (66%), tan solid. 1H
NMR (400 MHz, CDCl3): δ = 2.23 (m, 4 H, PCH2CH2P), 2.38 (s, and dried in air.
6 H, Me), 5.15 (s, 4 H, NCH2), 5), 6.43 (s, 2 H, H3), 7.05 (t, J =
trans-[Pt(CϵCR2)2(PPh3)2(AgPPh3)2](NO3)2 (11): Yield: 0.038 g
7.4 Hz, 2 H, H7), 7.10–7.22 (m, 10 H, m-Ph2P, H6), 7.23–7.32 (m,
4 H, p-Ph2P), 7.52 (d, J = 7.8 Hz, 2 H, H8), 7.57–7.72 (m, 10 H,
o-Ph2P, H5) ppm. 31P{1H} NMR (162 MHz, CDCl3): δ = 41.62
(81%), ivory solid. 1H NMR (400 MHz, CD2Cl2): δ = 3.21 (s, 4 H,
SCH2), 6.81–6.99 (m, 4 H, H3, H5), 7.23–7.76 (m, 62 H, Ph3P, H4),
8.05 (m, 2 H, H6) ppm. 31P{1H} NMR (162 MHz, CD2Cl2,
(JPt,P = 2295 Hz) ppm. IR (KBr disk): ν = 2138 (CϵC), 1650
˜
107Ag,P
–80 °C): δ = 17.67 (JPt,P = 2524 Hz), 11.07 (d, J109Ag,P = 538, J
(C=O) cm–1. FAB MS: m/z = 986 [M + H]+. C52H44N2O2P2Pt·H2O
(1003.3): calcd. C 62.20, H 4.62, N 2.79; found C 61.98, H 4.45, N
3.04.
= 465 Hz) ppm. IR (KBr disk): ν = 2126, 2054 (CϵC), 1398
˜
(N=O), 1294 (NO2) cm–1. FAB MS: m/z = 1385 [M – AgPPh3]+,
1123 [M – Ag – 2Ph3P]+. C88H72Ag2N4O6P4PtS2·CH2Cl2 (1965.3):
calcd. C 54.39, H 3.80, N 2.85; found C 53.99, H 3.95, N 2.93.
N-Propargylphthalimide (R4CH2CϵCH): Yield: 1.29 g (65%), pale
yellow oil. 1H NMR (400 MHz, CDCl3): δ = 2.22 (t, J = 2.3 Hz, 1
H, ϵCH), 4.44 (d, J = 2.3 Hz, 2 H, NCH2), 7.73 (m, 2 H, arom),
7.87 (m, 2 H, arom) ppm. 13C NMR (100 MHz, CDCl3): δ = 26.93
(NCH2), 71.46 (CϵCH), 77.12 (CϵCH), 123.52, 131.90, 134.17
(arom) ppm.
trans-[Pt(CϵCR5)2(PPh3)2(AgPPh3)2](NO3)2 (12): Yield: 0.040 g
(78%), ivory solid. 1H NMR (400 MHz, CD2Cl2): δ = 4.30 (s, 4 H,
NCH2), 6.10 (t, J = 2.2 Hz, 2 H, Pz-H4), 6.97 (d, J = 1.5 Hz, 2 H,
Pz), 7.14 (d, J = 1.5 Hz, 2 H, Pz), 7.22–7.72 (m, 60 H, Ph3P) ppm.
31P{1H} NMR (162 MHz, CD2Cl2, –80 °C): δ = 29.88 (JPt,P
=
trans-[Pt(CϵCR4)2(PPh3)2] (7): Yield: 0.286 g (82%), ivory solid.
1H NMR (400 MHz, CDCl3): δ = 3.75 (s, 4 H, NCH2), 7.11–7.31
(m, 18 H, p-, m-Ph3P), 7.60–7.76 (m, 20 H, o-Ph3P, arom) ppm.
2520 Hz), 11.18 (d, J109Ag,P = 540, J107Ag,P = 463 Hz) ppm. IR (KBr
disk): ν = 2138, 2083 (CϵC), 1384 (N=O), 1297 (NO ) cm–1.
˜
2
C84H70Ag2N6O6P4Pt·1/2CH2Cl2 (1836.7): calcd C 55.26, H 3.90, N
31P{1H} NMR (162 MHz, CDCl3): δ = 19.56 (JPt,P = 2646 Hz) 4.58; found C 55.39, H 4.12, N 4.62.
ppm. IR (KBr disk): ν = 1231 (CϵC), 1713 (C=O) cm–1. FAB MS:
˜
cis-[Pt(CϵCR2)2(dppe)(AgPPh3)]NO3 (13): Yield: 0.035 g (83%),
m/z = 1088 [M + H]+. C58H42N2O4P2Pt·H2O (1105.2): calcd. C
tan solid. 1H NMR (400 MHz, CD2Cl2): δ = 2.39–2.57 (m, 4 H,
PCH2CH2P), 3.77 (s, 4 H, SCH2), 6.90 (t, J = 4.4 Hz, 2 H, Py),
6.97 (d, J = 7.7 Hz, 4 H, Py), 7.27–7.79 (m, 37 H, Ph2P, Ph3P, Py),
8.31 (d, J = 4.0 Hz, 2 H, H6) ppm. 31P{1H} NMR (162 MHz,
62.97, H 4.01, N 2.53; found C 62.98, H 4.17, N 2.85.
cis-[Pt(CϵCR4)2(dppe)] (8): Yield: 0.148 g (41%), colourless solid.
1H NMR (400 MHz, CDCl3): δ = 2.28 (m, 4 H, PCH2CH2P), 4.50
(t, J = 7.0 Hz, 4 H, NCH2), 7.14–7.25 (m, 12 H, p-, m-Ph2P), 7.54–
7.80 (m, 16 H, o-Ph3P, arom) ppm. 31P{1H} NMR (162 MHz,
109Ag,P
CD2Cl2, –80 °C): δ = 40.13 (JPt,P = 2433 Hz), 11.10 (d, J
=
107Ag,P
541, J
= 469 Hz) ppm. IR (KBr disk): ν = 2098 (CϵC), 1384
˜
CDCl3): δ = 42.01 (JPt,P = 2289 Hz) ppm. IR (KBr disk): ν = 2140 (N=O) cm–1. FAB MS: m/z
=
997 [M
–
Ph3P]+.
˜
(CϵC), 1709 (C=O) cm–1. FAB MS: m/z = 962 [M + H]+.
C49H39N2O4P2Pt·H2O (994.2): calcd. C 59.14, H 4.16, N 2.82;
found C 59.10, H 4.17, N 3.06.
C60H51AgN3O3P3PtS2·CH2Cl2 (1407.0) C 52.07, H 3.80 N 2.98;
found C 52.06, H 4.00, N 3.09.
cis-[Pt(CϵCR5)2(dppe)(AgPPh3)]NO3 (14): Yield: 0.026 g (78%),
2-Propargylpyrazole (R5CH2CϵCH): Yield: 1.31 g (42%), pale yel-
ivory solid. H NMR (400 MHz, CD2Cl2): δ = 2.41–2.60 (m, 4 H,
1
low oil. 1H NMR (400 MHz, CDCl3): δ = 2.49 (t, J = 2.7 Hz, 1 H, PCH2CH2P), 4.76 (s, 4 H, NCH2), 6.21 (t, J = 2.2 Hz, 2 H, Pz-
ϵCH), 4.94 (d, J = 2.3 Hz, 2 H, NCH2), 6.29 (t, J = 2.3 Hz, 1 H, H4), 7.12–7.83 (m, 39 H, Ph2P, Ph3P, Pz) ppm. 31P{1H} NMR
Pz-H4), 7.53 (d, J = 1.6 Hz, 1 H, Pz-H5), 7.59 (d, J = 2.3 Hz, 1 H,
Pz-H3) ppm. 13C NMR (100 MHz, CDCl3): δ = 41.65 (NCH2),
(162 MHz, CD2Cl2, –80 °C): δ = 41.29 (JPt,P = 2400 Hz), 6.97 (d,
109Ag,P
107Ag,P
J
= 653, J = 566 Hz) ppm. IR (KBr disk): ν = 2120
˜
74.83 (CϵCH), 76.98 (CϵCH), 106.39 (C4), 129.02 (C5), 140.23 (CϵC), 1336 (N=O) cm–1. C56H49AgN5O3P3Pt·CH2Cl2 (1320.8):
(C3) ppm.
calcd. C 51.83, H 3.89, N 5.30; found C 51.71, H 4.04, N 4.94.
trans-[Pt(CϵCR5)2(PPh3)2] (9): Yield: 0.312 g (83%), colourless so-
cis-[Pt(CϵCR2)2(dppe)(AgPPh3)2](NO3)2 (15): Yield: 0.041 g
1
lid. 1H NMR (400 MHz, CDCl3): δ = 4.22 (s, 4 H, NCH2), 5.48 (76%), tan solid. H NMR (400 MHz, CD2Cl2): δ = 2.40–2.59 (m,
(br. s, 2 H, Pz-H4), 6.54 (br. s, 2 H, Pz-H5), 7.27 (br. s, 2 H, Pz-
H3), 7.31–7.44 (m, 18 H, p-, m-Ph3P), 7.70–7.80 (m, 12 H, o-Ph3P) 2 H, Py), 7.28–7.76 (m, 52 H, Ph2P, Ph3P, Py), 8.10 (m, 2 H, H6)
4 H, PCH2CH2P), 3.74 (s, 4 H, SCH2), 6.81 (m, 2 H, Py), 7.07 (m,
Eur. J. Inorg. Chem. 2007, 3115–3123
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3121

F. Mohr, A. Mendía, M. Laguna
FULL PAPER
Table 2. Crystal data and refinement details for complexes 1, 2, 5, 9 and 10.
1
2
5
9
10
Empirical formula
Formula mass
Crystal system
Space group
a [Å]
b [Å]
c [Å]
C52H40N2O2P2Pt
981.89
C42H36N2O2P2Pt
857.76
monoclinic
C2/c
14.973(6)
18.366(7)
12.819(5)
90
104.474(8)
90
C62H50N2O2P2Pt
1112.07
C50H42N4Cl6P2Pt
1168.61
C38H34N4P2Pt
803.72
orthorhombic
Pbca
17.6036(17)
13.4388(13)
28.890(3)
90
triclinic
triclinic
triclinic
¯
¯
¯
P1
P1
P1
9.0466(6)
10.5428(6)
11.3405(7)
96.486(1)
106.646(1)
90.901(1)
1028.34(19)
1
9.783(4)
10.836(5)
13.091(5)
104.27(4)
104.14(3)
108.94(3)
1189.9(9)
1
8.277(2)
12.177(3)
12.714(3)
73.332(5)
79.273(6)
82.584(5)
1202.2(5)
1
α [°]
β [°]
90
90
γ [°]
V [Å3]
3413(2)
4
1.669
6834.5(11)
1
1.562
Z
ρcalcd. [Mg/m3]
1.586
3.535
1.552
3.065
1.614
3.358
µ [mm–1]
4.245
4.232
F(000)
490
1.89–28.83
6692
3728
268
0.755
0.0384
0.0811
2.142 and –1.392
1704
1.79–25.00
16271
2997
222
1.182
0.0254
0.0792
0.728 and –1.204
634849
560
1.72–25.00
11140
4042
314
1.160
0.0240
0.0707
0.750 and –0.582
634850
580
1.69–25.00
11602
4209
286
1.084
0.0354
0.1116
0.710 and –0.979
634851
3184
1.41–28.13
63837
7983
406
1.004
0.0487
0.1521
0.964 and –3.012
634052
θ limits [°]
Measured reflections
Unique reflections
Parameters
GOF on F2
R1 [IϾ2σ(I)]
wR2 (on F2, all data)
∆ρmin/max [e/Å3]
CCDC deposition code 634848
ppm. 31P{1H} NMR (162 MHz, CD2Cl2, –80 °C): δ = 41.70 (JPt,P
= 2389 Hz), 11.14 (d, J = 593, J = 468 Hz) ppm. IR
Acknowledgments
109Ag,P
107Ag,P
(KBr disk): ν = 2097 (CϵC), 1384 (N=O) cm–1. FAB MS: m/z =
˜
We wish to thank the Spanish Ministry for Education and Science,
Junta de Castilla y León as well as the University of Burgos for
generous financial support (grant numbers BQU2005-0899,
BU033A06 and 112-541A-487.01). F. M. thanks the University of
Burgos for a visiting fellowship.
997 [M
– Ag –
2Ph3P]+. C78H66Ag2N4O6P4PtS2·1/2CH2Cl2
(1796.7): calcd. C 52.48, H 3.76 N 3.12; found C 52.42, H 3.99, N
3.13.
cis-[Pt(CϵCR5)2(dppe)(AgPPh3)]NO3 (16): Yield: 0.041 g (73%),
1
ivory solid. H NMR (400 MHz, CD2Cl2): δ = 2.40–2.57 (m, 4 H,
PCH2CH2P), 4.79 (s, 4 H, NCH2), 6.26 (t, J = 2.2 Hz, 2 H, Pz-
H4), 7.28–7.73 (m, 54 H, Ph2P, Ph3P, Pz) ppm. 31P{1H} NMR
(162 MHz, CD2Cl2, –80 °C): δ = 41.20 (JPt,P = 2416 Hz), 11.07 (d,
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109Ag,P
107Ag,P
= 468 Hz) ppm. IR (KBr disk): ν = 2097
˜
J
= 540, J
(CϵC), 1384 (N=O) cm–1. FAB MS: m/z = 911 [M – Ph3P]+.
C74H64Ag2N6O6P4Pt·1/2CH2Cl2 (1710.5): calcd. C 52.31, H 3.83,
N 4.91; found C 52.21, H 4.18, N 4.92.
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1
(colourless
block,
725–756.
block, 0.09ϫ0.12ϫ0.21 mm), (colourless
2
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0.10ϫ0.10ϫ0.20 mm), 5 (yellow prism 0.10ϫ0.20ϫ0.20 mm),
9·2CHCl3 (colourless prism, 0.20ϫ0.30ϫ0.50 mm) and 10
(colourless prism, 0.60ϫ0.10ϫ0.10 mm) were mounted in oil on
a glass fibre. Data was collected at 100 K (293 K for complex 10)
by using a Bruker Apex CCD diffractometer with graphite-mono-
chromated Mo-Kα radiation (λ = 0.71073 Å). Data reduction and
absorption corrections were applied by using SADABS.[52] The
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2
structures were solved by direct methods and refined to Fo by
using full-matrix least-squares.[53] All hydrogen atoms were placed
in calculated positions and refined as riding on their respective car-
bon atoms. Crystallographic and refinement details are collected in
Table 2.
CCDC-634848, -634849, -634850, -634851 and -634052 (for com-
pounds 1, 2, 5, 9 and 10, respectively) contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
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3122
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 3115–3123

Platinum(II) Alkynyl Complexes Containing N- and S-Propargylated Ligands
FULL PAPER
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Received: February 2, 2007
Published Online: May 14, 2007
Eur. J. Inorg. Chem. 2007, 3115–3123
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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