Synthesis and structural characterization of cobalt, nickel and copper phosphanylthiolato complexes

Article abstract of DOI:10.1002/ejic.200900941

Neutral cobalt, nickel and copper complexes of a series of phosphanylthiol ligands Ph_nP(C₆H₄SH-2)_3-n (n = 1, 2) have been synthesized and characterized by IR and NMR (¹H and ³¹P) spectroscopy, FAB mass spectrometry and X-ray structural analysis. All of the compounds, with the exception of [Co(Ph₂PC ₆H₄S-2}₂], were synthesized by electrochemical oxidation of the anodic metal (cobalt, nickel or copper) in an acetonitrile solution of the appropriate ligand and a small amount of tetramethylammonlum Perchlorate as an electro- lytic carrier. The presence of an additional coligand (PPh₃, dppe, dppm or bipy) in the cell led to the synthesis of mixed complexes in one step. The crystal structures of [Co[Ph₂P(O)C ₆H₄S-2}₂] (1), [Co₂{PhP(C ₆H₄S-2)₂}₂(μ-N ₂)(bipy)₂] (2), [Ni₂(PhP(C₆H ₄S-2)₂}₂] (3), [Ni₂{PhP(C ₆H₄S-2)₂}₂(μ-dppe)]CH ₂Cl₂ (4), [Cu₂[Ph₂PC ₆H₄S-2}₂(PPh₃)₂] (5), [Cu₂(PhP(C₆H₄S-2)₂}(PPh ₃)₂(CH₃CN)] (6), [Cu₂(Ph ₂PC₆H₄S-2}₂(μ-dppe)] (7) and [Cu₂(Ph₂PC₆H₄S-2} ₂(μ-dppm)] (8) are discussed.

Full text of DOI:10.1002/ejic.200900941

FULL PAPER
DOI: 10.1002/ejic.200900941
Synthesis and Structural Characterization of Cobalt, Nickel and Copper
Phosphanylthiolato Complexes
Patricia Fernández,[a] Antonio Sousa-Pedrares,[a] Jaime Romero,[a] María L. Durán,[a]
Antonio Sousa,[a] Paulo Pérez-Lourido,[b] and José A. García-Vázquez*[a]
Keywords: Cobalt / Nickel / Copper / Electrochemical synthesis / S ligands / Phosphane ligands
Neutral cobalt, nickel and copper complexes of a series of
phosphanylthiol ligands PhnP(C6H4SH-2)3–n (n = 1, 2) have
been synthesized and characterized by IR and NMR (1H and
31P) spectroscopy, FAB mass spectrometry and X-ray struc-
tural analysis. All of the compounds, with the exception of
[Co{Ph2PC6H4S-2}2], were synthesized by electrochemical
oxidation of the anodic metal (cobalt, nickel or copper) in
an acetonitrile solution of the appropriate ligand and a small
amount of tetramethylammonium perchlorate as an electro-
lytic carrier. The presence of an additional coligand (PPh3,
dppe, dppm or bipy) in the cell led to the synthesis of mixed
complexes in one step. The crystal structures of [Co{Ph2P(O)-
C6H4S-2}2] (1), [Co2{PhP(C6H4S-2)2}2(µ-N2)(bipy)2] (2),
[Ni2{PhP(C6H4S-2)2}2] (3), [Ni2{PhP(C6H4S-2)2}2(µ-dppe)]·
CH2Cl2 (4), [Cu2{Ph2PC6H4S-2}2(PPh3)2] (5), [Cu2{PhP-
(C6H4S-2)2}(PPh3)2(CH3CN)] (6), [Cu2{Ph2PC6H4S-2}2(µ-
dppe)] (7) and [Cu2{Ph2PC6H4S-2}2(µ-dppm)] (8) are dis-
cussed.
Scheme 1. The complexes were obtained by using an elec-
trochemical procedure in which the metal was the anode of
a cell containing the ligand in acetonitrile solution. This
method is a simple route and avoids the presence of other
anionic species that would be competitors for the ligands
under investigation. For this reason, the nature of the com-
pounds obtained could occasionally differ from those pre-
pared by more traditional methods. In addition, the method
also allowed the preparation of mixed complexes in one
step when a second ligand was added to the electrochemical
cell.
Introduction
There is considerable current interest in the chemistry of
metal complexes with heterodonor polydentate ligands that
combine tertiary phosphane groups with nitrogen,[1] oxy-
gen[2] or sulfur atoms.[3] Of these, phosphanylthiolato li-
gands incorporating both thiolato and tertiary phosphane
donor atoms form stable complexes with a wide range of
metals including lanthanides, transition- and post-transi-
tion metals. To date, most studies have focused on bidentate
Ph2PCH2CH2SH or Ph2PC6H4SH-2 ligands,[3] while the
potentially tridentate ligand PhP(C6H4SH-2)2 has received
less attention. In a previous paper, we reported the prepara-
tion and crystal structures of CoIII and NiII complexes with
the bidentate ligand Ph2PC6H4SH-2 and also with the tri-
methylsilyl derivative Ph2P{C6H4SH-2(Me3Si-3)}.[4] More
recently, the synthesis, by non-electrochemical methods, of
the dimeric compound [Ni2{PhP(C6H4S-2)2}] was reported,
and the crystal structure was examined in order to establish
the chemical connectivity – the data were not of sufficient
quality for a more detailed analysis.[5] Copper complexes
with these ligands have not been previously described.
As a result of our continued interest in the chemistry of
metal complexes with phosphanylthiolato ligands,[6] we now
report the synthesis and characterization of new cobalt,
nickel and copper complexes with the ligands described in
Scheme 1.
Results and Discussion
Cobalt Compounds
The reaction of CoCl2 with the potentially bidentate li-
gand Ph2PC6H4SH-2 in methanol in the presence of NEt3
led to the formation of the paramagnetic green compound
[Co{Ph2PC6H4S-2}2]. The formation of this CoII species
contrasts with that previously observed in the synthesis of
cobalt complexes with other bidentate phosphanylthiolato
[a] Departamento de Química Inorgánica, Universidad de Santi-
ago de Compostela,
15782 Santiago de Compostela, Spain
Fax: +34-981-547102
E-mail: josearturo.garcia@usc.es
[b] Departamento de Química Inorgánica, Universidad de Vigo,
36200 Vigo, Spain
814
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Cobalt, Nickel and Copper Phosphanylthiolato Complexes
ligands through an electrochemical procedure, in which the tris(diphenylphosphanylmethyl)ethane]dicobalt[9] and (µ2-
formation of diamagnetic octahedral CoIII complexes was dinitrogen)-bis{bis[2-(diisopropylphosphanyl)-4-methyl-
commonly observed.[4]
phenyl]amido}dicobalt.[10] In both of these cases, the bond
Crystals of [Co{Ph2P(O)C6H4S-2}2] (1) suitable for X- length between the nitrogen atoms and the presence of a
ray studies were obtained by slow air concentration of the linear Co–N–N–Co group are consistent with the situation
mother liquor, and structural studies show the presence of a found in the compound reported here.
CoII ion with a tetrahedral coordination environment. The
Description of the Structures
oxygen incorporated into the oxophosphanylthiolato moi-
Compounds [Co{Ph2P(O)C6H4S-2}2] (1) and [Co2{PhP-
(C6H4S-2)2}2(µ-N2)(bipy)2] (2) were studied by X-ray dif-
fraction. The molecular structure of 1 is shown in Figure 1
together with the atom labelling scheme adopted. Selected
bond lengths and angles (with the estimated standard devi-
ations) are listed in Table 1. The compound consists of dis-
crete molecules in which the metal is coordinated to two
monoanionic bidentate ligands bonded to the metal atom
through the oxygen and sulfur atoms. The environment
around the metal can be described as a slightly distorted
tetrahedral [CoO2S2], in which the bond angles correspond-
ing to six-membered chelate rings are slightly smaller than
those expected for compounds with a regular geometry.
ety could originate from adventitious oxygen during the
crystallization process. Such facile oxidation from phos-
phane to oxophosphane has been observed in other com-
pounds containing this type of ligand.[7]
The electrochemical oxidation of a sacrificial cobalt an-
ode in an electrochemical cell containing an acetonitrile
solution of the potentially tridentate ligand PhP(C6H4SH-
2)2 gave a brown solid, the analytical data for which are
consistent with the formation of the CoIII complex
[Co2{PhP(C6H4S-2)2}3]. The electrochemical efficiency
(moles of metal dissolved per Faraday of charge) of
0.50 molF–1 indicates that the anodic oxidation of the
metal leads to the formation of CoII, with subsequent oxi-
dation to CoIII in solution as soon as it is formed. The
compound is diamagnetic, and the 1H NMR spectrum con-
firms the presence of the coordinated ligand. The 31P NMR
spectrum shows signals at δ = 87 and 80 ppm and the FAB
mass spectrum shows the parent peak at m/z = 1092 with
the appropriate isotopic distribution, and this is consistent
with the proposed formula.
Attempts to obtain crystals suitable for an X-ray study
were unsuccessful and, as a result, the proposed structure
for this compound should be considered as tentative. How-
ever, the structure could be similar to that found for the
FeIII compound [Fe2{PhP(C6H4S-2)2}3], which has the
same ligand, an equivalent empirical formula,[8] and the X-
ray structure shows the presence of a dimer in which both
metal atoms are in a distorted octahedral geometry and the
two octahedra share a common face comprising three thiol-
ato sulfur atoms.
Figure 1. ORTEP diagram of the molecular structure of 1 with
50% thermal ellipsoid probability.
When 2,2Ј-bipyridine was added to the electrochemical
cell as a coligand, the procedure led to the formation of
the mixed CoII complex [Co{PhP(C6H4S-2)2}(bipy)]. The
presence of the coligand allows the stabilization of the
metal in the low oxidation state, as observed previously in
the synthesis of other mixed cobalt complexes containing
similar ligands.[8] The mother liquors from the synthesis
processes were concentrated gently by passing a stream of
nitrogen through in an attempt to avoid possible oxidation
of the metal and/or ligand. This process gave rise to brown
crystals that were suitable for X-ray diffraction. The re-
solved structure (vide infra) shows the presence of the spe-
Table 1. Selected bond lengths [Å] and angles for 1.
Co1–O1
Co1–O2
1.996(2)
1.989(2)
S2–C20
P1–O1
1.758(4)
1.522(3)
1.517(2)
1.765(4)
100.57(7)
113.40(4)
114.98(8)
Co1–S1
Co1–S2
O2–Co1–O1
O1–Co1–S1
O2–Co1–S1
2.2690(11)
2.2946(11)
102.55(10)
100.47(8)
125.05(8)
P2–O2
S1–C2
O2–Co1–S2
S1–Co1–S2
O1–Co1–S2
The Co–S [2.2690(11) and 2.2946(11) Å] and Co–O
cies [Co2{PhP(C6H4S-2)2}2(bipy)2(µ2-N2)] (2), in which two [1.996(2) and 1.989(2) Å] bond lengths are very close to
units of the initial compound are joined together by a dini- those reported for CoII complexes with related ligands.
trogen molecule that acts as a bridging ligand between the Thus, these values are similar to those found in the tetrahe-
two original molecules. Although not common, cobalt com- dral complex [Co{N(OPPh2)(SPPh2)-O,S}2] [av. Co–S
plexes that contain dinitrogen as a bridging ligand are 2.331 Å, av. Co–O 1.980(6) Å],[11] in the anion
known, usually with the metal in a relatively low oxidation [Co(SC10H13)3CH3CN]–
[av.
Co–S
2.28 Å],[12]
in
state and in the presence of phosphorus donor ligands. Ex- [Co{N(SPPh2)2}2] [av. Co–S 2.335(2) Å][13] or in other mo-
amples of such complexes include (µ2-dinitrogen)-bis[1,1,1- nomeric CoII compounds with a tetrahedral geometry.[14]
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J. A. García-Vázquez et al.
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The bond lengths and angles in the coordinated ligand described complexes that contain a dinitrogen molecule as
are similar to those in the free ligand.[15] The average value a bridge.[9,10] On the other hand, the bond length between
for the P–O bond, 1.519(3) Å, is slightly longer than that the two nitrogen atoms, 1.156(7) Å, is relatively short and
[1.493(3) Å] found in the free ligand, and this can be attrib- is similar to that in the aforementioned complexes and is
uted to the weakening of the P–O bond by coordination to also very similar to the value of 1.147(4) Å for the anion
the metal.
(µ2-dinitrogen)-bis{tris[bis(isopropyl)phosphanylmethyl]-
A view of the molecular structure of 2 is shown in Fig- phenylborato}dicobaltate.[16]
ure 2 together with the atom labelling scheme adopted. A
The bond lengths Co–S and Co–P are as one would ex-
selection of bond lengths and angles (with the estimated pect and are comparable to those found in related com-
standard deviations) is listed in Table 2. The compound is plexes.[4,17] Similarly, the Co–N(bipy) bond lengths are
dinuclear, and the two cobalt atoms are joined to one an- within the range found for these bonds in octahedral CoII
other through an –N–N– group that acts as a bridge be- complexes with a chelate bipyridine donor ligand.[18] Fi-
tween the two metal centres, which gives rise to an inversion nally, the shortest bond length corresponds to the Co–N3
centre between the two nitrogen atoms. A dianionic phos- bond, 1.910(4) Å, and is slightly greater than those in the
phanylthiolato ligand is also coordinated to each of the co- above-mentioned tetracoordinate dinitrogen cobalt com-
balt centres, and each of these is bound to the metal pounds,[9,10] which have values in the range 1.768–1.806 Å,
through the two thiolato sulfur atoms and the phosphorus and this difference can probably be attributed to the change
atom. The coordination sphere around each metal is com- in coordination number from four to six.
pleted with a bipyridine ligand coordinated in a chelate
manner through the two nitrogen donor atoms. The envi-
ronment around each metal is octahedral [CoN3S2P] and
Nickel Compounds
this is essentially regular, as can be seen from the bond
angles for this compound.
The electrochemical oxidation of a nickel anode in a
solution of PhP(C6H4SH-2)2 in acetonitrile led to the for-
mation of a crystalline product, the analytical data for
which are consistent with the formula [Ni{PhP(C6H4S-
2)2}]. The complex is diamagnetic, and the 131P NMR spec-
trum has a single signal at δ = 73 ppm, which is clearly at
a lower field than the corresponding signal in the free li-
gand (δ = –21 ppm); this indicates that the phosphorus is
coordinated to the metal in the complex. Crystals suitable
for study by X-ray diffraction were obtained directly from
the electrochemical cell. The resolved structure shows the
presence of a dimeric species in which the metal atoms are
joined by a double thiolato bridge, a situation that is consis-
tent with the spectroscopic data discussed above and with
previously reported data.[5]
The presence in the electrochemical cell of additional
phosphorus donor coligands enabled mixed complexes to
be obtained in a single step. For example, the presence in
the cell of PPh3 led to the formation of [Ni{PPh(C6H4S-
2)2}PPh3], the X-ray structure of which shows it to be struc-
turally equivalent to the complex [Ni{PPh(C6H4S-2)2}-
(PPh2Me)], previously synthesized from the precursor
[NiCl2(PPh2Me)2].[5] As a result, the structure of this com-
pound will not be discussed here.
The incorporation of diphosphane 1,2-bis(diphenylphos-
phanyl)ethane (dppe) as an additional ligand led to the for-
mation of the mixed complex [Ni2{PPh(C6H4S)2}2(µ-
dppe)]. The 31P NMR spectrum contains two signals at δ
= 73 and 34 ppm, which result from the presence of two
inequivalent phosphorus atoms in the complex. Crystals of
[Ni2{PhP(C6H4S-2)2}2(µ-dppe)]·CH2Cl2 (4) suitable for X-
ray studies were obtained by crystallization of the initial
product from dichloromethane/acetone.
Figure 2. ORTEP diagram of the molecular structure of 2 with
50% thermal ellipsoid probability.
Table 2. Selected bond lengths [Å] and angles [°] for 2.[a]
Co1–N3
Co1–N1
Co1–N2
1.910(4)
1.986(4)
1.991(4)
Co1–S1
Co1–S2
N3–N3#
2.2397(14)
2.2468(15)
1.156(7)
Co1–P1
2.1759(13) S1–C1
1.769(5)
N3–Co1–N1
N3–Co1–N2
N3–Co1–P1
N3–Co1–S1
N3–Co1–S2
N2–Co1–P1
N2–Co1–S1
P1–Co1–S1
91.31(17)
94.01(17)
N1–Co1–S2
N2–Co1–S2
95.17(16)
175.69(15)
86.14(5)
173.26(14) P1–Co1–S2
88.25(14)
87.58(14)
92.45(11)
96.02(13)
89.13(5)
S1–Co1–S2
N1–Co1–N2
N1–Co1–P1
N1–Co1–S1
N3#–N3–Co1
88.09(6)
80.77(19)
91.66(12)
176.73(15)
176.0(6)
[a] Symmetry transformations used to generate equivalent atoms:
#: –x, –y, –z + 1.
Description of the Structures
It is worth highlighting the presence of a Co–N–N–Co
group that is practically linear, with a N3#–N3–Co angle
Compounds [Ni2{PhP(C6H4S-2)2}2] (3) and [Ni2{PhP-
of 176.0(6)°, a situation similar to that found in previously (C6H4S-2)2}2(µ-dppe)]·CH2Cl2 (4) were studied by X-ray
816
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Cobalt, Nickel and Copper Phosphanylthiolato Complexes
diffraction. The molecular structure of 3 is shown in Fig- one another through a diphosphane ligand that acts as a
ure 3, together with the atom labelling scheme adopted. A bridge between the two nickel atoms; each metal is coordi-
selection of bond lengths and angles (with the estimated nated through one of the phosphorus atoms. The environ-
standard deviations) is listed in Table 3. The structural ment around each of the metals is square planar [NiS2P2],
analysis reveals that this compound is dinuclear and con- although the distortion in this case is more marked than
sists of two nickel–phosphanylthiolato units joined together that observed in the other complexes discussed here.
by two sulfur atoms, which act as bridges between the two
metal centres. The environment around each metal centre is
[NiS3P] square planar, and the Ni1 and Ni2 atoms are lo-
cated 0.1068 and 0.0814 Å, respectively, from the best plane
defined by the four donor atoms. The planes around each
of the nickel centres form a dihedral angle of 76.27°.
Figure 4. ORTEP diagram of the molecular structure of 4 with
50% thermal ellipsoid probability.
Figure 3. ORTEP diagram of the molecular structure of 3 with
Table 4. Selected bond lengths [Å] and angles in 4.[a]
50% thermal ellipsoid probability.
Ni1–P1
Ni1–S1
Ni1–S2
P1–Ni1–S1
P1–Ni1–S2
S2–Ni1–S1
2.1161(8)
2.1753(8)
2.1647(8)
87.03(3)
87.97(3)
163.51(4)
Ni1–P2
S1–C1
S2–C7
P1–Ni1–P2
S1–Ni1–P2
S2–Ni1–P2
2.2214(8)
1.777(3)
1.772(3)
165.34(3)
92.02(3)
96.71(3)
Table 3. Selected bond lengths [Å] and angles [°] for 3.
Ni1–P1
Ni1–S1
Ni1–S2
Ni1–S4
P1–Ni1–S1
P1–Ni1–S2
S1–Ni1–S2
P1–Ni1–S4
S1–Ni1–S4
2.110(2)
2.156(2)
2.197(2)
2.236(2)
89.07(9)
88.05(9)
168.08(10)
171.90(10)
99.01(9)
Ni2–S4
Ni2–P2
Ni2–S2
Ni2–S3
S2–Ni1–S4
P2–Ni2–S3
P2–Ni2–S4
S3–Ni2–S4
P2–Ni2–S2
2.199(2)
2.105(2)
2.234(2)
2.156(2)
83.94(8)
88.48(9)
87.69(9)
170.52(10)
171.59(9)
[a] Symmetry transformations used to generate equivalent atoms:
# –x, –y, –z + 1.
The Ni–S bond lengths, 2.1647(8) and 2.1753(8) Å, are
similar and are analogous to those found in
[Ni(Ph2PC6H4S-2)2][21] [2.151(3) Å] and [Ni{Ph2PC6H3S-2-
(Me3Si-6)}2][4] [2.180(1) Å]. These values fall within the
range 2.149–2.179 Å usually found in square planar nickel
complexes with chelating ligands that contain sulfur donor
atoms. The Ni–P distances, on the other hand, are different
[2.1161(8) Å and 2.214(8) Å] depending on the nature of the
ligand bound to the metal and are slightly shorter in the
case of the chelating ligand. This situation is consistent with
those found in the systems described above, in which the
constraints caused by the ligand lead to a shortening of
the bond length in question. The species crystallizes with a
molecule of dichloromethane, and this is located within the
network without establishing significant interactions with
the complex itself.
The Ni–Ni bond length in small molecules are in the
range of 2.914 to 3.555 Å, and the value of 2.7197(14) Å in
our compound could indicate the existence of some degree
of interaction between the metal centres.[19] The Ni–S(term-
inal) bond lengths, which involve sulfur atoms from the che-
late rings, are slightly shorter [2.156(2)–2.156(2) Å] than
those for Ni–S (bridge) distances, in the range 2.197(2)–
2.236(2) Å, as in the case in other systems with terminal
and bridging sulfur atoms.[20] The Ni–P bond lengths
[2.110(2) and 2.105(2) Å], although within the expected
range, are at the lower end of the range found in complexes
that contain this type of ligand.[4,21]
The molecular structure of 4 is shown in Figure 4, to-
gether with the atom labelling scheme adopted. A selection
of bond lengths and angles (with the estimated standard
deviations) is listed in Table 4. The molecule has an inver-
sion centre located at the mid-point of the C–C bond of the
ethylene group of the dppe ligand, and the structural analy-
Copper Complexes
Neutral complexes [Cu{Ph2PC6H4S-2}] and [Cu2{PhP-
sis shows that the compound consists of discrete dimers in (C6H4S-2)2}] were obtained by electrochemical oxidation of
which two Ni–phosphanylthiolato units are connected to anodic copper metal in a cell containing the ligand dis-
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J. A. García-Vázquez et al.
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solved in acetonitrile. Ef values of 1.0 molF–1 indicate that phenylphosphane. As a result, the ligand acts as a PS che-
the anodic oxidation of the metal leads to the formation of late system with respect to one of the copper atoms and as
CuI.
a bridge to both metals.
Both compounds were obtained at the bottom of the cell
as insoluble solids. The presence of a single ligand that does
not coordinatively satisfy the metal leads to a polymeriza-
tion process in which the thiolato sulfur atoms act as brid-
ges between the metal centres. As a consequence, these com-
pounds are insoluble in the majority of commonly used or-
ganic solvents, and attempts to obtain monocrystals suit-
able for X-ray diffraction proved unsuccessful. The IR spec-
tra of both compounds contain bands associated with the
coordinated ligands, and the FAB mass spectra of
[Cu{Ph2PC6H4S-2}] shows peaks corresponding to species
arising from different levels of polymerization (see Experi-
mental Section).
The FAB
mass
spectra
of
[Cu2{PhP(C6H4S-2)2}] could not be recorded because of
the lack of solubility of the compound in the matrix.
The presence in the cell of coligands that can coordina-
tively saturate the metal must to some extent inhibit the
polymerization process, and, as a result, the formation of Figure 5. ORTEP diagram of the molecular structure of 5 with
50% thermal ellipsoid probability.
oligomeric species with lower molecular masses was ob-
served. For example, the addition of PPh3 to the electro-
chemical cell enabled the isolation of the molecular species,
The environment around each copper atom is a slightly
the analytical and X-ray structural data of which are consis- distorted tetrahedron [P2S2]. The two copper centres are
tent with compounds with the empirical formulae 2.9566(16) Å from one another, and this distance is greater
[Cu2{Ph2PC6H4S-2}2(PPh3)2] (5) and [Cu2{PhP(C6H4S-2) than the sum of the radii for these two metal atoms
2}(PPh3)2(CH3CN)] (6). Similarly, the presence in the cell (2.56 Å)[22] and is sufficiently high as to preclude the pos-
of bidentate phosphorus donor ligands such as dppe or sibility of an interaction between the two metals. Despite
dppm led to the formation of species for which the analyti- the fact that X-ray structural data are not available for
cal and structural data are consistent with compounds with other copper complexes with phophinothiol ligands, the
the empirical formulae [Cu2{Ph2PC6H4S-2}2(µ-dppe)] (7) values for the Cu–S distances are similar to those found
and [Cu2{Ph2PC6H4S-2}2(µ-dppm)] (8).
in other dimeric tetrahedral copper complexes that contain
thiolato ligands – e.g. in [Cu2(3-Me3Sipyt)2(dppe)3] with a
Cu–S bond length of 2.320(3) Å.[23] The two Cu–P dis-
tances for the two phosphanes [2.2797(16) and
2.2581(13) Å] are similar to one another and are in the
range found in the indicated complex, i.e. [Cu2(3-Me3Sipyt)2-
(dppe)3].
Description of the Structures
Compounds 5–8 were studied by X-ray diffraction. A se-
lection of bond lengths and angles (with the estimated stan-
dard deviations) in listed in Tables 5–8.
The molecular structure of [Cu2{PhP(C6H4S-2)2}(PPh3)2-
(CH3CN)] (6) is shown in Figure 6, together with the atom
labelling scheme adopted. A selection of bond lengths and
angles (with the estimated standard deviations) is listed in
Table 6. The compound consists of dimeric units in which
the two copper atoms are joined by two sulfur atoms of the
dianionic ligand, which acts as a bridge between the two
metal centres. In this coordination mode the ligand acts as
a tripodal system – it chelates in a PS fashion to one of the
copper centres and doubly bridges the two metal centres.
The coordination spheres around the copper centres are
Table 5. Selected bond lengths [Å] and angles [°] for 5.[a]
Cu1–P1
Cu1–P2
Cu1–S1
P1–Cu1–S1
P2–Cu1–P1
P2–Cu1–S1
2.2797(16)
2.2581(13)
2.3323(8)
89.85(6)
114.69(3)
125.79(6)
S1–Cu1#
2.3916(16)
2.9566(12)
1.799(7)
109.21(6)
112.13(5)
102.52(5)
Cu1–Cu1#
S1–C2
P1–Cu1–S1#
P2–Cu1–S1#
S1–Cu1–S1#
[a] Symmetry transformations used to generate equivalent atoms:
#: –x + 2, –y, –z + 1.
The resolved structure of [Cu2{Ph2PC6H4S-2}2(PPh3)2]
(5) (Figure 5) shows that the compound is composed of cen- different. Cu1 is bonded to two bridging sulfur atoms, and
trosymmetric dimeric species in which the two thiolato sul- the coordination sphere is completed by a phosphorus atom
fur atoms from the two phosphanylthiolato ligands act as from the same phosphothiolato ligand and another phos-
bridges between the two metal atoms, and these are related phorus atom from a triphenylphosphane molecule. In con-
to one another through a centre of symmetry located at the trast, the second copper centre, Cu2, is bonded to the phos-
centre of the Cu2S2 ring. In addition, each copper atom is phorus atom of a triphenylphosphane molecule and the ni-
coordinated to a phosphorus atom of one of the phosphan- trogen atom of an acetonitrile molecule (which originates
ylthiolato ligands and to the phosphorus atom of the tri- from the solvent used in the synthetic process), in addition
818
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 814–823

Cobalt, Nickel and Copper Phosphanylthiolato Complexes
The bridging sulfur atoms are equidistant from the two
copper centres, i.e. the thiolato bridge is symmetrical, with
bond lengths in the range 2.3351(4)–2.4055(4) Å, values
very similar to those found in the compound described
above. The Cu–P bond lengths associated with the tri-
phenylphosphane ligand, 2.2178(4) and 2.2260(4) Å, are
practically identical whereas that corresponding to the thi-
olato ligand is slightly longer, 2.2395(4) Å. However, these
values are as one would expect and are analogous to those
found in [Cu{Ph2PC6H4S-2}PPh3]2 and in other CuI com-
plexes with phosphane ligands.[23]
The complex contains a coordinated acetonitrile mole-
cule that originates from the solvent used in the electro-
chemical synthesis. This molecule completes the coordina-
tion sphere of Cu2 by coordination through the nitrogen
atom. The Cu–N bond length, 2.0299(13) Å, and the C55–
N1–Cu2 bond angle, 163.29(13)°, are as one would expect,
with the former value analogous to the value 1.944(7) Å
found in the dimeric complex [Cu2(C6H7N3S2)2(CH3CN)2]-
(BF4)2, which also contains thiolato bridges and a coordi-
nated acetonitrile molecule.[24] The acetonitrile molecule is
essentially linear [N1–C55–C56 bond angle of 178.80(18)°],
and the N1–C55 bond length [1.136(2) Å] is indicative of a
triple bond between the carbon and nitrogen atoms.[25] The
compound crystallizes with three acetonitrile molecules that
are located within the network but do not interact signifi-
cantly with the complex.
The molecular structure of [Cu2{Ph2PC6H4S-2}(µ-dppe)]
(7) and [Cu2{Ph2PC6H4S-2}(µ-dppm)] (8) are shown in Fig-
ure 7, together with the atom labelling scheme adopted. A
selection of bond lengths and angles (with the estimated
standard deviations) is listed in Tables 7 and 8. The struc-
tures of both compounds are similar and consist of dimeric
species in which the copper atoms are joined by a double
thiolato bridge with sulfur atoms from two different ligands
and a phosphorus atom of the diphosphane ligand, which
also acts as a bridge. In this way, the environment around
each of the copper atoms is a slightly distorted tetrahedral
[P2S2]. This situation is reflected by the bond angles in the
Figure 6. ORTEP diagram of the molecular structure of 6 with
50% thermal ellipsoid probability.
Table 6. Selected bond lengths [Å] and angles [°] for 6.
Cu1–P1
Cu1–P2
Cu1–S1
Cu1–S2
Cu1–Cu2
P1–Cu1–S1
P1–Cu1–S2
P2–Cu1–P1
P2–Cu1–S1
P2–Cu1–S2
S1–Cu1–S2
2.2395(4)
2.2178(4)
2.3351(4)
2.3772(4)
2.8045(2)
90.636(14)
90.168(14)
127.744(15) N1–Cu2–S2
122.718(15) S2–Cu2–S1
112.256(14) N1–Cu2–S1
107.429(14) P3–Cu2–S1
Cu2–N1
Cu2–P3
Cu2–S2
Cu2–S1
N1–C55
N1–Cu2–P3
P3–Cu2–S2
2.0299(13)
2.2260(4)
2.3519(4)
2.4055(4)
1.136(2)
116.21(4)
124.646(14)
101.20(4)
105.957(13)
101.97(4)
104.390(14)
to the two bridging sulfur atoms. In both cases the copper
environment can be considered to be tetrahedral, in which
the two sulfur atoms form the common edge of the two
tetrahedra. A significant angular distortion is evident in the
Cu1 environment, and this is due to the chelating nature of
the phosphinothiolato ligand.
Figure 7. ORTEP diagrams of the molecular structures of 7 and 8 with 50% thermal ellipsoid probability.
Eur. J. Inorg. Chem. 2010, 814–823
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819

J. A. García-Vázquez et al.
FULL PAPER
metal environment, which cover a wide range of values; rous and one of the sulphur atoms are coordinated to one
the lowest angle corresponds to the five-membered chelate metal, while the other sulfur atom acts as a bridge. In com-
ring.
pound 6, the ligand behaves as a P(µ-S)2 donor; the P atom
is coordinated to one of the copper atoms, and the sulfur
atoms act as a bridge between the two metal centres.
Table 7. Selected bond lengths [Å] and angles [°] for 7.
Cu1–P1
Cu1–S2
Cu2–P2
Cu2–S1
Cu1–Cu2
P1–Cu1–P3
P3–Cu1–S2
P3–Cu1–S1
P2–Cu2–P4
P4–Cu2–S1
P4–Cu2–S2
2.2457(11)
2.3455(10)
2.2510(11)
2.3707(10)
2.6751(6)
126.26(4)
98.16(4)
112.99(4)
125.28(4)
100.42(4)
110.70(4)
Cu1–P3
Cu1–S1
Cu2–P4
Cu2–S2
2.2636(11)
2.4472(10)
2.2576(10)
2.4297(10)
1.781(4)
123.27(4)
84.99(4)
110.48(4)
123.27(4)
85.51(4)
Experimental Section
S1–C2
General Considerations: All manipulations were carried under an
inert atmosphere of dry nitrogen. Cobalt, nickel and copper (Ald-
rich Chemie) were used as plates (ca. 2ϫ2 cm). All other reagents
were used as supplied. The synthesis of the ligands was carried out
by using slight modifications of the standard literature pro-
cedure.[26] Elemental analyses were performed by using a Carlo–
Erba EA microanalyzer. IR spectra were recorded as KBr discs
P1–Cu1–S2
P1–Cu1–S1
S2–Cu1–S1
P2–Cu2–S1
P1–Cu2–S2
S1–Cu2–S2
109.92(4)
1
with a Bruker IFA-66 spectrophotometer. H and 31P spectra were
recorded on a Bruker AMX 300 MHz instrument with CDCl3 as
Table 8. Selected bond lengths [Å] and angles [°] for 8.
1
solvent. H NMR chemical shifts were determined against tms as
Cu1–P4
Cu1–S2
Cu2–P3
Cu2–S1
Cu1–Cu2
P4–Cu1–P2
P2–Cu1–S2
P2–Cu1–S1
P3–Cu2–P1
P1–Cu2–S1
P1–Cu2–S2
2.1998(13)
2.3516(11)
2.2269(12)
2.3946(11)
2.6223(7)
130.14(5)
88.80(4)
105.71(4)
126.89(4)
86.59(4)
Cu1–P2
Cu1–S1
Cu2–P1
Cu2–S2
2.2293(13)
2.4748(11)
2.2402(10)
2.4599(11)
1.782(4)
118.92(5)
109.01(4)
99.20(4)
internal standard and those of 31P against 85% H3PO4. The mass
spectra (FAB) were recorded on a Micromass Autospec spectrome-
ter by using 3-nitrobenzyl alcohol as the matrix material.
S1–C2
Synthesis of the Complexes
P4–Cu1–S2
P4–Cu1–S1
S2–Cu1–S1
P3–Cu2–S1
P3–Cu2–S2
S1–Cu2–S2
[Co{Ph2PC6H4S-2}2]: This compound was prepared by reaction of
anhydrous CoCl2 and the ammonium salt of the ligand. A solution
of the ligand (0.200 g, 0.680 mmol) in methanol (50 mL) was
treated with tetramethylammonium hydroxide (0.285 mL,
0.680 mmol) in the same solvent. The solution was evaporated to
dryness, the resulting solid was dissolved in acetonitrile, and a solu-
tion of anhydrous CoCl2 (0.044 g, 0.340 mmol) in acetonitrile was
113.22(4)
116.02(4)
98.44(4)
108.23(4)
The thiolato bridge can be considered to be symmetrical,
as the bond lengths are only slightly different. The values added. The colour of the solution changed to dark green, and the
resulting solid was recovered, washed with acetonitrile and ether,
and dried under vacuum. C36H28CoP2S2 (645.6): calcd. C 66.9, H
of the Cu–P and Cu–S bond lengths for these compounds
are similar to those reported for 5 and 6 and do not warrant
further discussion.
Compound 8 crystallizes with half a molecule of dichlo-
romethane that is located within the network but does not
interact significantly with the complex.
4.3, S 9.9; found C 66.6, H 4.5, S 9.6. IR (KBr): ν = 1571 (m),
˜
1482 (s), 1442 (s), 1243 (m), 1091 (s), 1001 (m) 738(s), 694 (s), 524
(s) cm–1. FAB MS: m/z = 645 [M]+. Crystals of [Co{Ph2P(O)-
C6H4S-2}2] (1) suitable for X-ray studies were obtained by slow air
concentration of the mother liquor.
Electrochemical Synthesis: The rest of the metal complexes were
obtained by using an electrochemical procedure.[27] The cell con-
sisted of an anode suspended from a platinum wire, and the cath-
ode was also a platinum wire. The ligand was dissolved in acetoni-
trile, and a small amount of tetramethylammonium perchlorate was
added to the solution as a supporting electrolyte (Caution: perchlo-
rate compounds are potentially explosive and should be handled in
small quantities and with great care). For the synthesis of the mixed
complexes, the additional coligand was also added to the solution.
Applied voltages of 5–10 V allowed sufficient current flow for
smooth dissolution of the metal. Under these conditions, the elec-
trochemical cell can be summarized as:
Conclusions
A number of CoII, NiII and CuI complexes with a series
of phosphanylthiol ligands PhnP(C6H4SH-2)3–n (n = 1, 2)
have been prepared and characterized. With the exception
of [Co{Ph2P(O)C6H4S-2}2] (1), the complexes have been
synthesized by electrochemical oxidation of a metal anode
(cobalt, nickel or copper) in a cell containing the appropri-
ate phosphanylthiol ligand or this ligand and a coligand
such as PPh3, dppe, dppm or bipy. With the ligand
Ph2P(C6H4SH-2), the complexes 5, 7 and 8 are dinuclear,
and the ligand acts as a bridging P(µ-S) ligand between
both metallic centres. However, 1 is mononuclear, and the
ligand oxophosphanylthiolato coordinated as bidentate
chelate (PS) ligand is the result of oxidation of the phos-
phanylthiolato ligand. In the dinuclear compounds 2, 3, 4
and 6, the ligand PhP(C6H4SH-2)2 acts as a tridentate li-
gand in all cases, but displays a different coordination be-
haviour. Thus, in 2 and 4, the ligand acts as a chelating PS2
ligand and is coordinated to each metal atom. In 3, the
Pt(–)/CH3CN + PhnP(C6H4SH-2)3–n/M(+)
Pt(–)/CH3CN + PhnP(C6H4SH-2)3–n+ LЈ/M(+)
n = 1, 2; M = Co, Ni, Cu; LЈ = PPh3, dppe, dppm, bipy.
[Co2{PhP(C6H4S-2)2}3]:
A solution of the ligand (0.225 g,
0.690 mmol) in acetonitrile (50 mL) was electrolyzed at 10 mA over
2.5 h, and 27.0 mg of the metal was dissolved from the anode (Ef
= 0.50 molF–1). The colour of the solution changed to deep red,
and by the end of the electrolysis a red product had been deposited
in the cell. The solid was washed with acetonitrile and ether and
ligand behaves as a PS(µ-S) system, in which the phospho- dried under vacuum. C54H39Co2P3S6 (1091.1): calcd. C 59.5, H 3.6,
820 Eur. J. Inorg. Chem. 2010, 814–823
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Cobalt, Nickel and Copper Phosphanylthiolato Complexes
S 17.6; found C 59.9, H 3.8, S 17.8. IR (KBr): ν = 1570 (m), 1442
precipitated in the cell was filtered off, washed with acetonitrile and
˜
(s), 1425 (s), 1250 (m), 1103 (s), 1047 (w), 740 (s), 696 (m), 532 (s) ether, and dried under vacuum. C18H13Cu2PS2 (451.5): calcd. C
1
cm–1. H NMR (300 MHz, CDCl3, 25 °C): δ = 8.0–6.6 (m, 13 H) 47.9, H 2.9, S 14.2; found C 47.8, H 3.0, S 13.9. IR (KBr): ν =
˜
ppm. 31P NMR (300 MHz, CDCl3, 25 °C): δ = 87, 80 ppm. FAB
MS: m/z = 1092 [M]+, 767 [M – PhP(C6H4S-2)2]+.
1573 (m), 143 (s), 1118 (s), 1035 (m), 748 (s), 696 (m), 551 (s) cm–1.
NMR: insoluble compound. FAB MS: insoluble compound.
[Co{PhP(C6H4S-2)2}(bipy)]: A solution of the ligand (0.124 g,
0.380 mmol) and 2,2Ј-bipyridine (0.060 g, 0.380 mmol) in acetoni-
trile (50 mL) was electrolyzed at 10 mA over 2 h, and 22.1 mg of
the metal was dissolved from the anode (Ef = 0.50 molF–1). The
solid formed was recovered, washed with acetonitrile and ether,
and characterized as [Co{PhP(C6H4S-2)2}(bipy)]. C28H21CoN2PS2
(539.5): calcd. C 62.3, H 3.9, N 5.2, S 11.9; found C 61.9, H 3.9,
[Cu{Ph2PC6H4S-2}(PPh3)]: Electrochemical oxidation of a copper
anode in a cell containing a solution of Ph2PC6H4SH-2 (0.120 g,
0.410 mmol) and PPh3 (0.110 g, 0.410 mmol) in acetonitrile
(50 mL) at 14 V, 10 mA for 1 h led to the dissolution of 24.8 mg of
copper (Ef = 1.1 molF–1). During electrolysis, hydrogen was
evolved at the cathode, and at the end of the reaction, a crystalline
solid appeared at the bottom of the vessel. The solid was filtered
off, washed with acetonitrile and ether, and dried under vacuum.
C36H29CuP2S (619.1): calcd. C 69.8, H 4.7, S 5.1; found C 69.4, H
N 5.6, S 12.0. IR (KBr): ν = 1569 (m), 1439 (s), 1427 (s), 1028 (w),
˜
767 (s), 742 (s), 735 (s), 698 (m) 530(s) cm–1. FAB MS: m/z = 540
[M]+, 384 [M–bipy]+. Brown crystals of [Co2{PhP(C6H4S-2)2}2(µ2-
N2)(bipy)2] (2) suitable for X-ray studies were obtained upon slow
concentration of the mother liquor by bubbling N2 gas through the
solution.
4.8, S 4.9. IR: ν = 1569 (m), 1479 (m), 1436 (s), 1417 (s), 1097 (s),
˜
997 (w), 745 (s), 695 (s), 508 (m) cm–1. 1H NMR (300 MHz, CDCl3,
25 °C): δ = 8.0–7.0 (m, 29 H) ppm. 31P NMR (300 MHz, CDCl3,
25 °C): δ = 32.7, 27.8 ppm. FAB MS: m/z = 1239 [M2]+, 619 [M+],
356 [M+ – PPh3]. Crystals of [Cu2{Ph2PC6H4S-2}2(PPh3)2] (5) suit-
able for X-ray analysis were obtained by crystallization of the solid
from dichloromethane/methanol.
[Ni{PhP(C6H4S-2)2}]: In a similar experiment with nickel as the
anode, a solution of the ligand (0.124 g, 0.380 mmol) in acetonitrile
(50 mL) was electrolyzed at 10 mA over 2 h, and 22.0 mg of the
metal was dissolved from the anode (Ef
C18H13NiPS2 (383.1): calcd. C 56.4, H 3.4, S 16.7; found C 56.0,
=
0.50 molF–1).
[Cu2{PhP(C6H4S-2)2}(PPh3)2(CH3CN)]: The same procedure was
used for the synthesis of this compound. Ph(PC6H4SH-2)2 (0.061 g,
0.190 mmol) and PPh3 (0.100 g, 0.380 mmol) in acetonitrile
H 3.4, S 16.5. IR (KBr): ν = 1571 (s), 1430 (s), 12157 (m), 1099
˜
(m), 999 (m), 736 (s), 524 (s) cm–1. 1H NMR (300 MHz, CDCl3,
25 °C): δ = 7.8–6.6 (m, 13 H) ppm. 31P NMR (300 MHz, CDCl3,
25 °C): δ = 73 ppm. FAB MS: m/z = 765 [M2]+, 383 [M]+. Crystals
of [Ni2{PhP(C6H4S-2)2}2] (3) suitable for X-ray studies were ob-
tained directly from the cell.
(50 mL), 12 V, 10 mA, 1 h, 24.4 mg of metal dissolved (Ef
=
1.0 molF–1). At the end of the electrolysis, the solid deposited in
the cell was recovered, washed with diethyl ether, and dried under
vacuum. C56H46Cu2NP3S2 (1017.1): calcd. C 66.1, H 4.6, N 1.4, S
6.3; found C 65.8, H 4.5, N 1.5, S 6.6. IR (KBr): ν = 1569 (m), 1434
˜
1
[Ni2{PhP(C6H4S-2)2}2(PPh3)]: A solution of the ligand (0.124 g,
0.380 mmol) and PPh3 (0.098 g, 0.380 mmol) in acetonitrile
(50 mL) was electrolyzed at 10 mA over 2 h, and 23.5 mg of the
(s), 997 (w), 742 (m) cm–1. H NMR (300 MHz, CD3Cl, 25 °C): δ
= 7.8–6.8 (m, 43 H) ppm. 31P NMR (300 MHz, CDCl3, 25 °C): δ
= 27.8, 25.3 ppm. FAB MS: m/z = 1017 [M+], 977 [M – CH3-
CN]+. Crystals of [Cu2{PhP(C6H4S-2)2}(PPh3)2(CH3CN)]·
metal was dissolved from the anode (Ef
=
0.53 molF–1).
C36H28NiP2S2 (645.35): calcd. C 67.0, H 4.3, S 9.9; found C 66.7, 3CH3CN (6) suitable for X-ray studies were obtained by slow con-
H 4.3, S 9.8. IR (KBr): ν = 1569 (s), 1480 (m), 1178 (m), 742 (m),
centration of the mother liquor.
˜
1
530 (s) cm–1. H NMR (300 MHz, CDCl3, 25 °C): δ = 7.8–6.8 (m,
[Cu2{Ph2PC6H4S-2}2(dppe)]: A solution of the ligand (0.230 g,
0.780 mmol) and dppe (0.620 g, 1.560 mmol) in acetonitrile was
electrolyzed for 1.5 h at 10 mA, and 37.0 mg of the metal was dis-
solved (Ef = 1.0 molF–1). At the end of the electrolysis, the yellow
solution was filtered to remove any impurities and concentrated by
bubbling through N2 gas. Crystals of [Cu2{Ph2PC6H4S-2}2(dppe)]
(7) were obtained that were suitable for X-ray studies.
C62H52Cu2P4S2 (1112.2): calcd. C 67.0, H 4.7, S 5.8; found C 66.8,
29 H) ppm. 31P NMR (300 MHz, CDCl3, 25 °C): δ = 35.6,
28.1 ppm. FAB MS: m/z = 382 [M – Ph3P]+.
[Ni2{PhP(C6H4S-2)2}2(µ-dppe)]: A solution of the ligand (0.124 g,
0.380 mmol) and dppe (0.150 g, 0.380 mmol) in acetonitrile
(50 mL) was electrolyzed at 10 mA over 2 h, and 21.9 mg of the
metal was dissolved from the anode (Ef
C62H50Ni2P4S4 (1164.6): calcd. C 63.9, H 4.3, S 11.0; found C 63.8,
=
0.50 molF–1).
H 4.3, S 10.9. IR (KBr): ν = 1568 (s), 1178 (m), 1000 (m), 718 (m)
˜
H 4.9, S 5.5. IR (KBr): ν = 1545 (m), 1433 (s), 1026 (m), 999 (w),
˜
1
cm–1. H NMR (300 MHz, CDCl3, 25 °C): δ = 8.0–7.0 (m, 33 H),
740 (m), 720 (m) cm–1. 1H NMR (300 MHz, CD3Cl, 25 °C): δ =
8.0–6.8 (m, 48 H), 2.2 (br. s, 4 H) ppm. 31P NMR (300 MHz,
CDCl3, 25 °C): δ = 33.6, 31.9 ppm. FAB MS: m/z = 1112 [M]+, 754
[M – Ph2PC6H4S-2]+.
2.0 (m, 4 H) ppm. 31P NMR (300 MHz, CDCl3, 25 °C): δ = 73,
34 ppm. FAB MS: m/z = 1165 [M]+, 780 [M – PhP(C6H4S-2)2]+.
Crystals of [Ni2{PhP(C6H4S-2)2}2(µ-dppe)]·2CH2Cl2 (4) suitable
for X-ray studies were obtained by crystallization of the initial
product from dichloromethane/acetone.
[Cu2{Ph2PC6H4S-2}2(dppm)]: Ligand (0.115 g, 0.390 mmol), dppm
(0.150 g, 0390 mmol) in acetonitrile, 1 h at 10 mA and 9 V, 24.9 mg
of metal dissolved from the anode (Ef = 1.0 molF–1). At the end
of the electrolysis, yellow needles were deposited in the cell. The
solid was filtered off, washed with acetonitrile and ether, and dried
under vacuum. C61H50Cu2P4S2 (1098.2): calcd. C 66.7, H 4.6, S
[Cu{Ph2PC6H4S-2}]: A solution of the ligand Ph2PC6H4SH-2
(0.230 g, 0.784 mmol) in acetonitrile (50 mL) was electrolyzed at
10 mA over 2 h, and 48 mg of the metal was dissolved from the
anode (Ef = 1.0 molF–1). Within a few minutes an insoluble solid
appeared at the bottom of the cell. This solid was recovered,
washed with acetonitrile and ether, and dried under vacuum.
C18H14CuPS (356.0): calcd. C 60.6, H 3.9, S 8.9; found C 60.1, H
5.8; found C 66.3, H 4.5, S 5.8. IR (KBr): ν = 1572 (m), 1478 (m),
˜
1165 (m), 1089 (s), 779 (m), 744 (m) cm–1. 1H NMR (300 MHz,
CD3Cl, 25 °C): δ = 7.9–6.9 (m, 48 H), 2.2 (s, 2 H) ppm. 31P NMR
(300 MHz, CDCl3, 25 °C): δ = 29.5, 23.4 ppm. FAB MS: m/z =
1098 [M]+, 805 [M – Ph2PC6H4S-2]+; 712 [M – dppm]+. Crystals
of [Cu2{Ph2PC6H4S-2}2(dppm)]·1/2(CH2Cl2) (8) suitable for X-ray
4.1, S 8.7.IR (KBr): ν = 1571 (s), 1436 (s), 1421 (s), 1095 (s), 999
˜
(w), 740 (s), 694 (s), 524 (m) cm–1. NMR: insoluble compound.
FAB MS: m/z = 1071 [M3]+, 714 [M2]+, 357 [M]+; 293 [L+].
[Cu2{PhP(C6H4S-2)2}]: Ph(PC6H4SH-2)2 (0.160 g, 0.495 mmol), analysis were obtained by crystallization of the solid from dichloro-
2.5 h, 60 mg of metal dissolved (Ef = 1.0). The insoluble solid that methane/methanol.
Eur. J. Inorg. Chem. 2010, 814–823
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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J. A. García-Vázquez et al.
FULL PAPER
X-ray Crystallography Studies: Intensity data sets for compounds
5–8 were collected with a Bruker X8 Kappa APEXII diffractometer
(Mo-Kα radiation, λ = 0.71073 Å) equipped with a graphite mono-
chromator. The ω- and φ-scan technique was employed to measure
intensities in these crystals. Intensity data for compounds, 1–4 were
of all compounds were solved by direct methods. Crystallographic
programs used for structure solution and refinement were those
of SHELX97.[29] Scattering factors were those provided with the
SHELX program system. Missing atoms were located in the differ-
ence Fourier map and included in subsequent refinement cycles.
collected by using a Smart-CCD-1000 Bruker diffractometer (Mo- The structures were refined by full-matrix least-squares refinement
Kα radiation, λ = 0.71073 Å) equipped with a graphite monochro-
mator. The ω-scan technique was employed in these cases. Com-
pounds 1, 5, 6, 7 and 8 were measured at 100 K, and 2, 3 and 4 at
293 K. Decomposition of the crystals did not occur during data
collection. The intensities of all data sets were corrected for Lorentz
and polarization effects. Absorption effects in all compounds were
corrected by using the program SADABS.[28] The crystal structures
on F2. Hydrogen atoms were placed geometrically and refined by
using a riding model with Uiso constrained at 1.2 times Ueq of the
carrier C atom. For all structures, non-hydrogen atoms were aniso-
tropically refined, with the exception of the half disordered mole-
cule of dichloromethane in compound 8 (occupancies 50:50). Dis-
order was typically handled by introducing split positions for the
affected groups into the refinement of the respective occupancies.
Table 9. Summary of crystal data and structure refinement for the cobalt and nickel compounds.
Compound
1
2
3
4
Empirical formula
Formula weight
Crystal size [mm]
Temperature [K]
Wavelength [Å]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C36H28O2P2S2Co
677.57
0.28ϫ0.18ϫ0.06
100(2)
C56H42Co2N6P2S4
1107.00
0.22ϫ0.10ϫ0.07
293(2)
0.71073
monoclinic
P2(1)/c
9.2411(16)
14.873(3)
19.511(3)
90
96.698(4)
90
2663.3(8)
2
0.883
C36H26Ni2P2S4
766.17
0.32ϫ0.26ϫ0.04
293(2)
0.71073
monoclinic
P2(1)/c
14.1076(17)
11.0368(14)
20.698(3)
90
96.678
90
C64H54Cl4Ni2P4S4
1334.41
0.14ϫ0.09ϫ0.02
293(2)
0.71073
monoclinic
P2(1)/n
9.55620(10)
13.8105(2)
22.8897(4)
90
99.4062(6)
90
2980.27(7)
4
1.100
0.71073
triclinic
¯
P1
11.5896(19)
11.6771(19)
12.699(2)
77.243(3)
74.252(3)
77.113
1588.8(2)
2
0.804
γ [°]
Volume [Å3]
Z
3200.8(7)
4
1.564
µ [mm–1]
No. reflections collected
No. of independent reflections 6953[R(int) = 0.0604]
Data/restraints/parameters
Goodness-of-fit
Final R indices [IϾ2σ(I)]
20164
20216
18590
12085
4537[R(int) = 0.0771]
4536/0/316
1.062
R1 = 0.0499
wR2 = 0.1179
3921 [R(int) = 0.0906]
3921/0/397
1.063
R1 = 0.0515
wR2 = 0.1180
6787 [R(int) = 0.0385]
6787/0/352
1.025
R1 = 0.0472
wR2 = 0.0958
6953/0/388
1.032
R1 = 0.0516[a]
wR2 = 0.1251[b]
2
[a] R1 = Σ[|Fo| – |Fc|/ΣFo]. [b] wR2 = [Σ(Fo2–Fc )/Σ(Fo2)]1/2
.
Table 10. Summary of crystal data and structure refinement for the copper complexes.
Compound
5
6
7
8
Empirical formula
Formula weight
Crystal size [mm]
Temperature [K]
Wavelength [Å]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C72H58Cu2P4S2
1238.26
0.14ϫ0.09ϫ0.08
100(2)
0.71073
monoclinic
P2(1)/c
13.6052(4)
13.2026(4)
17. b1891(5)
90
109.8820(10)
90
2913.14(15)
2
0.956
C62H55Cu2N4P3S2
1140.21
0.44ϫ0.30ϫ0.16
100(2)
C62H52Cu2P4S2
1112.12
0.33ϫ0.16ϫ0.16
100(2)
0.71073
orthorombic
Pca2(1)
22.3790(17)
10.8781(9)
20.8997(17)
90
90
90
C61.5H51ClCu2P4S2
1140.55
0.26ϫ0.21ϫ0.20
100(2)
0.71073
monoclinic
P2(1)/c
10.3654(8)
13.6462(12)
38.692(3)
90
93.606(2)
90
5462.1(8)
4
1.060
0.71073
triclinic
¯
P1
12. 7255(2)
13.2615(3)
18.6953(4)
74.7970(10)
87.0630(10)
64.2400(10)
2734(10)
2
γ [°]
Volume [Å3]
Z
5087.8(7)
4
1.086
µ [mm–1]
0.986
No. reflections collected
No. of independent reflections 7441 [R(int) = 0.064] 12784 [R(int) = 0.0206]
Data/restraints/parameters
Goodness-of-fit
Final R indices [IϾ2σ(I)]
30411
38949
44379
48313
10351 [R(int) = 0.0504]
10351/1/631
1.016
R1 = 0.0387
wR2 = 0.0824
11130 [R(int) = 0.0427]
11130/84/673
1.067
R1 = 0.0584
wR2 = 0.1263
7411/0/361
1.066
12784/0/662
1.062
R1 = 0.0270
wR2 = 0.0707
R1 = 0.0740[a]
wR2 = 0.1832[b]
[a] R1 = Σ[|Fo| – |Fc|/ΣFo]. [b] wR2 = [Σ(Fo2–Fc )/Σ(Fo2)]1/2
.
2
822
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 814–823

Cobalt, Nickel and Copper Phosphanylthiolato Complexes
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request/cif.
2
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Acknowledgments
This work was supported by the Xunta de Galicia (Spain) (grant
PGIDIT07PXIB203038PR) and by the Ministerio de Ciencia y
Tecnología (Spain) (grant CTQ2006–05298BQU).
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Received: September 21, 2009
Published Online: December 22, 2010
Eur. J. Inorg. Chem. 2010, 814–823
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
823