Polynuclear and mixed-ligand mononuclear CuI complexes with N-thiophosphorylated thioureas and 1,10-phenanthroline or PPh3

Article abstract of DOI:10.1039/c0dt00866d

Deprotonation of the N-thiophosphorylated thioureas RC(S)NHP(S)(OiPr) ₂ (R = Me₂N, HL^I; iPrNH, HL^II; 2,6-Me₂C₆H₃NH, HL^III, 2,4,6-Me ₃C₆H₂

Full text of DOI:10.1039/c0dt00866d

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www.rsc.org/dalton | Dalton Transactions
Polynuclear and mixed-ligand mononuclear CuI complexes with
N-thiophosphorylated thioureas and 1,10-phenanthroline or PPh3†
Damir A. Safin,a,b Maria G. Babashkina,*a Michael Bolte,c Tania Pape,d F. Ekkehardt Hahn,d
Maxim L. Verizhnikov,b Airat R. Bashirovb and Axel Klein*a
Received 19th July 2010, Accepted 23rd September 2010
DOI: 10.1039/c0dt00866d
Deprotonation of the N-thiophosphorylated thioureas RC(S)NHP(S)(OiPr)2 (R = Me2N, HLI; iPrNH,
HLII; 2,6-Me2C6H3NH, HLIII, 2,4,6-Me3C6H2NH, HLIV, aza-15-crown-5, HLV) and reaction with CuI
or Cu(NO3)2 in aqueous EtOH leads to the polynuclear complexes [Cu4(LI–S,S¢)4], [Cu8(LII–S,S¢)8],
1
and [Cu3(LIII–V–S,S¢)3]. The structures of these compounds were investigated by IR, 1H, 31P{ H} NMR,
UV-vis spectroscopy and elemental analyses. The crystal structures of [Cu4LI4], [Cu8LII8], [Cu3LIII,IV
]
3
were determined by single-crystal X-ray diffraction. Reaction of the deprotonated ligands (LI–V)- with a
mixture of CuI and 1,10-phenanthroline (phen) or PPh3 leads to the mixed-ligand mononuclear
complexes [Cu(phen)LI–V], [Cu(PPh3)LI–V] or [Cu(PPh3)2LI–V]. The same mixed-ligand complexes were
obtained from the reaction of [Cu4LI4], [Cu8LII8], [Cu3LIII–V3] with phen or PPh3.
talline or powder samples.7,8 In solution the binding modes of the
ambidentate ligands can be established by multinuclear NMR,
while information on the nuclearity are not feasible.
Introduction
Polynuclear CuI complexes are of great interest due to their
luminescent properties,1 their use as catalysts,2 as precursors
for chalcogenide nanoparticles,3 and as models for biolog-
ical systems.4 There is a growing family of ligands based
on dithio(seleno)phosphinic acids RR¢P(X)YH (X, Y = S,
Se) and imidodithio(seleno)diphosphinates R2P(X)NHP(X)R¢2
(IDP) forming polynuclear aggregates with CuI.3a,5 Con-
trary to the previously mentioned ligands, there is a lack
of information about structures of polynuclear CuI com-
plexes containing N-thiophosphorylated thioureas or thioamides,
In this study, we describe the structural and spectroscopic
characterisation of new oligonuclear CuI complexes [Cu4(LI–
S,S¢)4], [Cu8(LII–S,S¢)8], and [Cu3(LIII–V–S,S¢)3] with the thioureas
RC(S)NHP(S)(OiPr)2 (R = Me2N, HLI; iPrNH, HLII; 2,6-
Me2C6H3NH, HLIII; 2,4,6-Me3C6H2NH, HLIV; aza-15-crown-5,
HLV) which were prepared from ethanolic solutions of CuI or
Cu(NO3)2 and the deprotonated ligands. The final crystalline
materials were obtained from CH2Cl2–n-hexane solutions. Fur-
thermore, reactions of [Cu4LI4], [Cu8LII8], [Cu3LIII–V3] with the
diimine chelate ligand 1,10-phenanthroline (phen) or PPh3 were
performed on which we will also report in this contribution.
Detailed analytical, spectroscopic and structural characterisation
of all new complexes is provided.
RC(S)NHP(S)R¢2 (R
IDP¢s asymmetrical analogues containing a thiocarbonyl group
instead of thiophosphinic unit. The molecular struc-
= R¢2N, alkyl, aryl), which are the
a
tures of only four polynuclear CuI complexes namely the
cyclic trimers [Cu3{Et2NC(S)NP(S)(OPh)2}3],6 [Cu3{morpholin-
N-ylC(S)NP(S)(OiPr)2}3] ([Cu3QI3]),7 the hexanuclear aggregate
[(Cu3{PhNHC(S)NP(S)(OiPr)2}3)2] ([(Cu3QII3)2]),8 and the ionic
aggregate [Cu10{PhNHC(S)NP(S)(OEt)2}9]ClO4,9 have been re-
ported. Although the nature of the ligand generally has an impact
on the structures, very often the preparation or crystallisation
method determines the type(s) of aggregate(s) obtained in a sample
and the nuclearity of such compounds cannot be predicted. Thus,
for the investigation of such compounds it is important to compare
the structures obtained from single crystal X-ray diffraction to
solid state NMR spectroscopic investigation of bulk microcrys-
Results and discussion
The ligand HLV was prepared by the reaction of aza-15-crown-5
with (iPrO)2P(S)NCS. The IR spectrum of HLV shows a band at
642 cm-1 assigned to the P S group. The band at 1542 cm-1 is
assigned to the S C–N group.10 A unique band at 3197 cm-1 was
related to the NH group. In addition, there are broad intense bands
arising from the POC and COC groups at 1011 and 1142 cm-1,
1
respectively, in the spectrum of HLV. The 31P{ H} NMR spectrum
of HLV contains a signal at 58.3 ppm. In the 1H NMR spectrum of
HLV the signals for the methyl protons are observed at 1.37–1.40
ppm. The signal at 4.86 ppm corresponds to the CH protons. The
signals for the CH2 protons of the crown ether fragment are in
the range of 3.73–4.28 ppm. The signal for the NH-proton was
aInstitut fu¨r Anorganische Chemie, Universita¨t zu Ko¨ln, Greinstrasse 6, D-
50939, Ko¨ln, Germany. E-mail: maria.babashkina@ksu.ru.; Fax: +49 221
4705196; Tel: +49 221 4702913
bJSC «DANAFLEX», Rodina Str. 7, 420087, Kazan, Russian Federation
cInstitut fu¨r Anorganische Chemie J.-W.-Goethe-Universita¨t, Frankfurt/
Main, Germany
observed in the spectrum at 8.17 ppm.
Reaction of the deprotonated ligands (LI–V
-
dInstitut fu¨r Anorganische und Analytische Chemie, Westfa¨lische Wilhelms-
Universita¨t Mu¨nster, Corrensstrasse 36, D-48149, Mu¨nster, Germany
)
with CuI (see
Path A in Experimental section) or Cu(NO3)2 (see Path B in
Experimental section) in aqueous EtOH leads to the polynu-
clear complexes [Cu4LI4], [Cu8LII8], and [Cu3LIII–V3] (Scheme 1).
Although starting from copper sources with different oxidation
† Electronic supplementary information (ESI) available: Additional data.
CCDC reference numbers 684171, 717087, 739993 and 739994. For ESI
and crystallographic data in CIF or other electronic format see DOI:
10.1039/c0dt00866d
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were observed at 3.14–3.43 and 2.21–2.25 ppm, respectively. The
aryl protons signal in the spectra of [Cu3LIII,IV3] is observed at 6.82–
7.12 ppm. The signals for the crown ether protons in the spectra of
[Cu3LV3] is observed at 3.86–4.61 ppm. The 1H signal of the NHP
1
group is absent in the H NMR spectra, confirming the anionic
character of ligands. The arylNH proton signal is observed at
1
7.69–7.75 ppm. Both 31P{ H} and 1H NMR spectra point to the
presence of only one species for each complex in solution.
The ES (electrospray method) mass spectra of the positive
ions of the complexes [Cu4LI4], [Cu8LII8] and [Cu3LIII–V3] con-
tain characteristic peaks for [CuL], [Cu2L], [Cu2L], [Cu2L2],
[Cu3L2] and [Cu3L3]. The most intense peak corresponds to a
species of the composition [Cu4L3]. Recently CuI complexes of
such compositions [(Cu4L3)(CuCl2)]·CCl4 and [Cu4L3]·I3 (L =
[Ph2P(S)NP(S)PPh2]-) were described.5h,k It was established that
the tetrahedral complex core [Cu4L3]+ (Scheme 2) is rather stable
even in the presence of acids.5h
Scheme 1 Preparation of [Cu4LI4], [Cu8LII8] and [Cu3LIII–V3].
states (CuI or CuII), the products obtained from both paths
were identical as was established by microanalysis, IR and NMR
spectroscopy. Importantly, the reactions following Path B require
-
two equivalents of deprotonated ligand (LI–V
)
of which one
equivalent is obtained back after workup in its protonated form
HLI–V (IR and NMR). Under these conditions reactions following
Path A gave only slightly higher yields compared to Path B.
We thus suppose a reaction sequence for Path B (using CuII)
including the formation of the unstable [CuIIL2] species (eqn (1))
followed by oxidation of ethanol to acetaldehyde (eqn (2a–c))6 and
concomitant reduction of CuII. Consequently, one equivalent of
the protonated ligands HLI–V is obtained according to eqn (2a–c).
Cu2+ + 2 KLI–V → [CuIILI–V2] + 2 K+
(1)
4 [CuIILI2] + 2 EtOH → [Cu4LI4] + 2 CH3CHO + 4 HLI (2a)
8 [CuIILII2] + 4 EtOH → [Cu8LII8] + 4 CH3CHO + 8 HLII (2b)
6 [CuIILIII–V2] + 3 EtOH → 2 [Cu3LIII–V3] + 3 MeCHO + 6
Scheme 2 The structure of [Cu4L3]+ (L = [Ph2P(S)NP(S)PPh2]-).5k
(2c)
HLIII–V
The complexes obtained are microcrystalline materials. 1H,
Under the applied measurement conditions the molecular ion
[Cu4L4 + H + H2O + C2H5OH]+ was observed in the mass spectrum
of the complex [Cu4LI4]. The heaviest ions observed in the spectrum
of [Cu8LII8] correspond to [Cu4L4], [Cu5L4] and [Cu6L5] complex
cores. Interestingly, the ions [Cu5L4 + C2H5OH]+ and [Cu6L5]+
were observed having intensities of 9 and 5%, respectively.
The ES mass spectra of the negative ions of the com-
plexes [Cu4LI4], [Cu8LII8] and [Cu3LIII–V3] contain characteristic
peaks for [L] and [CuL2]. The [CuL2] backbone was previously
found by us in the polynuclear CuI complex [KCuL2]n (L =
[PhC(S)NP(S)P(OiPr)2]-).12 The heaviest ions observed in the
mass spectra of [Cu3LIII–V3] correspond to a [Cu2L3] complex
core. Similar ions were also found in the spectra of [Cu4LI4] and
[Cu8LII8]; however, here also the anions of heavier species [Cu3L4]
and [Cu4L5] were observed and in the case of the octanuclear
complex [Cu8LII8] the [Cu5L6]- anion with an intensity of 6% was
found.
1
31P{ H} NMR and IR spectroscopy data indicated that the
thioureas HLI–V are 1,5-S,S¢-ligands in all the complexes
obtained.
The IR spectra of the complexes show weak bands centred at
600–611 cm-1 which were assigned to the P S groups. They are
shifted to low frequencies relative to those observed for the parent
ligands HLI–V due to the coordination with the metal cation.
The broad and strong band at 1539–1557 cm-1 is assigned to
the conjugated SCN group10 and proves the formation of S,S¢-
chelates. A unique band at 3251–3268 cm-1 related to the arylNH
groups were also observed in the spectra of [Cu3LIII,IV3], while no
band for the NH group was observed in the spectra of [Cu4LI4]
and [Cu3LV3], as expected.
1
In the 31P{ H} NMR spectra of the complexes each one
singlet signal was observed in the range 49.1–50.8 ppm which is
characteristic for deprotonated N-thiophosphorylated thioamides
and thioureas.11 The 1H NMR spectra contain a set of signals for
the iPr protons: a doublet for the CH3 protons at 1.09–1.31 ppm
and a doublet of septets for the CH protons at 4.45–4.94 ppm for
From the mass spectrometric experiments we can conclude that
ES-MS is a very suitable method for the structure determination
of Cu-containing polynuclear complexes with RC(S)NHP(S)R¢2
ligands since an unequivocal assignment of the various oligomeric
each complex. The Me protons signal for [Cu4LI4] and [Cu3LIII,IV
]
3
11578 | Dalton Trans., 2010, 39, 11577–11586
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species is facilitated by the presence of the two copper isotopes
63Cu (69.15% natural abundance) and 65Cu (30.85%). It is also
noteworthy that the mass spectra of all trinuclear complexes
[Cu3LIII–V3] are rather similar, showing that the influence of the
ligand on the formation of oligonuclear species under ES-MS
conditions is very small. Finally, the frequent observation of
several oligomeric species at relatively equal intensities point to
similar energies of all these trimeric, tetrameric, hexameric and
octameric structures.
The crystal structures of the complexes [Cu4LI4], [Cu8LII8] and
[Cu3LIII,IV3] were determined by single crystal X-ray diffraction.
X-Ray suitable crystals were obtained by slow evaporation of
saturated solutions in CH2Cl2–n-hexane. The crystallographic data
is summarised in the Experimental section.
According to the X-ray data, the complex [Cu4LI4] is a cyclic
tetramer (Fig. 1), in which the Cu–S–Cu bridging bonds are
formed by the sulfur atoms of the C S groups. The Cu4S4
cyclic backbone is in a distorted saddle-like conformation and
the copper atoms are in a S3 trigonal-planar environment (Fig. 2).
The distances Cu(1) ◊ ◊ ◊ Cu(1C) 2.8682(13) and Cu(1A) ◊ ◊ ◊ Cu(1C)
˚
2.8956(13) A are rather close to the sum of the van der Waals
I
13
˚
radii of Cu , 2.80 A. The other distances Cu(1) ◊ ◊ ◊ Cu(1B)
˚
2.9420(13) and Cu(1A) ◊ ◊ ◊ Cu(1B) 2.9712(12) A indicate lack of
any distinct Cu ◊ ◊ ◊ Cu interactions.9 This variation in the Cu ◊ ◊ ◊ Cu
distances leads to an increase of the Cu(1)–S(1)–Cu(1B) and
Cu(1B)–S(2B)–Cu(1A) bond angles relative to the Cu(1C)–S(2C)–
Cu(1) and Cu(1A)–S(2A)–Cu(1C) angles (Table S1 in ESI†). The
four CuSCNPS six-membered chelate rings adopt a distorted
boat conformation. In these chelate rings, the C S and P
S
bonds are lengthened, while C–N and P–N bonds are shortened
(Table S1 in ESI†) in comparison to the typical values for N-
thiophosphorylated thioureas and thioamides.11 The C S bonds,
participating in the formation of the bridges, are especially
Fig. 1 Molecular structure of the complex [Cu4LI4] with thermal ellip-
soids at the 30% probability level (C = grey, Cu = brown, N = blue, O =
red, P = orange, S = yellow). Hydrogen atoms are omitted for clarity.
˚
lengthened to values of 1.776(9), 1.780(7), 1.780(8) and 1.787(8) A,
characteristic for single bonds.14
11
˚
1.779(4) A] than those found in other thioureas and thioamides.
The molecules of [Cu4LI4] in the crystal are interconnected
through four intermolecular C–H ◊ ◊ ◊ S P contacts forming a 2D
polymeric sheet (Scheme 3).
Eight [CuLII] moieties associate to form an octamer [Cu8LII8],
which can also described as two tetrameric units [Cu4LII4] attached
to each other by Cu–S interactions (Fig. 3).
X-Ray diffraction studies on a single crystal of [Cu8LII
]
The six-membered chelate rings are linked by the thiocarbonyl
S atoms resulting in an eight-membered Cu4S4 ring. Contrary
to our expectations, the octameric unit is also formed by Cu–
S interactions through the thiocarbonyl S atoms, while the
thiophosphoryl S atoms in each ligand moiety still form only
one Cu–S bond (Fig. 3). All Cu ◊ ◊ ◊ Cu separations (Table S2 in
8
shows that each metal cation is bound to the deprotonated
thiophosphoryl thiourea through the S atoms of the C S and
P
S groups forming a six-membered heterometallocyclic chelate
[CuLII] (Fig. 3). The phosphorus atom is out of plane of the
pseudo boat conformation. The C S bonds are longer [1.765(4) to
Fig. 2 A perspective view of the Cu4S4(S4), Cu8S8(S8) and Cu3S3(S3) cores in the complexes [Cu4LI4] (A), [Cu8LII8] (B) and [Cu3LIII,IV3] (C) with thermal
ellipsoids at the 30% probability level. Atom labeling for the Cu3S3(S3) core in the symmetric complex [Cu3LIII3] is given in parenthesis.
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Scheme 4 The simplified line diagram of the intermolecular H-contacts
in [Cu8LII8].
Scheme 3 The simplified line diagram of the intermolecular H-contacts
in [Cu4LI4].
Fig. 4 Molecular structure of the complex [Cu3LIII3] with thermal
ellipsoids at the 30% probability level (C = grey, Cu = brown, N = blue, O =
red, P = orange, S = yellow). Hydrogen atoms are omitted for clarity.
bonds are formed by the S atoms of the C S groups. The
Cu3S3 cyclic backbone is in a chair conformation and the Cu
atoms are in a S3 trigonal-planar environment (Fig. 2). The
three CuSCNPS six-membered chelate rings adopt a distorted
boat conformation. In these chelate rings, the C S and P
S
bonds are lengthened, while C–N and P–N bonds are shortened
in comparison to the typical values for N-thiophosphorylated
thioureas and thioamides.11 The three identical Cu ◊ ◊ ◊ Cu distances
in [Cu3LIII3] (3.8360(5) A) are considerably longer than the sum
Fig. 3 Molecular structure of the complex [Cu8LII8] with thermal
ellipsoids at the 30% probability level (C = grey, Cu = brown, N = blue, O =
red, P = orange, S = yellow). Hydrogen atoms are omitted for clarity.
˚
of the van der Waals radii of CuI.13 The Cu ◊ ◊ ◊ Cu distances
in [Cu3LIV3] (Table S5 in ESI†) are markedly shorter than in
[Cu3LIII3] and practically similar as in the [Cu3QII3] backbones of
8
ESI†) are close to twice the van der Waals radius of CuI.13 The Cu
atoms exhibit a distorted tetrahedral environment formed by four
S atoms.
the complex [(Cu3QII3)2] [3.6229(9), 3.6668(8) and 3.8053(9) A],
˚
˚
and 3.5374(5), 3.6392(5) and 3.7782(5) A. It is noteworthy that
[(Cu3QII3)2] also contains Cu ◊ ◊ ◊ Cu separations of 2.8015(7) A
˚
The complex [Cu8LII8] contains in the crystal eight intramolec-
ular iPr–NH ◊ ◊ ◊ S P hydrogen bonds between neighbouring
in the four-membered bridging unit.8 It seems that the presence
of the arylNH fragments in [Cu3LIII,IV3] and [(Cu3QII3)2] leads
to a considerable increase in Cu ◊ ◊ ◊ Cu distances in comparison
ligands in one molecule. Furthermore, the molecules of [Cu8LII
in the crystal are bound through four intermolecular C–H ◊ ◊ ◊ S
]
P
8
with the morpholine containing trinuclear CuI complex [Cu3QI3]
7
˚
contacts forming polymeric chains (Scheme 4). The hydrogen bond
parameters are listed in Table S3 in the ESI.†
described previously [2.7614(3), 2.8546(3) and 3.0789(4) A].
The complexes [Cu3LIII,V3] in the crystal both contain three
intramolecular aryl–NH ◊ ◊ ◊ S C hydrogen bonds between neigh-
bouring ligands similar to that observed for [Cu8LII8]. Further-
more, the molecules of [Cu3LIV3] in the crystal are interconnected
through ten intermolecular C–H ◊ ◊ ◊ O–P, C–H ◊ ◊ ◊ S C and C–
H ◊ ◊ ◊ S P contacts forming a 3D polymeric structure (Scheme 5).
The hydrogen bond parameters are listed in Table S3 in ESI.†
To the best of our knowledge this compound represents the first
example of an octagonal-prismatic core [Cu8S8(S8)] among CuI
complexes of deprotonated N-thiophosphorylated thioamides,
thioureas or imidodichalcogenphosphinates.
According to the X-ray data, the complexes [Cu3LIII,IV3] are
cyclic trimers (Fig. 4 and 5), in which the Cu–S–Cu bridging
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Fig. 6 UV-Vis absorption spectra of [Cu4LI4], [Cu8LII8] and [Cu3LIII3] in
CH2Cl2 at 25 ◦C. The absorption spectra of [Cu3LIV,V3] are very similar to
that of [Cu3LIII3].
4186 dm3 mol-1 cm-1) respectively, for the complexes [Cu3LIII–V3] is
slightly red-shifted and weaker than the corresponding absorption
of the tetranuclear compound. A much stronger absorption
band at 384 nm (e = 9754 dm3 mol-1 cm-1) is observed in the
spectrum of [Cu8LII8] which is markedly red-shifted from the
trimeric and tetrameric compounds. Absorption bands for the
free and protonated ligands RC(S)NHP(X)(OiPr)2 (X = O, S)
Fig. 5 Molecular structure of the complex [Cu3LIV3] with thermal
ellipsoids at the 30% probability level (C = grey, Cu = brown, N = blue, O =
red, P = orange, S = yellow). Hydrogen atoms are omitted for clarity.
abs
are rather high in energy (lmax < 250 nm) and were assigned
to intraligand transitions.15,16a For better comparison with the
complexes [Cu4LI4], [Cu8LII8] and [Cu3LIII–V3] in which the ligands
are deprotonated, we recorded the spectra of the corresponding
potassium salts KLI–V. The absorption spectra of KLI–V are all
similar and weak absorptions were observed in the range 294–303
nm (e = 181–193 dm3 mol-1 cm-1). The bands can be attributed
to ligand–ligand transitions in the deprotonated forms (LI–V)-.
From the huge differences between the absorption spectra of the
complexes [Cu4LI4] and [Cu3LIII–V3] and the spectrum of [Cu8LII8] in
CH2Cl2 solution we can assume that a certain degree of association
(trimer, tetramer, octamer) found in the crystal is retained in
solution, although we cannot say if the oligomeric structures
in solution were identical to those in the solid. The absorption
bands of the complexes are thus preliminarily assigned to ligand-
to-cluster or cluster-centred charge transfer transitions. Such
transitions have also been concluded from the luminescence of
many polynuclear CuI compounds.1 Support for our preliminary
assignment comes from the fact that the ligand (LII)- in [Cu8LII
]
8
exhibits a different coordination mode [m4-S(C),S(C),S(C),S¢(P) vs.
m3-S(C),S(C),S¢(P)] compared to (LI,III–V)- in the tri- or tetranuclear
complexes (Fig. 1–5). This binding mode leads to a shortening
of the Cu ◊ ◊ ◊ Cu separations in [Cu8LII8] (Table S3 in ESI†) and
thus to a stabilisation of cluster-type electronic states, in line
with the lower energy and higher intensity of the corresponding
absorption.
Recently, we have reported that the reaction of polynuclear
CuI complexes with RC(S)NP(S)(OiPr)2 (R = Ph,12,16a PhNH,16a
morpholin-N-yl16a) with PPh3, 2,2¢-bipyridine (bpy) or 1,10-
phenanthroline (phen) leads straightforward to the mononuclear
mixed-ligand complexes [Cu(PPh3)L] or [Cu(PPh3)2L], [Cu(bpy)L]
and [Cu(phen)L]. It is thus possible to establish the nuclearity
of such polynuclear complexes in solution by adding defined
amounts of ligands such as PPh3, bpy or phen, and measure the
Scheme 5 The simplified line diagrams of the intermolecular H-contacts
in [Cu3LIV3].
The UV-vis s◦pectra of [Cu4LI4], [Cu8LII8] and [Cu3LIII3] in CH2Cl2
solution at 25 C are depicted in Fig. 6. The absorption spectra
for [Cu3LIV,V3] are very similar to that of [Cu3LIII3]. For [Cu4LI4]
a strong absorption band at 347 nm (e = 7128 dm3 mol-1 cm-1) is
observed. The low-energy absorption band at 354 (e = 4170 dm3
mol-1 cm-1), 350 (e = 4193 dm3 mol-1 cm-1) or 352 nm (e =
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Scheme 6 The controlled decomposition of [Cu4LI4], [Cu8LII8] and [Cu3LIII–V3] using PPh3 and phen as additional donor ligands to provoke the
decomposition.
1
31P{ H} NMR spectra. These studies also showed that the use
According to the IR and NMR data the deprotonated thiourea
-
ligands (LI–V
)
are also coordinated in a 1,5-S,S¢-fashion in
of PPh3 is intricate due to the possible formation of two different
species [Cu(PPh3)L] or [Cu(PPh3)2L]. The complex [Cu(PPh3)2LII],
obtained by the reaction of [Cu(PPh3)2NO3] and KLII, was
previously described.2
Herein we have used PPh3 and phen as additional donor ligands
to provoke the controlled decomposition of [Cu4LI4], [Cu8LII
the mixed-ligand complexes [Cu(phen)LI–V], [Cu(PPh3)LI–V] and
[Cu(PPh3)2LI–V]. In the 31P{ H} NMR spectra singlet resonances
1
were observed at 51.3–54.6 ppm. These signals are down-field
shifted compared to the corresponding signal of [Cu4LI4], [Cu8LII
]
8
1
and [Cu3LIII–V3]. The signals of PPh3 in the 31P{ H} NMR
spectra of the complexes [Cu(PPh3)LI–V] exhibit chemical shifts
from 0.3 to 1.1 ppm and observed in the area typical for the
coordinated PPh3 in mononuclear mixed-ligand CuI complexes
with RC(S)NHP(S)(OR¢)2 and PPh3 ligands.17 The same signal
in the phosphorus spectrum of [Cu(PPh3)2LV] was observed
at -0.9 ppm, which is in the range typical for similar types
of complexes containing two PPh3 groups.7,8,18 The 1H NMR
spectra of [Cu(phen)LI–V], [Cu(PPh3)LI–V] and [Cu(PPh3)2LI–V] each
contain two sets of signals of the corresponding deprotonated
ligand (LI–V)- and phen or PPh3. The ratio of integral intensities
of the signals proofs the composition of the complexes.
]
8
and [Cu3LIII–V3] (Scheme 6). Using various stoichiometric ratios
of [CuL] and phen (Table 1) we found that even with small
amounts of phen the signal corresponding to the mononuclear
mixed-ligand complexes [Cu(phen)LI–V] appears together with the
signals of the excess parent copper complex and other signals of
yet unidentified fragments. The stoichiometric ratios of [CuL] and
PPh3 were 1 : 1 and 1 : 2 and led exactly and unequivocally to the
complexes [Cu(PPh3)LI–V] or [Cu(PPh3)2LI–V].
The
[Cu(PPh3)LI–V
same
mixed-ligand
and [Cu(PPh3)2LI–V
complexes
[Cu(phen)LI–V],
]
]
were obtained by the
reaction of KLI–V with a mixture of CuI and phen or PPh3.
1
Table 1 Signals of the P S phosphorus atom in the 31P{ H} NMR spectra of a mixture of [Cu4LI4], [Cu8LII8] or [Cu3LIII–V3] and phen in CDCl3
Ratio of [CuL] : phen
Complex
1 : 0
1 : x
1 : 1
2 : 1
3 : 1
4 : 1
5 : 1
6 : 1
7 : 1
8 : 1
[Cu4LI4]
49.1
x = 1.25; 52.2
x = 1.125; 54.1
x = 1.33; 51.3
x = 1.33; 51.6
x = 1.33; 53.6
52.2
54.1
51.3
51.6
53.6
50.8, 52.1
53.7, 54.0
49.7, 51.2
50.9, 51.4
51.5, 53.5
51.3, 52.1
51.9, 54.0
49.5, 51.0
49.8, 51.3
52.9, 53.3
49.2, 52.0
53.0, 53.9
—
—
—
—
—
—
—
[Cu8LII
]
50.616a
49.2
52.7, 53.9
51.3, 53.8
50.7, 53.5
50.9, 53.3
8
[Cu3LIII
[Cu3LIV
[Cu3LV
]
—
—
—
—
—
—
—
—
—
—
—
—
3
]
49.3
50.8
3
]
3
11582 | Dalton Trans., 2010, 39, 11577–11586
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then removed in a vacuum. The colourless oil was recrystallised
from a CH2Cl2–n-hexane mixture (1 : 3, v/v). Yield: 0.190 g, 83%.
IR: 642 (P S), 1011 (POC), 1142 (COC), 1508 (S C–N), 3197
(NH) cm-1. 1H NMR: 1.37 (d, 3JH,H = 6.1 Hz, 6 H, CH3, iPr), 1.40
(d, 3JH,H = 6.0 Hz, 6 H, CH3, iPr), 3.73–4.28 (m, 20 H, CH2, crown),
4.86 (d. sept, 3JH,H = 6.1 Hz, 3JP,H = 9.2 Hz, 2 H, OCH), 8.17 (br. s, 1
Conclusions
Reaction of CuI or Cu(NO3)2 with the deprotonated N-
thiophosphorylated thioureas HLI–V has allowed us to obtain
the polynuclear complexes [Cu4LI4], [Cu8LII8] and [Cu3LIII–V3].
Furthermore, the reaction of the deprotonated ligands with a
mixture of CuI and 1,10-phenanthroline (phen) or PPh3 leads
to the formation of the mononuclear complexes [Cu(phen)LI–V],
[Cu(PPh3)LI–V] or [Cu(PPh3)2LI–V]. The same mixed-ligand com-
plexes could be obtained by the reaction of [Cu4LI4], [Cu8LII8] and
[Cu3LIII–V3] with phen or PPh3. Thus, the addition of a-diimine
or phosphine ligands provides a controlled disassembly of the
polynuclear structures. IR and NMR experiments showed that
the deprotonated thioureas (LI–V)- are 1,5-S,S¢-ligands in all cases.
According to single crystal X-ray data the complex [Cu4LI4] is a
cyclic tetramer, while the complex [Cu8LII8] is a cyclic octamer.
The complexes [Cu3LIII,IV3] are cyclic trimers in the crystalline
phase. There are eight intramolecular iPr–NH ◊ ◊ ◊ S P or aryl–
NH ◊ ◊ ◊ S P hydrogen bonds between neighbouring ligands in the
molecules of [Cu8LII8] and [Cu3LIII,IV3], respectively. All complexes
exhibit intermolecular hydrogen bonds in the crystal, leading to
2D [Cu4LI4], 1D [Cu8LII8] or 3D [Cu3LIV3] polymeric networks. The
complex [Cu8LII8] is the first example of octanuclear CuI complexes
with N-thiophosphorylated thioamides and thioureas of common
formula RC(S)NHP(S)R¢2. An explanation of the different degrees
of association might lie in the bulkiness of the ligands allowing
only (LII)- (R = iPrNH) to form an octameric structure, while
the ligands (LIII–V)- are too bulky. Furthermore, the formation of
intramolecular hydrogen bonds of the type N–H ◊ ◊ ◊ S P is only
possible for the ligands (LII–V)-, but not for (LI)-, which in turn
might have an influence on the formation of oligomeric structures.
However, for a profound conclusion more examples with further
ligand derivatives are necessary.
1
H, NH) ppm. 31P{ H} NMR: 58.3 ppm. C17H35N2O6PS2 (458.57):
calcd. C 44.53, H 7.69, N 6.11; found: C 44.47, H 7.74, N 6.05.
Synthesis of [Cu4LI4], [Cu8LII8] and [Cu3LIII–V
]
3
The synthesis of [Cu8LII8] using CuI was described previously.16a
Path A. A suspension of HLI,III–V (0.852, 1.080, 1.125 or
1.376 g, respectively; 3 mmol) in aqueous ethanol (25 mL) was
mixed with KOH (0.185 g, 3.3 mmol). The resulting mixture
was added dropwise to a suspension of CuI (0.570 g, 3 mmol)
in aqueous ethanol (20 mL). The mixture was stirred at room
temperature for 8 h. The resulting precipitate of KI was filtered
off and the solvent was then removed in vacuum. The residue was
recrystallised from a CH2Cl2–n-hexane mixture (1 : 3, v/v).
Path B. A suspension of HLI–V (0.852, 0.894, 1.080, 1.125
or 1.376 g, respectively; 3 mmol) in aqueous ethanol (25 mL)
was mixed with KOH (0.185 g, 3.3 mmol). The resulting mixture
was added dropwise to a suspension of Cu(NO3)2·6H2O (0.444 g,
1.5 mmol) in aqueous ethanol (20 mL). The mixture was stirred
at room temperature for 3 h. The resulting complex was extracted
from the reaction mixture using CH2Cl2, the collected extracts
were dried over anhydrous MgSO4 and the solvent was finally
removed in vacuum. The residue was recrystallised from a CH2Cl2–
n-hexane mixture (1 : 3, v/v). After several minutes crystals
of the corresponding complex were deposited and isolated by
decantation. The mother liquor was left for three more days after
which a fine-crystalline solid of the starting ligand was isolated.
Complex [Cu4LI4] was obtained as yellow crystals. Yield (Path
A): 0.843 g, 81%. Yield (Path B): 0.465 g, 89%. M.p. 100–102 ◦C.
Experimental
1
IR: 603 (P S), 992, 1007 (POC), 1539 (SCN) cm-1. H NMR:
General procedures
3
3
1.30 (d, JH,H = 6.2 Hz, 24 H, CH3, iPr), 1.31 (d, JH,H = 6.2 Hz,
24 H, CH3, iPr), 3.14 (s, 12 H, CH3, Me), 3.43 (s, 12 H, CH3,
Infrared spectra (Nujol) were recorded with a Specord M-80
spectrometer in the range 400–3600 cm-1. NMR spectra (CDCl3)
were obtained on a Varian Unity-300 and Bruker Avance 300 MHz
3
3
Me), 4.69 (d. sept, JH,H = 6.2 Hz, JP,H = 10.5 Hz, 8 H, OCH)
ppm. 31P{ H} NMR: 49.1 ppm. ES-MS (positive ion): m/z (%) =
1
spectrometers at 25 ◦C. Electronic spectra of absorption in 10-4
M
347.6 (72) [CuL + H]+, 365.4 (18) [CuL + H + H2O]+, 393.5 (38)
[CuL + H + C2H5OH]+, 410.7 (22) [Cu2L]+, 456.8 (64) [Cu2L +
C2H5OH]+, 712.5 (41) [Cu2L2 + H + H2O]+, 775.1 (11) [Cu3L2 +
H2O]+, 821.2 (16) [Cu3L2 + H2O + C2H5OH]+, 1087.0 (82) [Cu3L3 +
H + C2H5OH]+, 1103.8 (100) [Cu4L3]+, 1121.6 (17) [Cu4L3 + H2O]+,
1451.2 (39) [Cu4L4 + H + H2O + C2H5OH]+. ES-MS (negative
ion): m/z (%) = 283.2 (34) [L]-, 676.1 (18) [CuL2 + C2H5OH]-,
976.8 (8) [Cu2L3]-, 1323.4 (100) [Cu3L4]-, 1369.6 (31) [Cu3L4 +
C2H5OH]-, 1716.1 (4) [Cu4L5 + C2H5OH]-. C36H80Cu4N8O8P4S8
(1387.67): calcd. C 31.16, H 5.81, N 8.07; found: C 31.29, H 5.72,
N 8.16.
solution of CH2Cl2 were measured on a Lambda-35 spectrometer
in the range 200–1000 nm. Electrospray ionisation mass spectra
were measured with a Finnigan-Mat TCQ 700 mass spectrometer
on a 10-6 M solution in CH3OH. The speed of sample submission
was 2 mL min-1. The ionisation energy was 4.5 kV. The capillary
temperature was 200 C. Elemental analyses were performed on
a Perkin–Elmer 2400 CHN and HEKAtech CHNS EuroEA 3000
microanalysers.
◦
Synthesis of HLI–V
Complex [Cu8LII8] was obtained as colourless crystals.16a Yield
(Path B): 0.368 g, 68%. ES-MS (positive ion): m/z (%) = 407.5
(38) [CuL + H + C2H5OH]+, 442.8 (19) [Cu2L + H2O]+, 768.4 (57)
[Cu2L2 + H + C2H5OH]+, 848.7 (26) [Cu3L2 + H2O + C2H5OH]+,
1191.4 (92) [Cu4L3 + C2H5OH]+, 1461.4 (44) [Cu4L4 + H +
H2O]+, 1551.8 (9) [Cu5L4 + C2H5OH]+, 1866.4 (5) [Cu6L5]+. ES-MS
(negative ion): m/z (%) = 297.2 (25) [L]-, 676.4 (39) [CuL2 + H2O]-,
HLI–IV
.
The N-thiophosphorylated thioureas were prepared
according to previously described methods.16
HLV. A solution of aza-15-crown-5 (0.110 g, 0.5 mmol) in
anhydrous CH2Cl2 (15 mL) was treated under vigorous stirring
with a solution of (iPrO)2P(S)NCS (0.143 g, 0.6 mmol) in the
same solvent. The mixture was stirred for 1 h. The solvent was
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1064.6 (61) [Cu2L3 + C2H5OH]-, 1379.9 (100) [Cu3L4]-, 1785.2 (24)
[Cu4L5 + C2H5OH]-, 2100.9 (6) [Cu5L6]-. C80H176Cu8N16O16P8S16
(2887.49): calcd. C 33.28, H 6.14, N 7.76; found: C 33.48, H 6.22,
N 7.59.
dropwise to a suspension of CuI (0.570 g, 3 mmol) and phen
(0.540 g, 3 mmol) in anhydrous CH2Cl2 (15 mL). The mixture
was stirred at room temperature for 4 h. The resulting precipitate
of KI and excess of CuI were filtered off and the solvent was
then removed in vacuum. The residue was recrystallised from a
CH2Cl2–n-hexane mixture (1 : 5, v/v).
Complex [Cu3LIII3] was obtained as colourless crystals. Yield
(Path A): 1.167 g, 92%. Yield (Path B): 0.561 g, 88%. M.p. 148 ◦C.
1
IR: 600 (P S), 1005 (POC), 1548 (SCN), 3268 (NH) cm-1. H
Complex [Cu(phen)LI] was obtained as brown crystals. Yield:
0.588 g, 93% (Path A); 1.344 g, 85% (Path B). M.p. 142 ◦C. IR: 597
NMR: 1.10 (d, 3JH,H = 6.2 Hz, 18 H, CH3, iPr), 1.15 (d, 3JH,H = 6.2
Hz, 18 H, CH3, iPr), 2.25 (s, 18 H, CH3, Me), 4.45 (d. sept, 3JH,H
=
(P S), 998 (POC), 1508 (SCN) cm-1. H NMR: 1.38 (d, JH,H
=
1
3
6.1 Hz, 3JP,H = 10.9 Hz, 6 H, OCH), 6.96–7.12 (m, 9 H, C6H3), 7.75
6.1 Hz, 6 H, CH3, iPr), 1.41 (d, JH,H = 6.0 Hz, 6 H, CH3, iPr),
3.18 (s, 3 H, CH3, Me), 3.36 (s, 3 H, CH3, Me), 4.78–4.99 (m, 2
H, OCH), 7.09–9.38 (m, phen, ovelapping with the solvent signal)
3
1
(d, 4JP,H = 8.8 Hz, 3 H, NH) ppm. 31P{ H} NMR: 49.2 ppm. ES-
MS (positive ion): m/z (%) = 469.8 (52) [CuL + H + C2H5OH]+,
550.2 (39) [Cu2L + H2O + C2H5OH]+, 864.4 (33) [Cu2L2 + H +
H2O]+, 954.6 (71) [Cu3L2 + C2H5OH]+, 1268.6 (61) [Cu3L3 + H]+,
1349.5 (100) [Cu4L3 + H2O]+. ES-MS (negative ion): m/z (%) =
359.3 (81) [L]-, 800.2 (64) [CuL2 + H2O]-, 1250.4 (100) [Cu2L3 +
C2H5OH]-. Anal. C45H72Cu3N6O6P3S6 (1269.02): calcd. C 42.59,
H 5.72, N 6.62; found: C 42.79, H 5.61, N 6.73.
ppm. 31P{ H} NMR: 52.2 ppm. C21H28CuN4O2PS2 (527.12): calcd.
1
C 47.85, H 5.35, N 10.63; found: C 47.72, H 5.39, N 10.56.
Complex [Cu(phen)LII] was obtained as light-brown crystals.
Yield: 1.117 g, 86% (Path A); 1.494 g, 92% (Path B). M.p. 127 ◦C.
IR: 595 (P S), 1011 (POC), 1552 (SCN), 3277 (NH) cm-1. H
1
3
3
NMR: 1.24 (d, JH,H = 6.6 Hz, 6 H, CH3, iPrN), 1.30 (d, JH,H
=
Complex [Cu3LIV3] was obtained as colourless crystals. Yield
(Path A): 1.088 g, 83%. Yield (Path B): 0.534 g, 81%. M.p. 104 ◦C.
6.1 Hz, 6 H, CH3, iPrO), 1.34 (d, 3JH,H = 6.0 Hz, 6 H, CH3, iPrO),
4.00–4.93 (m, 3 H, NCH + OCH), 6.79 (br. s, 1 H, NH), 6.98–
1
1
IR: 606 (P S), 1010 (POC), 1557 (SCN), 3251 (NH) cm-1. H
9.02 (m, phen, overlapping with the solvent signal) ppm. 31P{ H}
3
3
NMR: 1.09 (d, JH,H = 6.0 Hz, 18 H, CH3, iPr), 1.14 (d, JH,H
=
NMR: 54.1 ppm. C22H30CuN4O2PS2 (541.15): calcd. C 48.83, H
5.59, N 10.35; found: C 48.99, H 5.64, N 10.41.
6.0 Hz, 18 H, CH3, iPr), 2.21 (s, 18 H, CH3, Me), 2.23 (s, 9 H,
3
3
CH3, Me), 4.45 (d. sept, JH,H = 6.1 Hz, JP,H = 10.8 Hz, 6 H,
Complex [Cu(phen)LIII] was obtained as dark-brown crystals.
Yield: 0.478 g, 88% (Path A); 1.466 g, 81% (Path B). M.p. 162 ◦C.
4
OCH), 6.82 (s, 6 H, C6H2), 7.69 (d, JP,H = 8.7 Hz, 3 H, NH)
ppm. 31P{ H} NMR: 49.3 ppm. ES-MS (positive ion): m/z (%) =
IR: 594 (P S), 1000 (POC), 1562 (SCN), 3297 (NH) cm-1. H
1
1
437.7 (68) [CuL + H]+, 546.7 (41) [Cu2L + C2H5OH]+, 874.8 (14)
[Cu2L2 + H]+, 1000.4 (66) [Cu3L2 + H2O + C2H5OH]+, 1328.5
(25) [Cu3L3 + H + H2O]+, 1373.3 (100) [Cu4L3]+. ES-MS (negative
ion): m/z (%) = 373.2 (48) [L]-, 810.4 (38) [CuL2]-, 1264.6 (100)
[Cu2L3 + H2O]-. C48H78Cu3N6O6P3S6 (1311.10): calcd. C 43.97, H
6.00, N 6.41; found: C 44.17, H 5.86, N 6.50.
NMR: 1.18 (d, JH,H = 6.0 Hz, 6 H, CH3, iPr), 1.27 (d, JH,H =
3
3
6.1 Hz, 6 H, CH3, iPr), 2.28 (s, 6 H, CH3, Me), 4.59–4.81 (m,
2 H, OCH), 6.94 (br. s, 1 H, NH), 7.04–9.46 (m, C6H3 + phen,
1
overlapping with the solvent signal) ppm. 31P{ H} NMR: 51.3
ppm. C27H32CuN4O2PS2 (603.22): calcd. C 53.76, H 5.35, N 9.29;
found: C 53.62, H 5.31, N 9.34.
Complex [Cu3LV3] was obtained as colourless oil. Yield (Path
A): 1.125 g, 72%. Yield (Path B): 0.617 g, 80%. IR: 611 (P S),
Complex [Cu(phen)LIV] was obtained as brown crystals. Yield:
◦
0.450 g, 81% (Path A); 1.741 g, 94% (Path B). M.p. 173 C. IR:
1004 (POC), 1108 (COC), 1542 (SCN) cm-1. H NMR: 1.24 (d,
600 (P S), 996 (POC), 1542 (SCN), 3274 (NH) cm-1. 1H NMR:
1
3JH,H = 6.2 Hz, 18 H, CH3, iPr), 1.28 (d, 3JH,H = 6.2 Hz, 18 H, CH3,
1.20 (d, JH,H = 6.2 Hz, 6 H, CH3, iPr), 1.25 (d, JH,H = 6.1 Hz,
6 H, CH3, iPr), 2.28 (s, 6 H, CH3, Me), 2.33 (s, 3 H, CH3, Me),
4.62–4.88 (m, 2 H, OCH), 6.77 (s, 2 H, C6H2), 7.18–9.07 (m, NH +
3
3
3
iPr), 3.86–4.61 (m, 60 H, CH2, crown), 4.94 (d. sept, JH,H = 6.0
Hz, JP,H = 9.6 Hz, 6 H, OCH) ppm. 31P{ H} NMR: 50.8 ppm.
ES-MS (positive ion): m/z (%) = 586.1 (12) [CuL + H + H2O +
C2H5OH]+, 584.4 (39) [Cu2L]+, 1106.6 (38) [Cu2L2 + H + H2O +
C2H5OH]+, 1123.3 (100) [Cu3L2 + H2O]+, 1671.7 (94) [Cu4L3 +
C2H5OH]+. ES-MS (negative ion): m/z (%) = 457.4 (66) [L]-, 996.3
(47) [CuL2 + H2O]-, 1544.4 (100) [Cu2L3 + C2H5OH]-, 1563.1
(6) [Cu2L3 + H2O + C2H5OH]-. C51H102Cu3N6O18P3S6 (1563.32):
calcd. C 39.18, H 6.58, N 5.38; found: C 39.41, H 6.52, N 5.42.
3
1
1
phen, overlapping with the solvent signal) ppm. 31P{ H} NMR:
51.6 ppm. C28H34CuN4O2PS2 (617.24): calcd. C 54.49, H 5.55, N
9.08; found: C 54.60, H 5.62, N 9.02.
Complex [Cu(phen)LV] was obtained as light-brown crystals.
Yield: 0.450 g, 76% (Path A); 1.515 g, 72% (Path B). M.p. 104 ◦C.
1
IR: 605 (P S), 1009 (POC), 1116 (COC), 1538 (SCN) cm-1. H
3
3
NMR: 1.13 (d, JH,H = 6.1 Hz, 6 H, CH3, iPr), 1.20 (d, JH,H
=
6.2 Hz, 6 H, CH3, iPr), 3.76–4.68 (m, 20 H, CH2, crown), 4.73–
Synthesis of [Cu(phen)LI–V
]
5.18 (m, 2 H, OCH), 6.97–8.92 (m, phen, ovelapping with the
1
solvent signal) ppm. 31P{ H} NMR: 53.6 ppm. C29H42CuN4O6PS2
Path A. A suspension of [Cu4LI4], [Cu8LII8] or [Cu3LIII–V
]
3
(701.32): calcd. C 49.67, H 6.04, N 7.99; found: C 49.55, H 5.98,
N 7.92.
(0.416, 0.866, 0.381, 0.393 or 0.469 g, respectively; 0.3 mmol) in
anhydrous CH2Cl2 (15 mL) was added dropwise to a suspension of
a stoichiometric amount of phen (0.216, 0.432 or 0.162 g; 1.2, 2.4,
0.9 mmol) in anhydrous CH2Cl2 (15 mL). The mixture was stirred
at room temperature for 4 h. The solvent was then removed in
vacuum. The residue was recrystallised from a CH2Cl2–n-hexane
mixture (1 : 5, v/v).
Synthesis of [Cu(PPh3)LI–V
]
Path A. A suspension of PPh3 (0.314, 0.628 or 0.236 g; 1.2,
2.4, 0.9 mmol) in anhydrous CH2Cl2 (15 mL) was added dropwise
to a suspension of a stoichiometric amount of [Cu4LI4], [Cu8LII
]
8
Path B. A suspension of HLI–V (0.852, 0.895, 1.125 or 1.376 g,
respectively; 3 mmol) in aqueous ethanol (20 mL) was mixed
with KOH (0.185 g, 3.3 mmol). The resulting mixture was added
or [Cu3LIII–V3] (0.416, 0.866, 0.381, 0.393 or 0.469 g, respectively;
0.3 mmol) in anhydrous CH2Cl2 (15 mL). The mixture was stirred
at room temperature for 4 h. The solvent was then removed in
11584 | Dalton Trans., 2010, 39, 11577–11586
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vacuum. The residue was recrystallised from a CH2Cl2–n-hexane
Synthesis of [Cu(PPh3)2LI–V
]
mixture (1 : 5, v/v).
Path A. A suspension of PPh3 (0.628, 1.256 or 0.472 g; 2.4,
4.8, 1.8 mmol) in anhydrous CH2Cl2 (15 mL) was added dropwise
Path B. A suspension of HLI–V (0.852, 0.895, 1.125 or 1.376 g,
respectively; 3 mmol) in aqueous ethanol (20 mL) was mixed
with KOH (0.185 g, 3.3 mmol). The resulting mixture was added
dropwise to a suspension of CuI (0.570 g, 3 mmol) and PPh3
(0.786 g, 3 mmol) in anhydrous CH2Cl2 (15 mL). The mixture
was stirred at room temperature for 4 h. The resulting precipitate
of KI and excess of CuI were filtered off and the solvent was
then removed in vacuum. The residue was recrystallised from a
CH2Cl2–n-hexane mixture (1 : 5, v/v).
to a suspension of a stoichiometric amount of [Cu4LI4], [Cu8LII
]
8
or [Cu3LIII–V3] (0.416, 0.866, 0.381, 0.393 or 0.469 g, respectively;
0.3 mmol) in anhydrous CH2Cl2 (15 mL). The mixture was stirred
at room temperature for 4 h. The solvent was then removed in
vacuum. The residue was recrystallised from a CH2Cl2–n-hexane
mixture (1 : 5, v/v).
Path B. A suspension of HLI–V (0.852, 0.895, 1.125 or 1.376 g,
respectively; 3 mmol) in aqueous ethanol (20 mL) was mixed
with KOH (0.185 g, 3.3 mmol). The resulting mixture was added
dropwise to a suspension of CuI (0.570 g, 3 mmol) and PPh3
(1.572 g, 6 mmol) in anhydrous CH2Cl2 (15 mL). The mixture
was stirred at room temperature for 4 h. The resulting precipitate
of KI and excess of CuI were filtered off and the solvent was
then removed in vacuum. The residue was recrystallised from a
CH2Cl2–n-hexane mixture (1 : 5, v/v).
Complex [Cu(PPh3)LI] was obtained as colourless crystals.
Yield: 0.656 g, 90% (Path A); 1.754 g, 96% (Path B). M.p. 107 ◦C.
1
IR: 610 (P S), 1007 (POC), 1537 (SCN) cm-1. H NMR: 1.09
3
3
(d, JH,H = 6.2 Hz, 6 H, CH3, iPr), 1.15 (d, JH,H = 6.1 Hz, 6 H,
CH3, iPr), 3.20 (s, 3 H, CH3, Me), 3.34 (s, 3 H, CH3, Me), 4.72 (d.
sept, 3JH,H = 6.1 Hz, 3JP,H = 10.1 Hz, 2 H, OCH), 7.19–7.52 (m, Ph,
1
overlapping with the solvent signal) ppm. 31P{ H} NMR: 0.6 (s,
1 P, PPh3), 54.2 (s, 1 P, NPS) ppm. C27H35CuN2O2P2S2 (609.20):
calcd. C 53.23, H 5.79, N 4.60; found: C 53.14, H 5.87, N 4.66.
Complex [Cu(PPh3)LII] was obtained as colourless crystals.
Yield: 1.077 g, 72% (Path A); 1.552 g, 83% (Path B). M.p. 82 ◦C. IR:
603 (P S), 997 (POC), 1541 (SCN), 3260 (NH) cm-1. 1H NMR:
1.21 (d, 3JH,H = 6.4 Hz, 6 H, CH3, iPrN), 1.28 (d, 3JH,H = 6.0 Hz, 6
H, CH3, iPrO), 1.32 (d, 3JH,H = 6.2 Hz, 6 H, CH3, iPrO), 4.07–5.04
(m, 3 H, NCH + OCH), 6.94 (br. s, 1 H, NH), 7.31–8.05 (m, 15
The complexes [Cu(PPh3)2LI–IV] obtained by these routes anal-
ysed identically to those reported previously.18
Complex [Cu(PPh3)2LV] was obtained as colourless crystals.
Yield: 1.581 g, 84% (Path A); 2.321 g, 74% (Path B). M.p. 91 ◦C.
1
IR: 617 (P S), 1001 (POC), 1115 (COC), 1569 (SCN) cm-1. H
NMR: 1.03 (d, 3JH,H = 6.0 Hz, 6 H, CH3, iPr), 1.07 (d, 3JH,H = 6.0
Hz, 6 H, CH3, iPr), 3.83–4.51 (m, 20 H, CH2, crown), 4.66–5.10
1
(m, 2 H, OCH), 7.31–7.53 (m, 30 H, Ph) ppm. 31P{ H} NMR:
1
H, Ph) ppm. 31P{ H} NMR: 0.8 (s, 1 P, PPh3), 54.0 (s, 1 P, NPS)
-0.9 (s, 2 P, PPh3), 54.6 (s, 1 P, NPS) ppm. C53H64CuN2O6P3S2
(1045.69): calcd. C 60.88, H 6.17, N 2.68; found: C 60.70, H 6.24,
N 2.62.
ppm. C28H37CuN2O2P2S2 (623.23): calcd. C 53.23, H 5.79, N 4.60;
found: C 53.11, H 5.84, N 4.66.
Complex [Cu(PPh3)LIII] was obtained as colourless crystals.
Yield: 0.499 g, 81% (Path A); 1.419 g, 69% (Path B). M.p. 138 ◦C.
X-Ray crystallography†
1
IR: 608 (P S), 1002 (POC), 1524 (SCN), 3271 (NH) cm-1. H
NMR: 1.07 (d, 3JH,H = 6.2 Hz, 6 H, CH3, iPr), 1.10 (d, 3JH,H = 6.1
Hz, 6 H, CH3, iPr), 2.30 (s, 6 H, CH3, Me), 4.64 (d. sept, 3JH,H = 6.2
Hz, 3JP,H = 10.5 Hz, 2 H, OCH), 6.77 (br. s, 1 H, NH), 6.93–7.82
The X-Ray diffraction data for [Cu4LI4] and [Cu3LIII,IV3] was
collected on a STOE IPDS-II diffractometer. The images were
indexed, integrated and scaled using the X-Area package.19 Data
was corrected for absorption using the PLATON program.20
The structure was solved by direct method using SHELXS21
and refined first isotropically and then anisotropically using
SHELXL97.21 Hydrogen atoms were revealed from Dr maps and
those bonded to C were refined using appropriate riding models.
1
(m, C6H3 + Ph, ovelapping with the solvent signal) ppm. 31P{ H}
NMR: 0.3 (s, 1 P, PPh3), 52.6 (s, 1 P, NPS) ppm. C33H39CuN2O2P2S2
(685.30): calcd. C 57.84, H 5.74, N 4.09; found: C 57.90, H 5.82,
N 4.06.
Complex [Cu(PPh3)LIV] was obtained as colourless crystals.
Yield: 0.459 g, 73% (Path A); 1.887 g, 90% (Path B). M.p. 142 ◦C.
H atoms bound to N were freely refined for [Cu3LIII,IV3] or using
1
IR: 611 (P S), 1010 (POC), 1566 (SCN), 3290 (NH) cm-1. H
I
˚
a distance restraint of 0.91(1) A for [Cu4L 4]. All figures were
NMR: 1.11 (d, 3JH,H = 6.2 Hz, 6 H, CH3, iPr), 1.16 (d, 3JH,H = 6.2
Hz, 6 H, CH3, iPr), 2.30 (s, 6 H, CH3, Me), 2.37 (s, 3 H, CH3, Me),
4.70 (d. sept, 3JH,H = 6.0 Hz, 3JP,H = 10.9 Hz, 2 H, OCH), 6.82 (s,
generated using the program XP.22
The X-ray diffraction data for [Cu8LII8] was collected on a
Bruker AXS APEX CCD diffractometer. Diffraction data was
collected over the full sphere and corrected for absorption.
The data reduction was performed using the Bruker SMART
program package. Structure solutions was carried out using
the SHELXS9721 package applying the heavy-atom method and
refined using SHELXL9721 against F2. All non-hydrogen atoms
were refined anisotropically, while hydrogen atoms were added to
the structure models on calculated positions.
1
2 H, C6H2), 7.38–8.11 (m, 16 H, NH + Ph) ppm. 31P{ H} NMR:
1.1 (s, 1 P, PPh3), 51.9 (s, 1 P, NPS) ppm. C34H41CuN2O2P2S2
(699.33): calcd. C 58.40, H 5.91, N 4.01; found: C 58.22, H 5.99,
N 3.97.
Complex [Cu(PPh3)LV] was obtained as colourless crystals.
Yield: 0.451 g, 64% (Path A); 1.692 g, 72% (Path B). M.p. 71 ◦C.
1
IR: 614 (P S), 1000 (POC), 1118 (COC), 1569 (SCN) cm-1. H
3
3
NMR: 1.04 (d, JH,H = 6.2 Hz, 6 H, CH3, iPr), 1.08 (d, JH,H
=
6.1 Hz, 6 H, CH3, iPr), 3.80–4.72 (m, 20 H, CH2, crown), 4.94 (d.
Crystal data for [Cu4LI4]. C36H80Cu4N8O8P4S8, Mr = 1387.72 g
mol-1, monoclinic, space group Cc, a = 14.6549(9), b = 14.8054(8),
sept, 3JH,H = 6.0 Hz, 3JP,H = 10.3 Hz, 2 H, OCH), 7.30–8.11 (m, 15
◦
1
3
H, Ph) ppm. 31P{ H} NMR: 0.7 (s, 1 P, PPh3), 53.9 (s, 1 P, NPS)
c = 28.178(2) A, b = 95.782(5) , V = 6082.7(7) A , Z = 4, r = 1.515 g
cm-3, m(Mo-Ka) = 1.808 mm-1, reflections: 21 129 collected, 10 081
unique, Rint = 0.056, R1(all) = 0.0603, wR2(all) = 0.1348.
˚
˚
ppm. C35H49CuN2O6P2S2 (783.40): calcd. C 53.66, H 6.30, N 3.58;
found: C 53.81, H 6.26, N 3.61.
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The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 11577–11586 | 11585
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Crystal data for [Cu8LII8]. C80H176Cu8N16O16P8S16, Mr
2887.41 g mol , triclinic, space group P1, a = 16.742(2), b =
=
A. Garau, M. B. Hursthouse, S. L. Huth, F. Isaia, V. Lippolis, H. R.
Ogilvie and G. Verani, Eur. J. Inorg. Chem., 2006, 200; (i) D. J. Birdsall,
A. M. Z. Slawin and D. J. Woollins, Inorg. Chem., 1999, 38, 4152; (j) P.
Moore, W. Errington and S. P. Sangha, Helv. Chim. Acta, 2005, 88, 782;
(k) O. Siiman, C. P. Huber and M. L. Post, Inorg. Chim. Acta, 1977, 25,
L11.
-1
¯
˚
18.063(2)◦, c = 23.031(3) A, a = 78.498(3), b = 77.747(3), g =
3
-3
˚
79.888(3) , V = 6604.6(14) A , Z = 2, r = 1.452 g cm , m(Mo-
Ka) = 1.668 mm-1, reflections: 65 444 collected, 30 295 unique,
Rint = 0.052, R1(all) = 0.0870, wR2(all) = 0.1331.
6 E. Herrmann, R. Richter and N. T. T. Chau, Z. Anorg. Allg. Chem.,
1997, 623, 403.
Crystal data for [Cu3LIII3]. C45H72Cu3N6O6P3S6, Mr = 1268.98
7 F. D. Sokolov, M. G. Babashkina, D. A. Safin, A. I. Rakhmatullin, F.
Fayon, N. G. Zabirov, M. Bolte, V. V. Brusko, J. Galezowska and H.
Kozlowski, Dalton Trans., 2007, 4693.
8 F. D. Sokolov, M. G. Babashkina, F. Fayon, A. I. Rakhmatullin, D.
A. Safin, T. Pape and F. E. Hahn, J. Organomet. Chem., 2009, 694,
167.
9 M. L. Niven, P. Kyriacou and T. A. Modro, J. Chem. Soc., Dalton
Trans., 1988, 1915.
10 E. G. Yarkova, N. R. Safiullina, I. G. Chistyakova, N. G. Zabirov, F.
M. Shamsevaleev and R. A. Cherkasov, Zh. Obshch. Khim. (USSR),
1990, 60, 1790.
11 F. D. Sokolov, V. V. Brusko, N. G. Zabirov and R. A. Cherkasov, Curr.
Org. Chem., 2006, 10, 27.
-1
¯
g mol , trigonal, space group R3, a = 17.9577(7), b = 17.9577(7),
◦
3
˚
˚
c = 32.1945(17) A, g = 120 , V = 8991.1(7) A , Z = 6, r = 1.406 g
cm-3, m(Mo-Ka) = 1.391 mm-1, reflections: 16 656 collected, 3745
unique, Rint = 0.0498, R1(all) = 0.0351, wR2(all) = 0.0748.
Crystal data for [Cu3LIV3]. C48H78Cu3N6O6P3S6, Mr = 1311.05
g mol-1, monoclinic, space group P21/c, a = 9.1333(4), b =
◦
3
˚
˚
28.4411(9), c = 24.4109(10) A, b = 91.382(3) , V = 6339.2(4) A ,
Z = 4, r = 1.374 g cm-3, m(Mo-Ka) = 1.317 mm-1, reflections: 49 505
collected, 12 302 unique, Rint = 0.0753, R1(all) = 0.0623, wR2(all) =
0.0751.
12 M. G. Babashkina, D. A. Safin, F. Fayon, A. I. Rakhmatullin, F. D.
Sokolov, A. Klein, D. B. Krivolapov, T. Pape, F. E. Hahn and H.
Kozlowski, Dalton Trans., 2010, 39, 8261.
13 J. E. Huheey, E. A. Keiter, R. L. Keiter, in Inorganic Chemistry:
Principles of Structure and Reactivity, (Eds: Harper Collins College
Publishers), New York, 1993, 4th ed.
14 V. N. Solov’ev, N. G. Zabirov, R. A. Cherkasov and I. V. Martynov,
Zh. Strukt. Khim. (USSR), 1991, 32, 80.
15 (a) D. A. Safin, F. D. Sokolov, H. No¨th, M. G. Babashkina, T. R.
Gimadiev, J. Galezowska and H. Kozlowski, Polyhedron, 2008, 27,
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Krivolapov, I. A. Litvinov and H. Kozlowski, Polyhedron, 2009, 28,
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11586 | Dalton Trans., 2010, 39, 11577–11586
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©