Formation of carbonylrhenium cryptates with alkali metal cations: Coordination chemistry studies of [Ph2P(E)NP(E)Ph2] -, e = O, S, Se towards ReBr(CO)5

Article abstract of DOI:10.1016/j.poly.2010.08.011

Reaction of ReBr(CO)₅ with Li[Ph₂P(O)NP(O)Ph ₂] afforded the cryptate Li[Re₂(CO)₆{μ- Ph₂P(O)NP(O)Ph₂-κ²O,O'}₃]; whereas K[Ph₂P(O)NP(O)Ph₂

Full text of DOI:10.1016/j.poly.2010.08.011

Polyhedron 29 (2010) 3103–3110
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Polyhedron
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Formation of carbonylrhenium cryptates with alkali metal cations: Coordination
chemistry studies of [Ph2P(E)NP(E)Ph2]ꢀ, E = O, S, Se towards ReBr(CO)5
Ricardo Rodríguez-Palacios a, Marisol Reyes-Lezama a, Lucila Márquez-Pallares a,
Ana Adela Lemus-Santana a, Obdulia Sánchez-Guadarrama a, Herbert Höpfl b, Noé Zúñiga-Villarreal a,
⇑
a Instituto de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, Circuito Exterior, 04510 México, D.F., Mexico
b Centro de Investigaciones Químicas. Universidad Autónoma del Estado de Morelos. Av. Universidad 1001, C. P. 62210 Cuernavaca Morelos, Mexico
a r t i c l e i n f o
a b s t r a c t
Article history:
Reaction of ReBr(CO)5 with Li[Ph2P(O)NP(O)Ph2] afforded the cryptate Li[Re2(CO)6{
l
l
-Ph2P(O)NP(O)Ph2-
-Ph2P(O)NP(O)Ph2-
j
2O,O’}3]; whereas K[Ph2P(O)NP(O)Ph2] reacted with ReBr(CO)5 to give K[Re2(CO)6{
Received 14 June 2010
Accepted 12 August 2010
Available online 20 August 2010
j2O,O0}{Ph2P(O)NP(O)Ph2-j2O,O0}2]. Other chalcogen ligands’ salts M[Ph2P(E)NP(E)Ph2], E = Se and S,
M = K and Li gave dirhenium carbonyls with bromido and Ph2P(E)NP(E)Ph2, E = Se or S bridges upon reac-
tion with ReBr(CO)5.
Keywords:
Ó 2010 Elsevier Ltd. All rights reserved.
Carbonyl rhenates
Imidodichalcogenophosphinates
Alkali metal cations
Inorganic ligands
1. Introduction
Na[Re2(CO)6{l
-Ph2P(O)NP(O)Ph2-j2O,O0}3] occurred in high yields
[9]. Cryptate reaction yield was virtually quantitative when Re-
Br(CO)5 was used as starting material (Scheme 1). In order to
broaden the scope of this research we directed our attention to Li
and K cations; in addition, we turned our efforts to study the reac-
tion chemistry of the salts M[Ph2P(E)NP(E)Ph2], E = Se and S, M = Li
and K towards ReBr(CO)5 with the aim of preparing the corre-
sponding Se and S cryptates.
The anions [Ph2P(E)NP(E)Ph2]ꢀ, E = O, S and Se have been stud-
ied for some years [1–3]; however, it is only since the 1990s that
most of their coordination chemistry, both to transition and repre-
sentative elements, has been explored as evidenced by a large
number of reports on complexes containing these ligands [4].
The ability of the [Ph2P(E)NP(E)Ph2]ꢀ, (E = O, S and Se) anions to li-
gate in diverse fashions and to take on several ring conformations
is one of the reasons why these ligands have been extensively stud-
ied; their potential applications in photonic devices and sensors
[5], biological activity [6], and recently as potential biomolecule la-
bels in luminescent bioassays or materials for laser systems [7]
(particularly some imidodiphosphinate, [Ph2P(O)NP(O)Ph2]ꢀ, com-
plexes with long-lived near-infrared luminescent properties) have
further contributed to increase the interest in compounds contain-
ing these so-called inorganic (no carbon atoms in the backbone)
ligands.
2. Results and discussion
The cryptate Li[Re2(CO)6{l
-Ph2P(O)NP(O)Ph2-j2O,O0}3], 1 was
formed upon reaction of ReBr(CO)5 with Li[Ph2P(O)NP(O)Ph2] in
boiling toluene for 4 h in an 84% yield (Scheme 2).
Analytical and spectroscopic data showed that 1 is a dinuclear
rhenate(I) carbonyl complex. It is stable in the solid state for
months in air, but it decomposes in hours in halogen solvents.
Complex 1 is insoluble in nonpolar hydrocarbons.
We have systematically been developing the reaction chemistry
of the tetraphenyldichalcogenoimidodiphosphinate anions, [Ph2P-
(E)NP(E)Ph2]ꢀ, E = O, S and Se toward group 7 carbonyls specifically
Mn and Re [8]. We found that upon reaction of the rhenium
precursors ReBr(CO)5, Re2Br2(CO)6(THF)2, and ReOTf(CO)5 with
Na[Ph2P(O)NP(O)Ph2] a spontaneous assembly of the cryptate
The KBr IR spectrum of 1 consisted of two bands in the m(CO) re-
gion: 2020 s and 1895 vs cmꢀ1; in toluene, the IR spectrum showed
three strong bands at 2023, 1925, and 1900 cmꢀ1, all of the bands
arise from terminal CO’s. The 31P{1H} NMR spectrum of 1 in solu-
tion showed one singlet at 30.3 ppm (the 31P{1H} NMR signal of
Li[Ph2P(O)NP(O)Ph2] appears at 19.1 ppm [10]) due to three sym-
metrically bound Ph2P(O)NP(O)Ph2 ligands.
An X-ray analysis was performed on single crystals of 1 and its
structure is shown in Fig. 1 together with some selected bond
distances and angles. The structure of complex 1 is similar to that
⇑
Corresponding author. Tel.: +52 55 56 22 44 31; fax: +52 55 56 16 22 03.
E-mail address: zuniga@unam.mx (N. Zúñiga-Villarreal).
0277-5387/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2010.08.011

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R. Rodríguez-Palacios et al. / Polyhedron 29 (2010) 3103–3110
ReBr(CO)5
i
O
O
O
O
Na
(OC)3Re
Re(CO)3
O
O
iii
ii
ReOTf(CO)5
Re2(CO)6(Br)2(THF)2
i, [O,O], boiling toluene, 95% yield; ii, [O,O], CH2Cl2, rt, 70% yield; iii, [O,O], boiling THF, 80% yield
[O,O] = O
O = [Ph2P(O)NP(O)Ph2]
Scheme 1.
O
O
O
O
O
Li
O
Li[Ph2(O)PNP(O)Ph2]
(OC)3Re
Re(CO)3
O
1
Boiling toluene
ReBr(CO)5
CO
Re
O
CO
Re
O
K[Ph2(O)PNP(O)Ph2]
O
CO
CO
OC
OC
K
O
O
2
Scheme 2.
of the cryptate Na[Re2(CO)6{l
-Ph2P(O)NP(O)Ph2-j2O,O0}3] [9]: it
consists of two -Re(CO)3 fragments united by three end bound
Ph2P(O)NP(O)Ph2 ligands that make up an organometallacryptate
[11] wherein the Li cation is encased. The coordination geometry
around both rhenium centers is pseudooctahedral. There are six
O–Li interactions that render the coordination geometry around
the lithium cation a trigonal antiprism. The PNP angles of the
bridging ligands Ph2P(O)NP(O)Ph2 are all equal within experimen-
tal error (ca. 133°).
Reaction of the K[Ph2P(O)NP(O)Ph2] salt with ReBr(CO)5 in boil-
ing toluene for 2 h afforded complex 2 in 92% yield as depicted in
Scheme 2.
Analytical and spectroscopic data showed that the 2, just like 1,
is a dinuclear rhenate(I) carbonyl complex. It is stable in the solid
state in air for months, insoluble in nonpolar organic solvents and,
in contrast to 1, it is stable in low polarity halogen solvents.
The IR spectrum of 2 showed two bands in the m(CO) region:
2019 s and 1888 vs cmꢀ1 in KBr and 2022 and 1900 cmꢀ1 in CH2Cl2.
It can be inferred that the negative charge in rhenates 1 and 2 is
concentrated on the oxygen atoms of [Re2(CO)6{
l
-Ph2P(O)N-
Fig. 1. Molecular structure of 1 including the atom numbering scheme. Only phenyl
ipso carbon atoms are shown for clarity. Partial occupancy of crystallization solvent
is not shown. Selected bond lengths [Å] and angles [°]: Re–O(4) 2.171(4), Re–O(5)
2.159(4), Re–O(6) 2.162(4), Li–O(4) 2.159(5), Li–O(5) 2.165(8), Li–O(6) 2.142(12),
P(1)–O(4) 1.525(4), P(2)–O(5) 1.531(4), P(3)–O(6) 1.513(4). P(2)–N(1)–P(1A)
133.5(3), P(3)-N(2)-P(3A) 133.8(5), P(1)-N(1A)-P(2A) 133.5(3), C(1)–Re–O(5)
172.9(2), C(2)–Re–O(6) 171.6(2), C(3)–Re–O(4) 174.2(2), O(4)–Re–O(5) 76.3(1),
O(4)–Re–O(6) 76.0(1), O(5)–Re–O(6) 75.7(1).
P(O)Ph2-j2O,O0}3]ꢀ and [Re2(CO)6{
l
-Ph2P(O)NP(O)Ph2-j2O,O0}{Ph2-
P(O)NP(O)Ph2-j2O,O0}2]ꢀ, respectively, that interact with the
cation; since, it is known that carbonyl metallates give rise to car-
bonyl bands in the range 1600–2000 cmꢀ1 for terminal carbonyls
in solution; whereas the IR
m(CO) bands of 1 and 2 lie within the
range for neutral metal carbonyls (1900–2200 cmꢀ1) [12].

R. Rodríguez-Palacios et al. / Polyhedron 29 (2010) 3103–3110
3105
The 31P NMR{1H} spectrum of 2 showed two singlets: one at
28.5 ppm and the other at 26.8 ppm due to the inequivalence of
the Ph2P(O)NP(O)Ph2 ligands (see below).
The structure of 2 (determined by a single crystal X-ray analy-
sis, Fig. 2) shows two –Re(CO)3 moieties linked by two oxygen
atoms of a Ph2P(O)NP(O)Ph2 ligand. The other two Ph2P(O)N-
P(O)Ph2 ligands function in a chelating capacity at each rhenium
center of both –Re(CO)3 fragments. The K cation engages in four
interactions with the oxygen atoms of the Ph2P(O)NP(O)Ph2 li-
gands rendering it tetracoordinated.
thesis of heterometallic cryptates of transition and alkali metals
is significant as these cryptates have proven adequate for multi-
functional catalytic systems and electro- and photochemical de-
vices [17].
We explored the reaction chemistry of M[Ph2P(E)NP(E)Ph2],
E = Se and S; M = Li and K towards ReBr(CO)5 with a view to con-
struct chalcogen cryptates analogous to M[Re2(CO)6{l-Ph2P(O)N-
P(O)Ph2-j2O,O0}3], M = Li and Na. Reaction of K[Ph2P(E)NP(E)Ph2],
E = Se, S with ReBr(CO)5 under toluene reflux in a molar ratio 2:1
(ReBr(CO)5/K[Ph2P(E)NP(E)Ph2]) gave complexes 3 and 4 respec-
tively in good yields according to Scheme 3(a).
The coordination geometry around each rhenium center in 2 is
pseudooctahedral, whereas the coordination geometry around the
potassium atom cannot be described in terms of a regular polyhe-
dron: the oxygen atoms O(7), O(9), O(10), O(12) and the alkali me-
tal K(1) lie nearly on a plane (with mean deviations of ꢀ0.1249,
0.1078, ꢀ0.1346, 0.0549 and 0.0968 Å, resp.). There are no metall-
ophilic interactions between the rhenium and the potassium ions.
The OPNPO backbone is renowned for its flexibility, e.g., in com-
pound HN(OPPh2)2 the PNP angle measures 180° [13]. In the pres-
ent case the PNP angle of the bridging Ph2P(O)NP(O)Ph2 ligand in 2
measures 135.7(3)°; in comparison, the PNP angles of the
Ph2P(O)NP(O)Ph2 chelators measure 125.9(3)° and 124.5(3)°. It is
apparent that formation of 2 with only one bridging Ph2P(O)N-
P(O)Ph2 is due to the larger K cation (1.51 Å) as compared to Li
(0.9 Å) [14].
It is well known that most reported transition metallocryp-
tates of alkali metal cations are composed of arene ligands that,
on the one hand, bind the ‘hard’ alkali cations (in the sense of
Pearson’s ‘soft–hard’ acid–base model) with N or O atoms and,
on the other hand, ligate transition metals by a relatively ‘soft’
atom, e.g. phosphorus. In the present case the oxygen atoms of
the Ph2P(O)NP(O)Ph2 ligands in complex 1 bind both transition
and alkali metals. Unlike their organic counterparts, multinuclear
heterometallic cryptates are capable of binding metal ions either
through metallophilic interactions between the metal capping
groups and the guest ion or, as in the present case, through
strong Lewis base interactions of the donor groups of the ligands
[15]. In general heteronuclear complexes have been extensively
studied due to their application in molecular magnetism and
nonlinear optics [16], among other areas; in particular the syn-
Complexes 3 and 4 are partially soluble in chlororganic solvents
and insoluble in hexane. When exposed to air 3 and 4 are stable as
solids for months; in solution they decompose within ca. a month.
Under a nitrogen atmosphere these complexes can be stored as sol-
ids indefinitely at low temperature.
The IR spectra of complexes 3 and 4 show two strong bands
(2024, 1930 and 2028, 1935 cmꢀ1, resp. in CH2Cl2) indicative of a
fac disposition of the three carbonyl groups at each metal center
(an eclipsed conformation with a D3h local symmetry of the
(CO)3Re–Re(CO)3 carbonyl groups along the Re–Re axis, see be-
low).1 The 31P NMR{1H} spectra showed only one signal, at 28
and 41 ppm for 3 and 4 respectively, consistent with a symmetrical
ligation of the imidodichalcogenophosphinato ligand.
The structures of 3 and 4, shown in Fig. 3 and 4 resp., were
determined by single crystal X-ray diffraction analyses.
The unit cell of complex 4 contains two chemically identical but
crystallographycally independent molecules. The structures show
that the metal centers are linked by two bridges: one bromido
and one [Ph2P(E)NP(E)Ph2], E = Se for 3 and E = S for 4 bound in a
bimetallic tetraconnective fashion. The distance between the rhe-
nium centers (3.571 and 3.515 Å resp. for 3 and 4) indicates no
bonding interaction in both complexes (the Re–Re bonding dis-
tance in (OC)5Re–Re(CO)5 is 3.0413(11) Å [18]). The metal centers
in 3 and 4 display distorted octahedral geometry. The Re–Br–Re
angle in 3, 83.56(2)°, is somewhat larger than in 4, 82.05(3)°, such
flexibility of the bromido bridge Re–Br–Re is well known, e.g., in
the complex Re2Br2(CO)6(PhCH2SeSeCH2Ph) the Re–Br–Re angle
measures 94.6° [19]. The Re–Re nonbonding distance in 3 is longer
than in 4. The difference in angle size and Re–Re nonbonding dis-
tance in 3 compared to 4 are clearly due to the chalcogen size (Se
versus S, resp.). The dihedral angle between the Re(1)–E(1)–E(2)
and Re(2)–E(1)–E(2) planes measures 128.8° for E = Se (complex
3) and 132.6° for E = S (complex 4); this is a reflection of the longer
rhenium–chalcogen distance in 3 as compared to 4. The E–P–N–P–
E, E = Se, S fragment in both molecules is essentially planar (with a
mean plane deviation of 0.03 and 0.029 Å for 3 and 4, resp.). The
Re–E, E = Se or S distances in 3 and 4 are similar (see Figs. 3 and
4) indicating a symmetrical coordination of the inorganic ligands
to both –Re(CO)3 fragments.
IR reaction monitoring for formation of 3 showed the presence
of mononuclear complex Re(CO)4[Ph2P(Se)NP(Se)Ph2-j2Se,Se0] 5
(2098 m, 2005 s, 1984 s, 1941 s cmꢀ1 in toluene [8a]) as a reaction
intermediate; so, we decided to prepare dinuclear complexes 3 and
4 starting from Re(CO)4[Ph2P(E)NP(E)Ph2-j2S,S0], E = Se and S
respectively and ReBr(CO)5 according to Scheme 3(b). Mononu-
clear complexes Re(CO)4[Ph2P(E)NP(E)Ph2-j2E,E0], E = Se 5 [8a]
and E = S 6 were readily available upon reaction of ReBr(CO)5
with the corresponding K[Ph2P(E)NP(E)Ph2] salt as shown in
Eq. (1).
Fig. 2. Molecular structure of 2 including the atom numbering scheme. Only phenyl
ipso carbon atoms are shown for clarity. Partial occupancy of crystallization solvent
is not shown. Selected bond lengths [Å] and angles [°]: Re(1)–O(7) 2.180(3), Re(1)–
O(8) 2.152(3), Re(1)–O(9) 2.158(3), K(1)–O(7) 2.572(4), K(1)–O(9) 2.709(3),
K(1)–O(10) 2.746(4), K(1)–O(12) 2.565(3), P(1)–O(7) 1.518(4), P(2)–O(8) 1.522(4),
P(3)–O(9) 1.521(3), P(4)–O(10) 1.516(3), P(5)–O(11) 1.519(3), P(6)–O(12) 1.527(3).
P(2)–N(1)–P(1) 125.9(3), P(3)–N(2)–P(4) 135.7(3), P(6)–N(3)–P(5) 124.5(3), C(1)–
Re(1)–O(9) 177.6(2), C(2)–Re(1)–O(8) 173.0(2), C(3)–Re(1)–O(7) 175.0(2), C(4)–
Re(2)–O(10) 174.2(2), C(5)–Re(2)–O(11) 176.8(2), C(6)–Re(2)–O(12) 176.1(2),
O(7)–Re(1)–O(8) 83.4(1), O(7)–Re(1)–O(9) 80.9(1), O(8)–Re(1)–O(9) 80.9(1),
O(10)–Re(2)–O(11) 81.9(1), O(10)–Re(2)–O(12) 78.3(1).
1
Another possible symmetry group for 3 and 4 could be D3d with the Re(CO)3–
Re(CO)3 carbonyls staggered along the Re-Re axis; notwithstanding, the bonding
fashion of the ligands [Ph2 P(E)NP(E)Ph2 ] E = Se, S compels the carbonyls to adopt an
eclipsed conformation as attested by the X-ray diffraction analysis.

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R. Rodríguez-Palacios et al. / Polyhedron 29 (2010) 3103–3110
CO
E
E
OC
Toluene
K[Ph2(E)PNP(E)Ph2]
ReBr(CO)5
+
Re
OC
ð1Þ
E = Se, S
CO
E = Se 5
E = S 6
CO
Re
CO
E
E
E
OC
OC
E
(OC)3Re
(b)
(a)
ReBr(CO)5
K[Ph2(E)PNP(E)Ph2]
E = Se, S
ReBr(CO)5
+
+
Re(CO)3
Br
E = Se 3
E = S
4
E = Se
E = S
5
6
[Ph2(E)PNP(E)Ph2], E = Se, S
=
E
E
Scheme 3.
Fig. 3. Molecular structure of 3 including the atom numbering scheme. Only phenyl
ipso carbon atoms are shown for clarity. Partial occupancy of crystallization solvent
is not shown. Selected bond lengths [Å] and angles [°]: Re(1)–Se(1) 2.6313(5),
Re(1)–Se(1A) 2.6356(5), Re(1)–Br(1) 2.6800(6). Re(1)–Br(1)–Re(1A) 83.56(2), P(1)–
N(1)–P(1A) 138.8(4), Se(1)–Re(1)–Se(1A) 83.58(2), C(1)–Re(1)–Br(1) 174.8(2), C(2)–
Re(1)–Se(1) 171.8(2), C(3)–Re(1)–Se(1A) 171.4(2), Se(1)–Re(1)–Br(1) 77.30(1),
Se(1A)–Re(1)–Br(1) 77.22(1).
Fig. 4. Molecular structure of 4 including the atom numbering scheme. Only phenyl
ipso carbon atoms are shown for clarity. Partial occupancy of crystallization solvent
is not shown. Selected bond lengths [Å] and angles [°]: Re(1)–S(1) 2.526(2), Re(1)–
S(2) 2.548(2), Re(2)–S(1) 2.538(2), Re(2)–S(2) 2.543(2), Re(1)–Br(1) 2.673(1), Re(2)–
Br(1) 2.683(1). Re(1)–Br(1)–Re(2) 82.05(3), P(1)–N(1)–P(2) 134.8(5), S(1)–Re(1)–
S(2) 81.32(7), C(1)–Re(1)–Br(1) 177.1(3), C(2)–Re(1)–S(1) 171.7(3), C(3)–Re(1)–S(2)
169.1(3), C(28)–Re(2)–Br(1) 175.8(3), C(29)–Re(2)–S(2) 171.7(3), C(30)–Re(2)–S(1)
171.6(3), S(1)–Re(1)–Br(1) 77.87(5), S(2)–Re(1)–Br(1) 76.96(5), S(1)–Re(2)–Br(1)
77.48(5), S(2)–Re(2)–Br(1) 76.87(5).
The new complex 6 was prepared upon reaction of equimolar
amounts of ReBr(CO)5 and the K[Ph2P(S)NP(S)Ph2] salt in hot tolu-
ene (see Experimental). It is an off-white material soluble in
dichloromethane, partially soluble in toluene and insoluble in non-
polar organic solvents. In the solid state 6 is stable in air for several
days; however, in solution it decomposes within hours giving a
yellow solution of unidentified products. The IR spectrum of 6
shows four bands in the carbonyl stretching region. The disposition
of the carbonyl groups gives rise to a C2v local symmetry corre-
sponding with the 2A1 + B1 + B2 vibration modes [12]. The struc-
ture of 6 was determined by an X-ray analysis and can be
described as a regular octahedron wherein the inorganic ligand
Ph2P(S)NP(S)Ph2 is bound to the metal center in a monometallic
biconnective fashion that renders a six membered metallo-ring
with a twist boat conformation; see Fig. 5 for selected bond lengths
and angles.

R. Rodríguez-Palacios et al. / Polyhedron 29 (2010) 3103–3110
3107
the spectroscopic data available we may infer this material to be
complex 7 as shown in Scheme 4.
3. Conclusions
Self-assembly of an Li organometallic cryptate was achieved
upon reaction of Li[Ph2P(O)NP(O)Ph2] salt with ReBr(CO)5. Coordi-
nation of three Ph2P(O)NP(O)Ph2 ligands’ oxygen atoms in a
bridging capacity rendered cryptate formation possible. This coor-
dination fashion can be realized due to the well known flexibility of
the OPNPO backbone of the imidodiphosphinate ligand; however,
when K, a larger cation, was tried to be placed in the cryptand’s
cavity a complex of identical Li cryptate stoichiometry, but differ-
ent spatial arrangement was formed. Organometallic cryptates of
other imidodichalcogenophosphinate ligands were elusive; how-
ever, their reaction chemistry towards ReBr(CO)5 contributed to
our understanding of the assembly process of the organometal-
lic-imidodiphosphinate cryptates. It is apparent that the length of
the Ph2P(O)NP(O)Ph2 ligand is not adequate to encase a K atom;
notwithstanding, K coordination can still be achieved. The assem-
bly of organometallic cryptates of imidodiphosphinate ligands
with longer backbones to encase atomic or molecular cations re-
mains a promising research area due to their potential applications
in multifunctional catalytic systems, electro- and photochemical
devices, and biological processes as well.
Fig. 5. Molecular structure of 6 including the atom numbering scheme. Only phenyl
ipso carbon atoms are shown for clarity. Selected bond lengths [Å] and angles [°]:
Re(1)–S(1) 2.522(1), Re(1)–S(2) 2.540(1), P–Sav 2.015(2), P–Nav 1.590(3). P(1)–N(1)–
P(2) 127.3(2), S(1)–Re(1)–S(2) 97.44(4), S(1)–P(1)–N(1) 117.7(1), P(1)–S(1)–Re(1)
108.21(6), C(2)–Re(1)–C(1) 177.4(2), C(3)–Re(1)–S(1) 173.5(2), C(4)–Re(1)–S(2)
175.8(2).
The difference between both Re–S bond lengths is small
(0.018(1) Å); so, it can be stated that the tetraphenylimidodithio-
phosphinate coordination is symmetrical: the 31P{1H} NMR spec-
trum of 6 in solution shows one signal at 37.0 ppm for both
phosphorus atoms of the coordinated ligand. The P–S (P–Sav
2.015(2) Å) and P–N (P–Nav 1.590(3) Å) bond lengths are equal
and lie within P–S and P–N simple and double bonds (P–S
2.057(1) and P@S 1.945(1) Å; P–N 1.612(3) and P@N 1.557(3) Å
in [2-(Me2NCH2)C6H4]Te–S-PPh2@N-PPh2@S [20]). The flexibility
of the PNP fragment is apparent from the PNP angle in 6
(127.3(2)°) compared with the PNP angle in 4 (134.8(5)°).
4. Experimental
4.1. General details
All preparations were conducted under an atmosphere of nitro-
gen using standard Schlenk techniques with Schlenk-type glass-
ware on a dual-manifold vacuum line. All solvents were distilled
over standard drying agents under an inert atmosphere directly be-
fore use and deoxygenated. ReBr(CO)5, chlorodiphenylphosphine,
hexamethyldisilazane, and potassium tert-butoxide were acquired
from Strem Chemicals, Inc. and used with no further purification
except for chlorodiphenylphosphine, which was distilled under
vacuum (102 °C, 1 mmHg). n-BuLi was acquired from Aldrich
Chemical Co. Gray selenium was acquired from Fisher Reagents Sci-
entific Company. HN(PPh2)2, HN(EPPh2)2, E = O, S, and Se; and
M[(EPPh2)2N], E = O, M = Li; E = O, S and Se, M = K [3] and Re2(-
CO)6Br2(THF)2 [22] were prepared according to literature proce-
dures. Details concerning crystal data and refinement are given in
Table 1. Reactions were monitored by IR spectroscopy in the char-
In order to investigate the difference in the reaction chemistry
of ReBr(CO)5 towards the oxygen salts M[Ph2P(O)NP(O)Ph2],
M = Li and K on the one hand, and the selenium and sulfur salts
K[Ph2P(E)NP(E)Ph2] on the other hand, we conducted an IR moni-
toring experiment of the assembling process of 1 in the
gion at 85–90° C for 16 h (Fig. 6).
m(CO) re-
We detected reaction intermediates that could not be isolated;
however, we could propose band assignations by comparison with
analogous complexes: the band at 2006 cmꢀ1 was tentatively as-
signed to the oxygen analogous of 6, Re(CO)4[Ph2P(S)NP(S)Ph2-
j2S,S0] (step 1, Scheme 4). The band at 1939 cmꢀ1 was assigned
to Re2(CO)6(
l-Br)[l
-Ph2P(O)NP(O)Ph2-j2O,O0] (the oxygen analo-
acteristic region for carbonyl stretching vibrations, m(CO). All ORTEP
gous of 3 and 4, step 2 Scheme 4). At 1858 cmꢀ1 appears a band
drawings for reported structures depict 50% probability ellipsoids.
IR spectra were obtained in solution (4000–580 cmꢀ1) using a
that we assigned to the complex Re2(CO)6[l-Ph2P(O)NP(O)Ph2-
j2O,O0]2, the oxygen analogous of C (step 3, Scheme 4). The bands
at 2023, 1925, and 1900 cmꢀ1 arise from CO’s vibrations of 1. Band
overlap precluded detection of the expected number of bands in all
intermediates.
Nicolet FT-IR 55X spectrometer and in KBr disk (4000–200 cmꢀ1
)
in a Perkin Elmer 283B spectrometer. NMR spectra were obtained
at room temperature on Varian Unity 300, Perkin Elmer 283B, and
Jeol GX300 spectrometers. 1H NMR spectra were referenced to
residual solvent peaks with chemical shifts (d) reported in ppm
downfield of tetramethylsilane. 31P{1H} NMR spectra were exter-
nally referenced to 85% H3PO4. FAB(+) mass spectra were recorded
on a JEOL SX-102A instrument.
The report that carbonylrhenium complexes with bromido
bridges undergo nucleophilic attack by MER (M = Na, Li; E = S, Se,
Te; R = organic substituent) to give the corresponding chalcogeni-
do bridged dirhenium complexes [21] encouraged us to attempt
the substitution of the [Ph2P(Se)NP(Se)Ph2] ligand for the bromido
bridge in 4 in order to move one step further to cryptate assembly
(step 3, Scheme 4). Reaction of 4 and K[Ph2P(Se)NP(Se)Ph2] with a
1:2 molar ratio resp. under toluene reflux resulted in an off-white
poorly soluble material in all standard organic solvents.2 The lack
of solubility precluded a sound characterization, however, with
4.1.1. Synthetic procedure for 1 and 2
ReBr(CO)5 was added to a solution of M[Ph2P(O)NP(O)Ph2],
M = Li, 1 and M = K, 2 in 100 mL of dry degassed toluene. The reaction
mixture was refluxed and then cooled to room temperature. The sol-
ids were filtered out and toluene was removed under reduced pres-
sure leaving behind a solid. The solid was washed with 3 ꢁ 10 mL
portions of hot toluene and the product extracted with 3 ꢁ 10 mL
of dichloromethane at room temperature and dried under vacuum.
2
We also tested reactions of both K[Ph2 P(E)NP(E)Ph2] E = Se and S toward 3 and
K[Ph2 P(S)NP(S)Ph2] toward 4: all of them led to insoluble materials.

3108
R. Rodríguez-Palacios et al. / Polyhedron 29 (2010) 3103–3110
Fig. 6. Self-assemblage IR monitoring of 1 in toluene (85–90 °C). (a) Time 0; (b) 1 h; (c) 4 h; (d) 8 h; (e) 12 h; and (f) 16 h.
CO
OC
OC
E
E
Re
M[Ph2(E)PNP(E)Ph2]
+
ReBr(CO)5
Step1
CO
E = S 6
ReBr(CO)5
Step 2
E
E = Se 3
E
M[Ph2(E')PNP(E')Ph2]
E
(OC)3Re
E'
E
(OC)3Re
4
E = S
Re(CO)3
Step 3
Re(CO)3
Br
E'
E' = Se
E = S
7
E = S, Se
[Ph2(E)PNP(E)Ph2]
=
E
E
Scheme 4.
4.1.2. Li[Re2(CO)6{
[(hexacarbonyl)tris-(
O,O0)dirhenate] (1)
l
-Ph2P(O)NP(O)Ph2-j2O,O0}3], lithium
l
P(O)NP(O)Ph2}]+; 424, Li[Ph2P(O)NP(O)Ph2]+. Suitable crystals for
an X-ray analysis were obtained from a 2:1 mixture of chloro-
form–hexane, respectively, at 4 °C for several days.
ꢀtetraphenylimidodiphosphinatoꢀj2
Reaction time: 4 h. 0.063 g (0.15 mmol) Li[N(OPPh2)2] and
0.03 g (0.074 mmol) ReBr(CO)5. Molar ratio: 2:1 (Li[N(OPPh2)2], Re-
Br(CO)5; resp.) Product: off-white solid, (0.057 g, 84%), mp 265-
4.1.3. K[Re2(CO)6{l
-Ph2P(O)NP(O)Ph2-j2O,O0}{Ph2P(O)NP(O)Ph2-
j2O,O0}2], potassium [(hexa-carbonyl) (
l-tetraphenylimidodiphos-
phinatoꢀj2O,O0)bis(tetraphenylimidodiphosphinato-j2O,O0)-
dirhenate] (2)
270 °C (from dichloromethane). (Anal. Calc. for
C
78H60Li-
N3O12P6Re2: C, 52.15; H, 3.37. Found: C, 51.86; H, 3.59%.).
mmax(KBr)
cmꢀ1 2020 s, 1895 vs (CO), 1226 s
m
(P2N).
m
max(Toluene) cmꢀ1 2023
Reaction time: 2 h. 0.2 g (0.44 mmol) K[N(OPPh2)2] and 0.09 g
(0.22 mmol) ReBr(CO)5. Molar ratio: 2:1 (K[N(OPPh2)2], ReBr(CO)5;
resp.) Product: off-white solid (0.185 g, 92%), mp 285–290 °C (from
dichloromethane). (Anal. Calc. for C78H60KN3O12P6Re2: C, 51.23; H,
s, 1925 s, and 1900 s (CO). 1H NMR (CDCl3, 300 MHz): d/ppm: 7.64
3
3
[dd, Ho, JHo–P = 12 Hz, Ho, JHo–Hm = 7 Hz], 7.3–6.8 [m, Hm and Hp].
31P NMR{1H} (CDCl3, 121.7 MHz): d/ppm: 30.3 [s(broad), Ph2P@O],
MS (m/e): 1796, [M+1], Li[Re2(CO)6{Ph2P(O)NP(O)Ph2}3]+; 1453,
[Re2(CO)5{Ph2P(O)NP(O)Ph2}2–OPNPO]+; 873, [Re2(CO)3{Ph2P(O)N-
P(O)Ph2}]+; 687, [Re(CO)3{Ph2P(O)NP(O)Ph2}]+; 659, [Re(CO)2{Ph2-
3.31. Found: C, 50.95; H, 3.28%).
(CO); 1217 m (P2N).
max(CH2Cl2) cmꢀ1 2022 vs, 1900 vs (CO).
31P NMR{1H} (CDCl3, 121.7 MHz): d/ppm: 28.5 [s, Ph2P@O] 26.8
m
max(KBr) cmꢀ1: 2019 s, 1888 vs
m

R. Rodríguez-Palacios et al. / Polyhedron 29 (2010) 3103–3110
3109
Table 1
Crystal data for 1, 2, 3, 4, and 6.
1
2
3
4
6
Chemical formula
Formula weight
T (K)
Crystal system
Space group
a (Å)
C
78H60LiN3O12P6Re2ꢂ2CHCl3 C78H60KN3O12P6Re2ꢂ3C6H14 C30H20BrNO6P2Re2Se2ꢂ2CHCl3 C30H20BrNO6P2Re2S2ꢂ1.5CH2Cl2 C28H20NO4P2ReS2
2035.19
298(2)
2087.13
173(2)
1401.38
2392.46
100(2)
746.71
293(2)
triclinic
100(2)
monoclinic
C2/c
24.6612(11)
13.9224(6)
25.6469(12)
triclinic
P1
monoclinic
C2/c
monoclinic
C2/c
ꢀ
ꢀ
P1
14.3420(10)
18.2436(13)
20.8643(15)
107.6020(10)
104.0000(10)
103.4130(10)
4766.3(6)
2
26.677(3)
10.0201(10)
18.0301(18)
42.079(6)
9.7175(14)
18.330(3)
9.058(1)
12.530(1)
13.163(1)
89.936(1)
81.331(1)
84.025(1)
1468.7(2)
2
b (Å)
c (Å)
a
(o)
b (o)
109.2910(10)
122.4100(10)
97.169(5)
c
(o)
V (Å3)
8311.3(6)
4
4068.8(7)
4
7436.5(19)
8
Z
Absorption
coefficient
3.279
2.741
9.232
8.037
4.421
(mmꢀ1
)
Reflections collected 44 472
45 948
18 408
16 622
17 517
Independent
7316
16 700
3578
6376
5172
reflections (Rint
)
(0.0879)
(0.0442)
(0.0471)
(0.0511)
(0.0802)
Final R indices
R1 = 0.0430,
wR2 = 0.0904
R1 = 0.0629,
wR2 = 0.0976
R1 = 0.0417,
wR2 = 0.0982
R1 = 0.0514,
wR2 = 0.1030
R1 = 0.0289,
wR2 = 0.0725
R1 = 0.0298,
wR2 = 0.0731
R1 = 0.0486,
wR2 = 0.1040
R1 = 0.0585,
wR2 = 0.1080
R1 = 0.0335,
wR2 = 0.0570
R1 = 0.0390,
wR2 = 0.0583
[F2 > 2 (F2)]
r
R indices (all data)
(more intense signal) [s, Ph2P@O]. MS (m/e): 1826, [K{Re2-
(CO)6[Ph2P(O)NP(O)Ph2]3}-1]+; 1787, [Re2(CO)6{Ph2P(O)NP(O)Ph2}3]+;
1619, [Re2{Ph2P(O)NP(O)Ph2}3]+; 602, [Re{Ph2P(O)NP(O)Ph2}]+;
456, [K{Ph2P(O)NP(O)Ph2}]+.
When the reaction was effected with a 1:1 molar ratio the yield
was 70%; while a molar ratio of 3:2 (K[N(OPPh2)2], ReBr(CO)5;
resp.) afforded 2 in 81% yield. Suitable crystals for an X-ray analysis
were obtained from a 2:1 mixture of chloroform–hexane, respec-
tively, at 4 °C for several days.
roform-hexane, respectively, at 4 °C for several days. (Anal. Calc. for
30H20BrNO6P2Re2Se2: C, 30.99; H, 1.74. Found: C, 31.2; H, 1.81%).
max(KBr) cmꢀ1: 2024 s, 1922 vs, (CO); 1255 m, (P2N), 529 m (P–
Se).
max(CH2Cl2) cmꢀ1 2024 s, 1930 s (CO). 1H NMR (CDCl3,
C
m
m
3
3
4
300 MHz): d/ppm: 8.0 [ddd, Ho, JHo–P = 14 Hz, JHo–m = 8 Hz, JHo–
P = 2 Hz], 7.5 [m, Hm and Hp]. 13C NMR{1H} (CDCl3, 75.6 MHz): d/
ppm: 188.5 [s, Re–CO], 134.0 [d, Ci, JCi–P = 98 Hz], 132.7 [s, Cp],
3
130.0 [d, Cm, JCm–P = 8 Hz], 128.8 [d, Co, 2JCo–P = 15 Hz]. 31P
NMR{1H} (CDCl3, 121.7 MHz): d/ppm: 28.0 [s, Ph2P@Se].
4.1.4. IR monitoring experiment of formation of 1
4.1.7. Synthesis of Re2(CO)6(
-bromido)(hexacarbonyl)(
S,S0)dirhenium (4)
l
l
-Br)[
l
-Ph2P(S)NP(S)Ph2-j2S,S0],
(l
-tetraphenylimidodithiophosphinato-j2
ReBr(CO)5 (0.06 g, 0.16 mmol) was added to a solution of Li[Ph2
P(O)NP(O)Ph2] (0.2 g, 0.47 mmol) in 100 mL of dry degassed tolu-
ene. The reaction mixture was heated to 85 °C and maintained at
85–90 °C for 16 h. Samples were taken at 1, 4, 8, 12 and 16 h of
0.5 g, 1.02 mmol of K[N(SPPh2)2] and 0.83 g, 2.04 mmol of Re-
Br(CO)5 were added to 100 mL of dry degassed toluene. The reac-
tion mixture was refluxed for 1 h 40 min after which it was
passed through a bed of diatomaceous earth. The solvent was re-
tired under vacuum. Complex 6 was extracted from the resulting
off-white solid with hot dichloromethane (3 ꢁ 10 mL). Yield 84%,
0.92 g. When the reaction was achieved with a 1:1 molar ratio
the yield was 68%.
reaction and their IR spectra in the m(CO) region were obtained.
4.1.5. Synthesis of Re2(CO)6(
-bromido)(hexacarbonyl)(
j2Se,Se0)dirhenium (3)
l
-Br)[
l
-Ph2P(Se)NP(Se)Ph2-j2Se,Se0],
(l
l-tetraphenylimidodiselenophosphinato-
K[N(SePPh2)2] (0.5 g, 0.86 mmol) and 0.69 g, 1.7 mmol of Re-
Br(CO)5 were dissolved in 100 mL of dry degassed toluene. The
reaction mixture was set at toluene reflux temperature for 1.5 h.
The reaction color turned yellow-brown. Filtration of the hot
reaction mixture was achieved over diatomaceous earth. A light
brown powder was obtained. Compound 3 was extracted from
the powder with hot dichloromethane (3 ꢁ 10 mL) with a yield
of 85%, 0.85 g. When the reaction was carried out with a 1:1 molar
ratio the yield was 70%; while a molar ratio of 3:2 (ReBr(CO)5,
K[N(SePPh2)2]; resp.) afforded 3 with 78% yield.
4.1.8. Alternative preparation of 4
0.1 g, 0.13 mmol of 6, Re(CO)4[Ph2P(S)NP(S)Ph2-j2S,S0], and
0.054 g, 0.13 mmol of ReBr(CO)5 were added to 100 mL of dry de-
gassed toluene. The reaction mixture was refluxed for 90 min after
which it was cooled to room temperature and the solvent was
eliminated under vacuum. Complex 4 was extracted from the
resulting off-white solid with hot dichloromethane (5 ꢁ 10 mL).
Yield 91%, 0.13 g. Suitable crystals for an X-ray analysis in the solid
state were obtained from a mixture 2:1 dichloromethane–hexane
at 4 °C for several days. mp 125–126 °C (from CH2Cl2). (Anal. Calc.
for C30H20BrNO6P2Re2S2: C, 33.71; H, 1.89. Found: C, 33.39; H,
4.1.6. Alternative preparation of 3
Re(CO)4[Ph2P(Se)NP(Se)Ph2-j2Se,Se0], 5, [8C] (0.22 g, 0.26 mmol)
and 0.106 g, 0.23 mmol of ReBr(CO)5 were dissolved in 100 mL of
dry degassed toluene. The reaction mixture was heated at toluene
reflux temperature for 1 h. The reaction color turned yellow-brown.
Filtration of the hot reaction mixture was achieved over diatoma-
ceous earth. A light brown powder was obtained. Compound 3
was extracted from the powder with hot dichloromethane
(5 ꢁ 10 mL) in an 80% (0.24 g) yield. Suitable crystals for an X-ray
analysis in the solid state were obtained from a 2:1 mixture of chlo-
2.15%)
m
m
max(KBr) cmꢀ1 2028 s, 1929 vs (CO); 1248 m (P2N).
max(CH2Cl2) cmꢀ1 2028 s, 1935
s
(CO). 1H NMR (CDCl3,
3
3
300 MHz): d/ppm: 8.1 [ddd, Ho(PNP), JHo-P = 14 Hz, JHo–m = 8 Hz,
4JHo–P = 1 Hz], 7.4 [m, Hm and Hp]. 13C NMR{1H} (CDCl3,
75.6 MHz): d/ppm: 189.7 [s, Re–CO], 133.7 [d, Ci, JCi–P = 112 Hz],
132.7 [s, Cp], 130.2 [d, Cm, JCm–P = 15 Hz], 129.1 [d, Co, 2JCo–P
=
3
15 Hz]. 31P NMR{1H} (CDCl3, 121.7 MHz): d/ppm: 41.0
[s, Ph2P@S]. MS (m/e): 1068, [Re2(CO)6Br{Ph2P(S)NP(S)Ph2}]+; 988,

3110
R. Rodríguez-Palacios et al. / Polyhedron 29 (2010) 3103–3110
[Re2(CO)6{Ph2P(S)NP(S)Ph2}]+; 691, [{Re(CO)2[Ph2P(S)NP(S)Ph2]} +
1]+; 635, [{Re[Ph2P(S)NP(S)Ph2]} + 1]+.
can be obtained free of charge via http://www.ccdc.cam.ac.uk/con-
ts/retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-
336-033; or e-mail: deposit@ccdc.cam.ac.uk.
4.1.9. Synthesis of Re(CO)4[Ph2P(S)NP(S)Ph2-j2S,S0], (tetracarbonyl)-
(tetraphenyl-imidodithiophosphinatoꢀj2S,S0)rhenium, 6
0.25 g (0.62 mmol) of the rhenium precursor ReBr(CO)5 were
dissolved in 200 mL of dry degassed toluene in a previously nitro-
gen purged device. K[N(SPPh2)2] (0.3 g; 0.62 mmol) was added and
the solution was heated to 80 °C and maintained for 0.5 h after
which the solution was filtered through diatomaceous earth to re-
move KBr. Toluene was eliminated under reduced pressure
remaining an off-white solid from which the product was ex-
tracted with dichloromethane (0.45 g, 98% yield). Adequate
crystals for X-ray analysis were grown from dichloromethane at
4 °C for several days; mp 150 °C (dec) (from CH2Cl2). (Anal. Calc.
for C28H20NO4P2Re2S2: C, 45.04; H, 2.7. Found: C, 44.76; H,
Acknowledgements
The authors thank M.I. Chávez-Uribe, E. García-Ríos, L. Velasco-
Ibarra, and F. J. Pérez-Flores for technical assistance (Instituto de
Química, UNAM). M.O. S-G, M. R.-L. and A.A. L.-S. gratefully
acknowledge student grants from CONACyT. N. Z.-V. expresses
gratitude to CONACyT for partial funding of this project through
Grant P47263-Q and PAPIIT (DGAPA) through Grant IN217706-2.
References
max(KBr) cmꢀ1 2100 s, 2006 vs, 1983 sh, 1935 vs (CO);
max(CH2Cl2) cmꢀ1 2105 vs, 2010 vs, 1987 vs, 1940
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1215 s (P2N).
vs (CO). 1H NMR (CDCl3, 300 MHz): d/ppm: 7.9 [ddd, Ho(PNP),
m
m
3
4
3JHo–P = 14 Hz, JHo–m = 8 Hz, JHo–P = 1 Hz], 7.4 [m, Hm and Hp].
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4.1.10. Preparation of (hexacarbonyl) (
l
-tetraphenylimidodiseleno-
phosphinatoꢀj2Se,Se0) (
l
-tetraphenylimidodithiophosphinato-j2
-
S,S0)dirhenium 7
0.15 g (0.14 mmol) of Re2(CO)6(l-Br)[l
-Ph2P(S)NP(S)Ph2-j2S,S0]
(e) N. Zúñiga-Villarreal, M. Reyes-Lezama, S. Hernández-Ortega, C. Silvestru,
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in 100 mL of dry degassed toluene in an nitrogen purged 200 mL
two-neck flask. The solution was refluxed for 24 h after which an
off-white precipitate was formed. After cooling to ambient temper-
ature the solid was filtered off and washed with hot toluene
(3 ꢁ 10 mL) affording the product. Complex 7 was obtained in
75.0% yield (0.16 g, 0.11 mmol), mp 280–285 °C (from toluene).
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171;
m
m
max(KBr) cmꢀ1 2015 s, 1931 vs, 1899 vs (CO); 1210 s, (P2N).
max(CH2Cl2) cmꢀ1 2013 s, 1932 vs, 1897 vs (CO). 31P NMR{1H}
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(CDCl3, 121.7 MHz): d/ppm: 37.99 [s, Ph2P@S], 28.53 [s, Ph2P@Se].
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4.2. Crystal data
See Table 1.
[e] J.-M. Lehn, J.-B. Regnouf de Vains, Helv. Chim. Acta 75 (1992) 1221.
[12] F.P. Pruchnik, Organometallic Chemistry of the Transition Elements, Plenum,
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4.3. Crystal structure determinations
[13] H. Nöth, Z. Naturforsch. 37b (1982) 1491.
[14] J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry: Principles of Structure
and Reactivity, HarperCollins, New York, 1993. pp. 114 and 292.
[15] For metallophylic interactions in multiheteronuclear matallocryptates see: J.V.
Catalano, M.A. Malwitz, J. Am. Chem. Soc. 126 (2004) 6560. and refs. therein.
[16] H. Fenton, I.S. Tidmarsh, M.D. Ward, Dalton Trans. 39 (2010) 3805. and refs.
therein.
Data for complexes were collected on a Bruker Smart Apex CCD
diffractometer and used in the full matrix least squares refinement.
The structures were solved by direct methods from final difference
Fourier syntheses. All non-hydrogen atoms were refined anisotrop-
ically. Suitable crystals of 1 and 3 were obtained from concentrated
solutions of chloroform and 2 from hexane all of them after several
days at ꢀ4 °C, while crystals for 4 and 6 were obtained by slow va-
por phase diffusion of their methylene chloride solutions and hex-
ane at 5 °C.
[17] V.J. Catalano, B.L. Bennet, M.A. Malwitz, R.L. Yson, H.M. Kar, S. Muratidis, S.
Horner, Comments Inorg. Chem. 24 (2003) 39.
[18] M.R. Churchill, K.N. Amoth, H.J. Wasserman, Inorg. Chem. 20 (1981) 1609.
[19] E.W. Abel, S.K. Bhargava, M.M. Bhatti, M.A. Mazid, K.G. Orrell, V. Sik, M.B.
Hursthouse, K.M. Abdul Malik, J. Organomet. Chem. 250 (1983) 373.
[20] J.E. Drake, M.B. Hursthouse, M. Kulcsar, M.E. Light, A. Silvestru, J. Organomet.
Chem. 623 (2001) 153.
[21] H. Egold, S. Klose, U. Flörke, Z. Anorg. Allg. Chem. 627 (2001) 164.
[22] D. Vitali, F. Calderazzo, Gazz. Chim. It. 102 (1972) 587.
5. Supplementary data
CCDC 780509, 780510, 780511, 780512 and 780513 contain the
supplementary crystallographic data for 1, 2, 6, 3, and 4. These data