Formation of 1,3-diphosphacyclobutadiene complexes from phosphaalkynes and their coordination behavior

Article abstract of DOI:10.1002/ejic.201301299

By using [(Cp″′Co)₂tol] (Cp″′ = η⁵-C₅H₂tBu₃, tol = toluene), a new synthesis of the 1,3-diphosphete complexes [Cp″′Co(η⁴-P₂C₂tBu₂)] (1a) and [Cp″′Co(η⁴-P₂C₂iPr₂)] (1b) was found, and their reactions with the Lewis acids W(CO)₄ and Cu^I halides were investigated. The reaction of 1b with W(CO)₄(nbd) (nbd = norbornadiene) leads to the complex [(Cp″′Co)(μ,η^4:1-{PCiPr}₂)]₂W(CO)₄ (2) with the two diphosphete complexes 1b coordinated trans to a central W(CO)₄ moiety. The reactions of 1a with Cu^I halides result in different products depending on the stoichiometry. In a 1:1 ratio, the dimeric compounds 3a-c [(Cp″′Co)(μ,η^4:1-{PCtBu}₂)Cu(μ-X)]₂ (3a: X = Cl; 3b: X = Br, 3c: X = I) were isolated, whereas an excess of CuX gave the two-dimensional polymers [({Cp″′Co}{μ₃,η^4:1:1-(PCtBu)₂})₂(Cu{μ₃-X})₄]_n (6a: X = Cl, 6b: X = Br, 6c: X = I). From the reaction of 1a and 1b with CuBr and CuI in a 1:2 or 2:3 ratio, the one-dimensional polymers [({Cp″′Co}{μ₃,η^4:1:1-(PCR)₂})({Cp″′Co}{μ,η^4:1-(PCR)₂})(Cu{μ₃-X})₄]_n (4a: X = Br, R = iPr, 4b: X = I, R = iPr, 4c: X = I, R = tBu) are formed. From the reaction of 1a with CuI, a second product, [({Cp″′Co}{μ₃,η^4:1:1-(PCtBu)₂})(Cu{μ₃-I})₄(MeCN)₂]_n (5), was isolated by using CH₃CN for crystallization. The products were comprehensively characterized by spectroscopic methods, X-ray crystallography, and ³¹P magic angle spinning (MAS) NMR spectroscopy. A new synthetic route to diphosphete complexes of cobalt was developed and their reactivity towards W(CO)₄(nbd) (nbd = norbornadiene) and Cu^I halides was investigated. For the latter, dimeric, 1D, or 2D polymeric compounds are obtained depending on the stoichiometry used, and their structures reveal (CuX)₄ cubes connected by diphosphete units in which each P atom is able to coordinate to a copper atom.

Full text of DOI:10.1002/ejic.201301299

FULL PAPER
CLUSTER
ISSUE
DOI:10.1002/ejic.201301299
Formation of 1,3-Diphosphacyclobutadiene Complexes
from Phosphaalkynes and Their Coordination Behavior
Eva-Maria Rummel,[a][‡] Maria Eckhardt,[a][‡]
Michael Bodensteiner,[a] Eugenia V. Peresypkina,[b]
Werner Kremer,[c] Christian Gröger,[c] and Manfred Scheer*[a]
COVER PICTURE
Keywords: Phosphaalkynes / Diphosphete ligands / Coordination polymers / Heterometallic complexes / Copper / Cobalt
By using [(CpЈЈЈCo)2tol] (CpЈЈЈ = η5-C5H2tBu3, tol = toluene),
new synthesis of the 1,3-diphosphete complexes
an excess of CuX gave the two-dimensional polymers
[({CpЈЈЈCo}{μ3,η4:1:1-(PCtBu)2})2(Cu{μ3-X})4]n (6a: X = Cl, 6b:
X = Br, 6c: X = I). From the reaction of 1a and 1b with CuBr
and CuI in a 1:2 or 2:3 ratio, the one-dimensional polymers
[({CpЈЈЈCo}{μ3,η4:1:1-(PCR)2})({CpЈЈЈCo}{μ,η4:1-(PCR)2})(Cu{μ3-
X})4]n (4a: X = Br, R = iPr, 4b: X = I, R = iPr, 4c: X = I, R =
tBu) are formed. From the reaction of 1a with CuI, a second
product, [({CpЈЈЈCo}{μ3,η4:1:1-(PCtBu)2})(Cu{μ3-I})4(MeCN)2]n
(5), was isolated by using CH3CN for crystallization. The
products were comprehensively characterized by spectro-
scopic methods, X-ray crystallography, and 31P magic angle
spinning (MAS) NMR spectroscopy.
a
[CpЈЈЈCo(η4-P2C2tBu2)] (1a) and [CpЈЈЈCo(η4-P2C2iPr2)] (1b)
was found, and their reactions with the Lewis acids W(CO)4
and CuI halides were investigated. The reaction of 1b with
W(CO)4(nbd) (nbd = norbornadiene) leads to the complex
[(CpЈЈЈCo)(μ,η4:1-{PCiPr}2)]2W(CO)4 (2) with the two diphos-
phete complexes 1b coordinated trans to a central W(CO)4
moiety. The reactions of 1a with CuI halides result in different
products depending on the stoichiometry. In a 1:1 ratio, the
dimeric compounds 3a–c [(CpЈЈЈCo)(μ,η4:1-{PCtBu}2)Cu(μ-
X)]2 (3a: X = Cl; 3b: X = Br, 3c: X = I) were isolated, whereas
the neutral bisphosphacyclobutadiene complex [Fe(η4-
P2C2tBu2)2]. As all of these complexes and also a large
number of others carry diphosphete ligands with free elec-
tron pairs on the phosphorus site, it is astonishing that very
few examples of the coordination behavior of diphosphete
complexes are known. Mainly, their coordination to metal
carbonyl complexes[1e,3a] and CpRM fragments[1b,1c] can be
found in the literature. Recently, the coordination of dipho-
sphete complexes to silver and gold was reported;[4] how-
ever, no coordination to copper halides is known so far.
Within our systematic studies of the coordination behav-
ior of polyphosphorus ligand complexes towards Lewis ac-
ids such as CuI halides, the behavior of this class of ligand
is of special interest. As CR groups are isolobal with the
P moiety, the diphosphetes are related to cyclo-P4 ligands.
Remarkably, for complexes containing cyclo-P4 ligands, we
have so far only obtained spherical clusters,[5] whereas for
cyclo-P5 ligand complexes, we have isolated fullerene-like
nanoballs[6] as well as oligomers and polymers.[7] As an ex-
tension of these studies, we introduced isolobal CR groups
into the ring systems of cyclo-P5 ligand complexes and in-
vestigated the coordination behavior of the 1,2,4-tri-
Introduction
The (cyclo)oligomerization chemistry of λ3-phospha-
alkynes is of broad interest owing to the similarity of their
reactivity to that of their organic alkyne relatives. Numer-
ous oligomerization products from dimers to pentamers
have been isolated to date.[1]
Since the first isolation of 1,3-diphosphacyclobutadiene
complexes in 1986 by Nixon et al.[1d] and Regitz et al.,[1b]
this kind of complex has been thoroughly studied. As these
first examples represent heteroleptic complexes with di-
phosphete and cyclopentadiene (Cp) ligands, the Regitz
group also prepared the first homoleptic diphosphete com-
plex, [Ni(η4-P2C2tBu2)2], in 1990.[2] Only recently, Lam-
mertsma et al. showed that not only Ni0 but also Co–I and
Fe–I can bear two diphosphete ligands to form homoleptic
complexes.[3] The iron derivative could be oxidized to form
[a] Institut für Anorganische Chemie, Universität Regensburg,
93040 Regensburg, Germany
E-mail: manfred.scheer@ur.de
http://www.ur.de/chemistry-pharmacy/inorganic-chemistry-
scheer/index.html
[b] Nikolaev Institute of Inorganic Chemistry,
Siberian Division of RAS,
phosphaferrocene derivatives [FeCpR(P3C2tBu2)] [CpR
=
Acad. Lavrentiev str. 3, 630090 Novosibirsk, Russia
[c] Institut für Biophysik und Physikalische Biochemie,
Universität Regensburg,
Cp, C5Me5 (Cp*), C5H2tBu3 (CpЈЈЈ)][8] and the hexaphos-
phaferrocene [Fe(η5-P3C2tBu2)2][9] towards CuI halides to
examine the effect of the bulkiness of the CpR moiety and
the neighboring tBu group on the resulting complexes.
Here, the coordination behavior is mainly determined by
93040 Regensburg, Germany
[‡] Both authors contributed equally to this work.
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201301299.
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the adjacent P atoms, whereas we only found few examples
in which the single P atom also coordinates to Cu centers.
However, the 1,3-diphosphete complexes possess only iso-
lated P atoms and these display a large bite angle. Thus,
the coordination behavior was of interest to understand the
dependence on the steric bulk of the R group at the adja-
cent C atoms.
Herein, we report a new synthetic method to obtain tBu-
and iPr-substituted 1,3-diphosphete complexes of cobalt
and their unusual coordination behavior towards the
W(CO)4 unit and CuI halide complexes.
Results and Discussion
Synthesis and Characterization of the Starting Materials
[CpЈЈЈCo(η4-P2C2R2)] (1a: R = tBu, 1b: R = iPr)
Whereas the first examples of diphosphete complexes
were derived from the half-sandwich complexes
[CpRM(C2H4)2][1d,2] (M = Co, Rh, Ir; R = H, Me), we re-
port a new synthesis from the triple-decker complex
[(CpЈЈЈCo)2tol] (tol = toluene).[10] In reactions with phos-
phaalkyne derivatives, the desired orange-red diphosphete
complexes were obtained in good isolated yields [Equa-
tion (1)].
Figure 1. Molecular structure of 1b. Selected bond lengths [Å] and
angles [°]: P1–C1 1.798(4), P1–C2 1.800(3), P2–C1 1.795(3), P2–
C2 1.798(5), Co–P1 2.2531(14), Co–P2 2.2391(13), Co–C1 2.060(3),
Co–C2 2.096(5), Co–CpЈЈЈcent 1.6789(6), Co–(P2C2iPr2)cent
1.7513(7), P1–C1–P2 98.68(18), P1–C2–P2 98.49(18), C1–P1–C2
81.18(18), C1–P2–C2 81.31(16).
(1)
Complexes 1a and 1b were identified by 1H, 31P, 31P{1H},
and 13C NMR spectroscopy, field desorption (FD) mass
spectrometry, elemental analysis, and X-ray structure deter-
mination (Figure 1 and Supporting Information).
The 1,3-diphosphacyclobutadiene moieties in 1a and 1b
are essentially planar with torsion angles P1–C1–P2–
C2 ≈ 6° (1a) and 4° (1b). Owing to the steric hindrance of
the tBu groups of the CpЈЈЈ moiety, the tBu groups of 1a
and the iPr groups of 1b arrange themselves to minimize
interactions.
Figure 2. Variable-temperature 31P{1H} NMR spectra of 1a in
[D8]toluene.
Interestingly, the 31P NMR spectrum of 1b at ambient
temperatures shows a broadened singlet at δ = 41.3 ppm,
which reveals the equivalence of both P atoms; however, for
1a, two separate singlets at δ = 23.4 and 42.3 ppm are de- determined to be 64.5 kJmol–1. These values are in agree-
tected. Owing to the slightly larger tBu groups in the dipho- ment with the results of Green et al.[11] who first measured
sphete ligand of 1a, the four-membered ring cannot rotate the rotational barrier of this type of complexes. A solution
at ambient temperature, whereas 1b has a lower barrier to of 1b has to be cooled to determine the rotational barrier
ring whizzing. To determine the rotational barrier, variable- in the 31P{1H} NMR measurements, and the coalescence
temperature 31P{1H} NMR spectra were recorded (Fig- temperature is 228 K. The complete separation of the two
ures 2 and 3).
signals (Δν = 143.9 Hz) was found at 193 K (Figure 3), and
‡
Complex 1a shows the coalescence of the signals at the resulting ΔGc value is 44 kJmol–1. As for 1a, no cou-
373 K, and complete separation is found at 313 K (Δν = pling between the two phosphorus atoms could be iden-
‡
3067.2 Hz; Figure 2). The free activation energy ΔGc was tified for 1b.
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Figure 3. Variable-temperature 31P{1H} NMR spectra of 1b in [D8]toluene.
As both 1a and 1b bear phosphorus atoms with a lone product 2, which could be isolated as orange-red crystals
pair, we studied their reactivity towards W(CO)4(nbd) (nbd [Equation (2)]. Afterwards, the 31P NMR spectrum of the
= norbornadiene, C7H8) and copper(I) halides.
mother liquid showed signals for 2 and an unidentified
minor product at δ = 49.6 ppm.
Investigations of the Coordination Behavior of the
Diphosphete Complexes
Synthesis and Characterization of [(CpЈЈЈCo)(μ,η4:1
{PCiPr}2)]2W(CO)4 (2)
-
The synthesis of 2 was accomplished by layering a solu-
tion of W(CO)4(nbd) in tetrahydrofuran (THF) over a solu-
tion of 1b in n-pentane. After ten days, the resulting red
solution showed two sets of signals in the 31P NMR spec-
trum: one singlet at δ = 49.6 ppm that possessed tungsten
(2)
The EI mass spectrum of 2 shows the molecular ion
satellites (1JP,W = 225.9 Hz) and accounted for 10% of the peak. Fragment peaks for the successive elimination of
overall P content of the reaction mixture, and two singlets three carbonyl groups are observed as well as for the elimi-
in a 1:1 ratio at δ = –24.6 (no tungsten satellites) and nation of one diphosphete complex 1b and the four carb-
56.4 ppm (1JP,W = 275.4 Hz), which accounted for 90% of onyl groups. The IR spectrum of 2 in solution reveals ter-
the P content. These two singlets correspond to the main minal carbonyl groups.
Figure 4. Molecular structure of 2. Selected bond lengths [Å] and angles [°]: P1–C1 1.781(4), P2–C1 1.795(3), P1–C5 1.772(3), P2–C5
1.796(3), P1–W 2.4316(7), [CpЈЈЈ]Centr–Co1 1.688, [C2P2]Centr–Co1 1.760; C5–P2–C1 82.02(17), C5–P1–C1 83.
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Scheme 1. Products of the reaction of the diphosphete complexes 1a or 1b with CuI halides in different stoichiometries at ambient
temperature in mixtures of CH2Cl2 and CH3CN.
Notably, in 2 a trans-coordinated W(CO)4 unit is found mers
[({CpЈЈЈCo}{μ3,η4:1:1-(PCR)2})({CpЈЈЈCo}{μ,η4:1
-
and not a cis complex like the starting material W(CO)4-
(nbd). The steric constraints imposed by the diphosphete
compounds must force the rearrangement of the CO ligands
to form the trans product. The structure of 2 was confirmed
by X-ray crystallography. Orange-red blocks of 2 crystallize
in the monoclinic space group C2/c and there is an inver-
sion center within the molecule (Figure 4).
Compared with those of the starting material 1b, the P–
C bond lengths in the diphosphete rings of 2 are slightly
shorter [1.772(3)–1.796(3) Å; 1b: 1.795(3)–1.800(3) Å]. The
angles differ only slightly (by ca. 2°) from those in 1b, and
the P–W bond lengths of 2.4316(7) Å are typical. The X-
ray crystallographic data for 1–2 are summarized in Table 4.
(PCR)2})(Cu{μ3-X})4]n (4a: R = iPr, X = Br; 4b: R = iPr,
X = I; 4c: R = tBu, X = I). The product of the reaction of
1b and CuCl was isolated in low yields as a microcrystalline
powder. Unfortunately, no crystals suitable for X-ray crys-
tallography could be obtained from this reaction. However,
spectroscopic data suggest the formation of the same poly-
mer. The same products are obtained if the reaction is per-
formed with more CuX (1:2 ratio). However, in this case, a
side-product
in
the
reaction
to
form
4c,
[({CpЈЈЈCo}{μ3,η4:1:1-(PCtBu)2})(Cu{μ3-I})4(MeCN)2]n (5),
was isolated by crystallization from CH3CN/n-hexane. The
31P{1H} NMR spectrum of this reaction mixture reveals
another product in very low concentration that could not
be isolated or identified.
Synthesis and Characterization of Products Obtained from
the Reactions of 1a and 1b with CuI Halides
If a large excess of CuX is used in the layering reactions
with 1a, the 2D polymers [({CpЈЈЈCo}{μ3,η4:1:1-(PCtBu)2})2-
(Cu{μ3-X})4]n (6a: X = Cl, 6b: X = Br, 6c: X = I) are
formed in yields of 63–65% (Scheme 1). Again, the 31P{1H}
The reaction of diphosphete complex 1a with CuX in a
1:1 ratio leads to the dimeric products [(CpЈЈЈCo)(μ,η4:1
-
1
and H NMR spectra of the reaction mixture do not indi-
{PCtBu}2)Cu(μ-X)]2 (3a: X = Cl; 3b: X = Br, 3c: X = I),
which were obtained in moderate yields (34–69%) by stir-
ring the reaction mixtures at ambient temperatures
(Scheme 1), but quantitative conversion to the products was
observed by NMR spectroscopy. Unfortunately, crystals of
3c show strong twinning, which could not be completely
refined. Nevertheless, the data strongly suggest the forma-
tion of a complex similar to 3a and 3b. Interestingly, oligo-
meric products were not obtained by reaction of 1b in a 1:1
ratio with CuX.
cate the formation of any other phosphorus-containing
products.
The yellow to orange products 3–6 are sparingly soluble
in common solvents. For NMR spectroscopy and mass
spectrometry, mixtures of CD2Cl2 and CD3CN have been
used. Therefore, it is not clear whether the structure of the
polymers is retained in solution or if smaller units are
formed by replacement of the P atom coordination with
acetonitrile donors. Therefore, 31P NMR magic angle spin-
Layering a CH2Cl2 solution of 1 in a 2:3 ratio with CuX ning (MAS) spectra were also recorded for selected prod-
in CH3CN solution results in the formation of the 1D poly- ucts (vide infra).
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X-ray Crystallographic Characterization of 3–6
[(CpЈЈЈCo)(μ,η4:1-{PCtBu}2)Cu(μ-X)]2 (3a: X = Cl; 3b:
X = Br)
The molecular structure of 3a is shown in Figure 5. The
P atom of each diphosphete ligand is bound to a Cu(1)
atom and, thus, has a trigonal planar coordination mode,
and the CpЈЈЈCo fragments face opposite sides to minimize
steric repulsion.
Figure 6. Section of the 1D polymer structure of 4a and 4b. H
atoms omitted for clarity. Selected bond lengths [Å] and angles [°]
for 4a (X = Br): P1–C1 1.774(8), P1–C5 1.777(8), P3–C26 1.788(8),
P3–C30 1.775(8), Cu3–P3 2.193(2), Cu4–P1 2.1899(19), Cu1–Br1
2.5119(13), Cu1–Br4 2.5575(12), P1–Co1 2.227(2), P3–Co2
2.230(2), P4–Co2 2.246(2), C5–Co1 2.069(9), C1–Co1 2.111(7),
C26–Co2 2.103(8), C30–Co2 2.087(9), P1–C1–P2 97.6(4), P1–C5–
P2 97.5(4), C1–P1–C5 82.9(4), C1–P2–C5 81.8(4), Cu1–Br1–Cu2
82.94(4), P1–Cu4–Br4 110.33(7), Cu1–Br4–Cu3 83.16(4), P1–Cu4–
Br1 131.88(7), Br1–Cu1–Br2 96.61(5), P5–Cu1–Br4 106.35(7), Br1–
Cu1–Br4 101.32(4). Selected bond lengths [Å] and angles [°] for 4b
(X = I): P1–C1 1.781(5), P1–C2 1.783(6), P3–C3 1.778(4), P3–C4
1.788(4), Cu2–P3 2.2354(11), Cu1–P1 2.2457(12), Cu1–I1
2.6811(7), Cu1–I4 2.7257(6), P1–Co1 2.2317(13), P2–Co1
2.2496(12), P3–Co2 2.2323(12), P4–Co2 2.2492(12), C2–Co1
2.093(4), C1–Co1 2.076(5), C3–Co2 2.080(4), C4–Co2 2.096(4),
P1–C1–P2 97.6(3), P1–C2–P2 97.6(3), C1–P1–C2 82.7(2), C1–P2–
C2 81.8(2), Cu1–I1–Cu2 68.31(2), P1–Cu1–I1 107.51(4), Cu1–I4–
Cu3 78.89(2), P1–Cu1–I2 111.00(4), I1–Cu1–I2 98.72(2), P1–Cu1–
I4 125.33(3), I1–Cu1–I4 105.34(2).
Figure 5. Molecular structure of 3a. H atoms omitted for clarity.
Selected bond lengths [Å] and angles [°]: P1–C1 1.774(2), P2–C1
1.794(2), P1–C6 1.781(2), P2–C6 1.800(2), C6–C7 1.518(3), C1–C2
1.516(3), P1–Cu1 2.1485(6), Cu1–Cl1 2.2721(6), Cu1–Cl1Ј
2.2766(7), [CpЈЈЈ]Centr–Co1 1.7015(3), [C2P2]Centr–Co1 1.7743(3);
C6–P2–C1 82.29(9), P1–Cu1–Cl1 129.94(2), C6–P1–C1 83.39(9),
P1–Cu1–Cl1Ј 130.32(2), P2–C1–P1 97.27(10), Cu1–Cl1–Cu1Ј
80.28(2), P2–C6–P1 96.83(9), Cl1–Cu1–Cl1Ј 99.72(2), C6–P1–Cu1
138.13(7).
Compound 3a has similar P–C bond lengths to those of
1a [3a: 1.774(2)–1.794(2) Å, 1a: 1.784(2)–1.789(2) Å]. The
angles P(1)–C(1)–P(2) [96.83(9)–97.27(10)°] for 3a are
within the same range as those for 1a. The diphosphete ring
is essentially planar.
The asymmetric unit of 3b is occupied by two halves of
two independent molecules (see Supporting Information).
The P–C bond lengths are in the same range as those of 3a.
Compound 3b has four different phosphorus atoms, two are
bound to copper atoms and two are non-coordinating. This
is the main difference in comparison to 3a, which is also
revealed by the 31P MAS NMR spectra of both com-
pounds.
uncoordinated. Therefore, six independent phosphorus
atoms are found in the asymmetric unit, four are coordi-
nated to copper atoms, whereas two are not coordinated.
As with 3, the P–C bond lengths and angles of 4 vary
little from those of 1. However, the (CuX)4 units are very
distorted from ideal cubes, likely because of steric pressure.
The X-ray crystallographic data for 3 and 4 are found in
Table 5. The X-ray crystallographic data for 4c in the tri-
clinic crystal system are summarized in the Supporting In-
formation.
[({CpЈЈЈCo}{μ3,η4:1:1-(PCR)2})({CpЈЈЈCo}{μ,η4:1-(PCR)2})-
(Cu{μ3-X})4]n (4a: X = Br, R = iPr, 4b: X = I, R = iPr,
4c: X = I, R = tBu)
Compounds 4a–4c crystallize as yellow needles or orange
¯
plates in the space group P1. The solid-state structures of
In 4c, the same structural features can be found as in 4a
and 4b. Here, four phosphorus atoms coordinate to copper
atoms, whereas two remain in a non-coordinating mode.
The bond lengths between the P and Cu atoms are compar-
able to those in the iPr derivatives 4a and 4b.
4a and 4b are depicted in Figure 6. Crystals of 4c in the
monoclinic space group P21/c were also obtained (Fig-
ure 7).
The polymeric 1D structures of 4 are formed by (CuX)4
cubes in which each copper is coordinated to a P atom of
the diphosphete complex 1a or 1b. However, only one di-
phosphete complex bridges two (CuX)4 cubes, and this re-
sults in a 1D polymer. The other two copper atoms of each
copper(I) halide cube are coordinated by ancillary diphos-
[({CpЈЈЈCo}{μ3,η4:1:1-(PCtBu)2})(Cu{μ3-I})4(MeCN)2]n
(5)
Compound 5 crystallizes as orange needles in the space
¯
phete complexes 1a or 1b, which have one phosphorus atom group P1 (Figure 8).
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Figure 8. Section of the 1D polymeric structure of 5. H atoms omit-
ted for clarity. Selected bond lengths [Å] and angles [°]: P11–C11
1.785(7), P11–C12 1.796(6), P12–C11 1.780(7), P12–C12 1.788(7),
P12–Cu11 2.2548(18), Cu11–I7 2.6975(10), [CpЈЈЈ]Centr–Co1
1.7123, [C2P2]Centr–Co1 1.7827; C11–P11–C12 83.5(3), P11–C11–
P12 96.6(3), C11–P12–Cu11 130.9(2), C12–P12–Cu11 135.7(2), I1–
Cu12–I4 104.01(4), Cu11–I1–Cu12 72.37(3), Cu11–I4–Cu12
71.09(3).
Figure 7. Section of the 1D polymeric structure of 4c in space
group P21/c. H atoms omitted for clarity. Selected bond lengths [Å]
and angles [°]: P1–C16 1.779(8), P3–C26 1.777(11), P1–C17
1.783(8), P3–C27 1.786(10), P2–C16 1.790(8), P4–C26 1.798(11),
P2–C17 1.804(8), P4–C27 1.784(11), P1–Cu1 2.215(2), P3–Cu2
2.224(3), P5–C36 1.793(8), P6–C37 1.801(8), P5–C37 1.775(8), P5–
Cu3 2.236(2), P6–C36 1.769(8), [CpЈЈЈ]Centr–Co1 1.7100, [C2P2]
Centr–Co1 1.7803; C16–P1–C17 83.4(4), C16–P2–C17 82.4(4), C36–
P5–C37 83.3(4), C36–P6–C37 83.2(4), C26–P3–C27 82.2(5), C26–
P4–C27 81.7(5), P3–C27–P4 98.1(6), P3–C26–P4 97.9(6), P1–C17–
P2 96.8(4), P2–C16–P1 97.4(4), P5–C36–P6 96.4(4), P5–C37–P6
96.4(4).
The 2D polymeric structures are formed by (CuX)4
cubes, which bind diphosphete units on all copper edges.
Unlike 4a–4c, the phosphorus atoms of the diphosphetes
are all linked by copper atoms and are all trigonal planar.
One macrocyclic unit is formed by four (CuX)4 cubes and
four diphosphete complexes 1a (Figure 10). As one cyclic
unit requires only half of the (CuX)4 cube, the 2D structure
is built up by linking two of those units through one
(CuX)4 cube.
Two edges of the distorted (CuI)4 cube of 5 are linked
by diphosphete complexes 1a to form a one-dimensional
polymer. The remaining Cu atoms are saturated by acetoni-
trile ligands in contrast to the polymers 4a–4c, which bear
terminal diphosphete complexes 1a or 1b at the two remain-
ing copper atoms. However, two independent strands of the
polymeric compound 5 can be found in the asymmetric
unit. This results in the presence of four independent phos-
phorus atoms, which can also be distinguished in the MAS
NMR spectrum. The bond lengths and bond angles of the
diphosphete moiety in 5 are comparable with those in the
free diphosphete 1a.
The bonding features of 6 will be exemplified by those
of 6a, as they are similar to those of 6b and 6c. The P–C
bonds in 6a are 1.7815(19)–1.7891(17) Å and are compar-
able to those in the starting material 1a. The same is true
for the bond angles inside the four-membered rings of 6a.
The C–P–C angles of 83.28(8)–83.68(8)° and the P–C–P
angles of 96.238(78)–96.575(88)° differ only slightly (Ϯ 2°)
from those in 1a. The P–Cu bond lengths of 2.1913(5)–
2.2003(6) Å are marginally longer than that of 3a
[2.1485(6) Å]. However, the coordination mode for the cop-
per atoms is different in both complexes. The distance be-
tween the center of the diphosphete ring and the capping
cobalt atom is slightly elongated to 1.7814 Å (3a: 1.7743 Å,
1a: 1.7674 Å).
[({CpЈЈЈCo}{μ3,η4:1:1-(PCtBu)2})2(Cu{μ3-X})4]n (6a: X =
Cl, 6b: X = Br, 6c: X = I)
There are differences in the angles of 6a–6c. Whereas 6a
All compounds crystallize as yellow to orange blocks in possesses Cl–Cu–Cl angles that are nearly perpendicular
the monoclinic space group P21/c. The asymmetric unit of [89.64(1)–90.80(1)°], the Br–Cu–Br angles in 6b are much
all three compounds consists of one (CuX)4 cube and two more obtuse [102.68(2)–103.96(2)°]. The I–Cu–I angles in
diphosphete units 1a; therefore, there are four independent 6c are somewhat between those values [95.98(3)–97.16(3)°]
phosphorus atoms in the unit cell (Figure 9). Each copper owing to the more readily polarized iodide ligand. Whereas
atom of a cube is coordinated by three halogen ions and 6a has nearly perfect (CuCl)4 cubes, both other (CuX)4
one phosphorus atom of the diphosphete ring in a tetra- cubes (X = Br, I) are distorted, but these distortions do not
hedral coordination mode.
affect the overall structure of the 2D polymers.
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Figure 9. Section of the solid-state structure of 6a–6c. H atoms are omitted for clarity. Selected bond lengths [Å] and angles [°] for 6a (X
= Cl): P1–C23 1.7815(18), P2–C23 1.7876(18), P1–C18 1.7852(18), P2–C18 1.7876(18), P2–Cu1 2.2003(6), P3–Cu2 2.1913(5), P3–C50
1.7844(18), P4–C45 1.7891(17), P3–C45 1.7837(18), P4–C50 1.7853(18), Cu2–Cl3 2.4853(4), Cu2–Cl2 2.3816(4), [CpЈЈЈ]Centr–Co1 1.7099,
[C2P2]Centr–Co1 1.7814; C18–P1–C23 83.52(8), C18–P2–C23 83.28(8), C50–P4–C45 83.50(8), P1–C23–P2 96.58(9), P1–C18–P2 96.44(9),
P3–C45–P4 96.24(9), Cl2–Cu2–Cl3 90.80(1), Cl2–Cu1–Cl3 89.64(1). Selected bond lengths [Å] and angles [°] for 6b (X = Br): P1–C23
1.785(2), P2–C23 1.782(2), P1–C18 1.788(2), P2–C18 1.783(2), P2–Cu1 2.2003(7), P3–Cu2 2.1958(7), P3–C50 1.791(2), P4–C50 1.783(3),
P3–C45 1.791(2), Cu2–Br3 2.5282(4), Cu2–Br2 2.5523(5), [CpЈЈЈ]Centr–Co1 1.7119, [C2P2]Centr–Co1 1.7850; C18–P1–C23 83.20(11), C18–
P2–C23 83.42(11), C50–P4–C45 83.61(11), P1–C23–P2 96.68(12), P1–C18–P2 96.54(12), P3–C45–P4 96.28(12), Br2–Cu2–Br3 103.96(2),
Br2–Cu1–Br3 102.68(2). Selected bond lengths [Å] and angles [°] for 6c (X = I): P1–C23 1.784(6), P2–C23 1.784(6), P1–C18 1.774(6),
P2–C18 1.776(6), P2–Cu1 2.2550(17), P3–Cu2 2.2452(16), P3–C50 1.784(6), P4–C50 1.780(7), P3–C45 1.791(6), P4–C45 1.793(6), Cu2–
I3 2.7067(10), Cu2–I2 2.7409(10), [CpЈЈЈ]Centr–Co1 1.7101, [C2P2]Centr–Co1 1.7847; C18–P1–C23 82.6(3), C18–P2–C23 82.4(3), C50–P4–
C45 83.2(3), P1–C23–P2 97.1(3), P1–C18–P2 97.6(3), P3–C45–P4 96.4(3), I2–Cu2–I3 95.98(3), I2–Cu1–I3 97.16(3).
the phosphorus atoms in 1a are not equivalent in solution
owing to hindered rotation, the room-temperature 31P{1H}
NMR spectra of 3a and 3b also show two singlets (3a: δ =
14.1 and 30.9 ppm, 3b: δ = 8.2 and 24.8 ppm, 3c: δ =14.4
and 32.4 ppm). The downfield-shifted signals are assigned
to the phosphorus atom coordinated to the copper atom;
this is confirmed by the 31P{1H} MAS NMR spectra. Here
for 3a, a singlet at δ = –2.0 ppm and a superimposed quar-
tet at δ = 28.7 ppm [owing to coupling with the copper
atom (I = 3/2)] are found (Figure 11).
Figure 11. 31P{1H} MAS NMR spectrum of 3a. Experimental
Figure 10. The 2D structure of 6a showing intertwined cycles. CpЈЈЈ
curve in blue, fitted curve in red.
and tBu moieties are omitted for clarity.
From the simulated spectrum, the coupling constant
1JP,Cu = 1850 Hz has been determined. The 31P{1H} MAS
NMR spectra of 3b and 3c are different but are consistent
with the X-ray crystallographic data. Two singlet signals
Spectroscopic Characterization of 3–6
Dimeric Compounds 3a–3c
1
In their respective H and 13C NMR spectra, the ligands with two partially overlapping quartet signals are found,
of 3a–3c show the expected resonances for the CpЈЈЈ moiety exemplified for 3b in Figure 12. The coupling constants
as well as for the tBu groups of the diphosphete rings. As 1JP,Cu for these complexes are 1900 (3b) and 1500 Hz (3c).
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4b show large fragments for different combinations of di-
phosphete complexes and CuX moieties (Table 2). Com-
pound 4c shows essentially the same fragmentation as that
of 6c (Table 3).
Table 2. Comparison of different fragments in the ESI mass spectra
for 4a and 4b.
Fragment[a][b]
m/z for 4a
m/z for 4b
[L4Cu6X5]+
[L4Cu5X4]+
[L4Cu4X3]+
2636.1
2494.5
2350.8
–
–
2492.9
Figure 12. 31P{1H} MAS NMR of 3b. Experimental curve in blue,
fitted curve in red.
[a] L = 1b = CpЈЈЈCo(P2C2iPr2). [b] Other fragments were found
and are listed in the Experimental Section.
As expected for 5, two singlets at δ = 12.3 and 30.2 ppm
could be found in the 31P{1H} NMR of the reaction mix-
By comparing the solution NMR spectra of 3a–3c with
those of 4–6, it is evident that all of them show signals in
similar regions, although the differences with their respec-
tive solid-state NMR spectra are substantial. The results
suggest that disassembly and reassembly in solution are
most likely. This hypothesis is reinforced by the fact that all
ESI mass spectra for the dimeric compounds (recorded in
1:1 mixtures of CH2Cl2 and CH3CN) show only fragments
of different ratios for copper halide and 1a, whereas no mo-
lecular ion peak M+ could be observed (Table 1). Moreover,
for all compounds 3a–c, fragments bigger than the M+
peaks were observed, which indicates a dynamic disas-
sembly and reassembly of fragments in solution.
1
ture as well as of the pure isolated substance. The H and
13C{1H} NMR spectra show distinct signals for the tBu and
CpЈЈЈ moieties. Solutions of 5 in CH3CN/CH2Cl2 mixtures
were measured by ESI mass spectrometry, and amongst
others, there are peaks for the ions [CpЈЈЈ2Co2(C2tBu2P2)2-
Cu4I3]+ (m/z = 1618.8), [CpЈЈЈ2Co2(C2tBu2P2)2Cu3I2]+ (m/z
=
1429.3), and [CpЈЈЈ2Co2(C2tBu2P2)2Cu2I]+ (m/z
1239.4).
=
The solid-state NMR spectra of 5 showed complicated
patterns of superimposed signals (see Supporting Infor-
mation). Modeling of the MAS NMR spectrum was pos-
sible when it was fitted for four independent phosphorus
signals each coupled to one copper nucleus. These assump-
tions were made in accordance with the results of the X-ray
crystallographic measurements (vide supra). Thus, all four
phosphorus atoms that coordinate to copper atoms are split
into four quartets with coupling constants of 1400–
1500 Hz.
Table 1. Comparison of different fragments in the ESI mass spectra
of 3a–3c.
Fragment
m/z for 3a
m/z for 3b
m/z for 3c
[L2Cu3X2]+[a]
1245.3
1147.5
1047.5
696.1
1335.4
1191.5
1047.5
740.2
1429.4
1239.5
1047.5
786.2
[L2Cu2X]+
[L2Cu]+
[LCu2X + CH3CN]+
[LCu + CH3CN]+
2D Polymeric Compounds 6a–6c
596.2
596.2
596.2
Despite their only moderate solubility, 1H and 13C NMR
spectra could be recorded for these compounds in 1:1 mix-
tures of CD2Cl2/CH3CN. These spectra show the expected
signals for the CpЈЈЈ moiety as well as for the tBu groups,
[a] L = 1a = CpЈЈЈCo(P2C2tBu2).
1D Polymeric Compounds 4 and 5
Compounds 4a–4c are soluble in a mixture of CD2Cl2 similar to the spectra of 3–5. The 31P{1H} NMR spectra of
and CD3CN and can be analyzed by NMR spectroscopy. 6a–6c show two nonequivalent phosphorus atoms at δ =
1
Here, the H NMR spectra again show peaks for the CpЈЈЈ 12.7 and 29.4 (6a), 2.3 and 18.6 (6b), and 8.6 and 26.6 ppm
and iPr/tBu moieties. As the solubility is limited, the (6c). Again, the possibility of dynamic behavior in solution
13C{1H} NMR spectra could not be recorded for all of the is evident by comparison with the solid-state structure,
1D polymers, and the quality of the 31P{1H} NMR spectro- which predicts four different signals for the independent
scopic data is quite poor. Complexes 4a and 4b show similar phosphorus atoms. Also, all of the ESI mass spectra for the
31P{1H} NMR spectra with broad singlets at δ = 23.8 (4a) 2D polymeric compounds show the assembly of different
and 26.9 ppm (4b), whereas 4c shows two resonances at δ building blocks of 1a and CuI halides (Table 3).
= 15.4 and 33.3 ppm. The possibility of a dynamic behavior
To confirm that the solid-state structure contains only
in solution is again evident as four different signals should the two-dimensional polymers, 31P{1H} MAS NMR were
be observed for these compounds. As solubility of the poly- recorded for 6a–6c and are exemplified for 6a in Figure 13.
mers decreases rapidly at lower temperatures, no VT NMR The 31P{1H} MAS NMR spectra of 6b and 6c are given in
studies could be conducted. However, 31P MAS NMR spec- the Supporting Information.
troscopy could be performed for 4c and gave evidence for
the existence of the independent P atoms as observed in the posed signals and could be modeled with the assumption
solid state (cf. Supporting Information). of four independent phosphorus atoms, as found in the so-
All of the spectra show complicated patterns of superim-
ESI mass spectra could be recorded for the compounds lid-state structures of 6a–6c. All of these phosphorus atoms
in a mixture of CH2Cl2 and CH3CN. Compounds 4a and are split into quartets owing to coupling with the copper
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clusion of oxygen and moisture. All solvents were dried by using
standard procedures and distilled freshly before used. The starting
materials tBuCϵP,[12] [W(CO)4(nbd)],[13] and [(CpЈЈЈCo)2tol][10]
were synthesized according to literature procedures. iPrCϵP[14] was
synthesized according to a modified literature procedure (cf. Sup-
porting Information). Commercial CuI halides were stored under
argon and used as received (Sigma Aldrich). Deuterated solvents
were degassed, dried, and distilled prior to use. NMR spectra were
Table 3. Comparison of different fragments in the ESI mass spectra
of 6a–6c.
Fragment[a][b]
m/z for 6a
m/z for 6b
m/z for 6c
[L3Cu5X4]+
[L3Cu4X3]+
[L3Cu3X2]+
[L2Cu4X3]+
1937.8
1838.1
1739.8
1345.4
–
–
–
–
–
–
1335.3
1429.2
recorded with
a
Bruker Avance 400 spectrometer (1H:
[a] L = 1a = CpЈЈЈCo(P2C2tBu2). [b] As for 3a–3c, other fragments
were observed and are listed in Table 1 and the experimental sec-
tion.
400.130 MHz, 31P: 161.976 MHz, 13C: 100.613 MHz) at ambient
temperature unless otherwise noted. The chemical shifts are re-
ported in ppm relative to internal tetramethylsilane (TMS) or exter-
nal phosphoric acid. Elemental analyses (CHN) were determined
by using a Vario EL III instrument. IR spectra were obtained with
a Varian-Digilab Scimitar FTS800 spectrometer, and FD mass
spectra were measured with a Finnigan MAT95 spectrometer.
31P{1H} MAS NMR spectra were recorded with a Bruker Advance
300 spectrometer equipped with a double resonance 2.5 mm MAS
probe. The 31P resonance was 121.495 MHz. The spectra were ac-
quired at MAS rotation frequencies of 30 and 34 kHz, a 90° pulse
length of 2.3 μs, and with relaxation delays between 120 and 450 s.
Simulation of the experimental 31P MAS NMR spectra was per-
formed with the program dmfit.[15]
[CpЈЈЈCo(η4-P2C2R2)] (1a: R = tBu, 1b: R = iPr): [(CpЈЈЈCo)2tol]
(140 mg, 207 μmol) was dissolved in hexane (10 mL), and the solu-
tion was cooled to –80 °C. Upon addition to a solution of the cor-
responding phosphaalkyne (836 μmol) in Et2O, the brown solution
was left to slowly reach room temperature. The solvent was re-
moved in vacuo, and the orange-brown residue was dissolved in
Et2O (2 mL). Slow evaporation of the solvent led to the formation
of orange-red crystals suitable for X-ray structure determination
(crystalline yield: 1a: 162 mg, 41%; 1b: 104 mg, 36%).
Figure 13. 31P{1H} MAS NMR spectrum of 6a. Experimental
curve printed in blue, sum of fitted curves in red. The contributions
of the four different quartets are shown in green and violet.
atoms and overlap to form the observed overall spectra.
1
The coupling constants JP,Cu are 2000 Hz for all quartets
in 6a; 1850, 1800, 1900 and 1850 Hz for quartets in 6b; and
1600, 2000, 1600 and 1400 Hz for quartets in 6c.
1
[CpЈЈЈCo(η4-{PCtBu}2)] (1a): H NMR (C6D6): δ = 1.13 [s, 18 H,
C5(C4H9)3H2], 1.43 [s, 9 H, C5(C4H9)3H2], 1.51 {s, 18 H, [(CH3)3-
CCP]2}, 4.76 [s, 2 H, C5(C4H9)3H2] ppm. 13C{1H} NMR (C6D6): δ
= 31.7 {s, C5H2[C(CH3)3]}, 32.2 {t, C5H2[C(CH3)3]}, 32.5 {s,
Conclusions
3
C5H2[C(CH3)3]}, 32.6 {t, JP,C = 4.9 Hz, [(CH3)3CCP]2}, 35 {s,
We have reported a new synthesis of 1,3-diphosphacyclo-
butadiene complexes and their characterization. Subse-
quent reactions with Lewis acidic compounds depend on
the stoichiometry and concentration of the starting materi-
als and lead to numerous molecular complexes and coordi-
nation polymers. With a 1:1 stoichiometry of the starting
materials 1a/1b and CuX, dimeric compounds were iso-
lated, whereas with increasing CuX, 1D polymers and fi-
nally 2D polymers are formed. In all of these polymers, the
polymeric strand is formed from (CuX)4 cubes and bridging
diphosphete moieties of the Co complexes; this demon-
strates the excellent coordination ability of the single P
atom of the 1,3-diphosphete units. All these compounds
display dynamic behavior in solution. Spectroscopic data
from solution NMR and ESI MS measurements suggest
that these units can disassemble and assemble quite freely.
The structures in the solid state were determined by
31P{1H} MAS NMR, which confirmed the bonding found
in the X-ray structural determinations.
2
C5H2[C(CH3)3]}, 35.1 {t, JP,C = 8.3 Hz, [(CH3)3CCP]2}, 76.6 {s,
1
C5H2[C(CH3)3]}, 105.7 {t, JP,C = 53.2 Hz, [(CH3)3CCP]2}, 110.6
{s, C5H2[C(CH3)3]}, 113 {s, C5H2[C(CH3)3]} ppm. 31P NMR
(C6D6): δ = 23.4 (s), 42.3 (s) ppm. 31P{1H} NMR (C6D6): δ = 23.4
(s), 42.3 (s) ppm. EI-MS (70 eV): m/z (%) = 492 (67) [M]+, 435 (5)
[M – tBu]+, 378 (6) [M – 2tBu]+, 354 (100) [M – 2CtBu]+, 57 (39)
[C4H9]+. C27H47CoP2 (492.52): calcd. C 65.84, H 9.62; found C
66.32, H 9.09.
1
3
[CpЈЈЈCo(η4-{PCiPr}2)] (1b): H NMR (C6D6): δ = 1.00 {d, JH,H
= 6.66 Hz, 12 H, [PCCH(CH3)2]2}, 1.42 [s, 18 H, C5(C4H9)3H2],
3
1.47 [s, 9 H, C5(C4H9)3H2], 2.02 {sept, JH,H = 6.66 Hz, 2 H,
[PCCH(CH3)2]2}, 4.57 [s, 2 H, C5(C4H9)3H2] ppm. 13C{1H} NMR
(C6D6): δ = 25.7 {s, [PCCH(CH3)2]2}, 31.5 {s, C5[C(CH3)3]3H2},
32.1 {s, [PCCH(CH3)2]2}, 32.2 {s, C5[C(CH3)3]3H2}, 32.8 {s,
C5[C(CH3)]3H2}, 34.4 {s, C5[C(CH3)3]3H2}, 78.3 [s, C5(C4H9)3H2],
101.4 {t, 1JP,C = 52.8 Hz, [PCCH(CH3)2]2}, 110.2 [s, C5(C4H9)3H2],
113 [s, C5(C4H9)3H2] ppm. 31P NMR (C6D6): δ = 41.3 ppm (s, 2
P). 31P{1H} NMR (C6D6): δ = 41.3 ppm (s, 2 P). FD-MS: m/z (%)
= 464.2 (100) [M]+. C25H43CoP2 (464.22): calcd. C 64.23, H 9.92;
found C 64.40, H 9.35.
[(CpЈЈЈCo)(μ,η4:1-{PCiPr}2)]2W(CO)4 (2): A solution of W(CO)4-
(nbd) (51.4 mg, 0.13 mmol) in THF (10 mL) was layered with a
solution of 1b (32.5 mg, 0.07 mmol) in pentane (10 mL). After 10
days, complete diffusion resulted in the formation of a deep red
solution, which was filtered through a Teflon® capillary. The sol-
Experimental Section
General: All manipulations were performed by using standard
Schlenk techniques under an atmosphere of N2 with rigorous ex-
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1
vent was removed in vacuo, and the residue was dissolved in pent-
ane (2 mL). Crystals suitable for X-ray crystallography were grown
at 5 °C. The crystals were washed with cold pentane and dried in
ppm. 31P{1H} MAS NMR: δ = 15.3 (s), 1.3 (s), 14.0 (q, JCu,P
=
1
1500 Hz), –2.3 (q, JCu,P = 1500 Hz) ppm. ESI-MS (CH2Cl2/
CH3CN): m/z (%) = 1429.4 (4) [CpЈЈЈ2Co2(C2tBu2P2)2Cu3I2]+,
1
vacuo (crystalline yield: 23 mg, 53%). H NMR (C6D6): δ = 1.07
1239.5
(1)
[CpЈЈЈ2Co2(C2tBu2P2)2Cu2I]+,
1047.6
(2)
{d, 3JH,H = 6.7 Hz, 12 H, [PCCH(CH3)2]2}, 1.49 [s, 9 H, C5(C4H9)3-
[CpЈЈЈ2Co2(C2tBu2P2)2Cu]+, 786.2 (6) [CpЈЈЈCo(C2tBu2P2)Cu2I +
H2], 1.54 [s, 18 H, C5(C4H9)3H2], 2.25 {m, 2 H, [PCCH(CH3)2]2}, CH3CN]+, 596.2 (100) [CpЈЈЈCo(C2tBu2P2)Cu + CH3CN]+.
4.62 [s, 2 H, C5(C4H9)3H2] ppm. 13C{1H} NMR (C6D6): δ = 25.7
[({CpЈЈЈCo}{μ3,η4:1:1-(PCR)2})({CpЈЈЈCo}{μ,η4:1-(PCR)2})(Cu{μ3-
{s, [PCCH(CH3)2]2}, 31.5 {s, C5[C(CH3)3]3H2}, 32.1 {s,
X})4]n (4a: X = Br, R = iPr, 4b: X = I, R = iPr, 4c: X = I, R =
[PCCH(CH3)2]2}, 32.2 {s, C5[C(CH3)3]3H2}, 32.8 {s, C5[C(CH3)]
tBu): A solution of CuX (0.033 mmol) in CH3CN (5 mL) was lay-
3H2}, 34.4 {s, C5[C(CH3)3]3H2}, 78.3 [s, C5(C4H9)3H2], 101.5 {t,
ered over a solution of 1a or 1b (0.047 mmol) in CH2Cl2 (5 mL).
1JP,C = 52.8 Hz, [PCCH(CH3)2]2}, 110.2 [s, C5(C4H9)3H2], 113 [s,
After complete diffusion, the reaction mixture was filtered through
1
C5(C4H9)3H2] ppm. 31P NMR (C6D6): δ = 56.4 (s, JP,W = 274 Hz,
a Teflon® capillary, and all volatile components were removed in
1
2 P), –24.6 (s, 2 P) ppm. 31P{1H} NMR (C6D6): δ = 56.4 (s, JP,W
vacuo. The orange-yellow residue was dissolved in CH3CN (2 mL)
= 274 Hz, 2 P), –24.6 (s, 2 P) ppm. IR (n-hexane): ν (terminal)
˜
CO
and CH2Cl2 (2 mL). After three days of storage at +5 °C, yellow
needles of 4a–4c formed, which were suitable for X-ray structure
determination. The crystals were washed with n-hexane and dried
in vacuo (crystalline yield: 4a: 7 mg, 36%; 4b: 10 mg, 45%; 4c:
10 mg, 27%).[{Cu(µ3-Br)}4{(CpЈЈЈCo)(µ3,4:1:1-(PCiPr)2)}3]n
= 2072 (w), 2044 (s), 2014 (s) cm–1. EI-MS: m/z (%) = 1224.6 (10)
[M]+, 1196.6 (6) [M – CO]+, 1168.6 (5) [M – 2CO]+, 1140.6 (1)
[M – 3CO]+, 648.3 (8) [1bW]+, 464.4 (100) [1b]+, 407.4 (30) [1b –
C4H9]+. C54H86Co2O4P4W (1224.89): calcd. C 52.95, H 7.08; found
C 49.27, H 7.06.
[(Cu{μ3-Br})4({CpЈЈЈCo}{μ3,η4:1:1-(PCiPr)2})3]n (4a): 1H NMR
[(CpЈЈЈCo)(μ,η4:1-{PCtBu}2)Cu(μ-X)]2 (3a: X = Cl; 3b: X = Br, 3c:
X = I): A solution of 1a (40 mg, 0.081 mmol) in CH2Cl2 (5 mL)
was added to a solution of CuX (0.081 mmol) in CH3CN (5 mL),
and the mixture was stirred for three days at room temperature.
After filtration, the orange solution was concentrated and left for
crystallization at room temperature. Orange plates of 3a–3c suitable
for X-ray structure determination were deposited after a few days.
The crystals were washed with n-hexane and dried in vacuo (crys-
talline yield: 3a: 33 mg, 69%; 3b: 17 mg, 57%; 3c: 11 mg 34%).
3
(CD2Cl2/CD3CN):
δ
=
0.92 {d, JH,H
=
6.45 Hz, 12 H,
[PCCH(CH3)2]2}, 1.42 [s, 18 H, C5(C4H9)3H2], 1.49 [s, 9 H,
C5(C4H9)3H2], 2.45 {m, 2 H, [PCCH(CH3)2]2}, 4.63 [s, 2 H,
C5(C4H9)3H2] ppm. 31P NMR (CD2Cl2/CD3CN): δ = 23.8 (s) ppm.
31P{1H} NMR (CD2Cl2/CD3CN): δ = 23.8 (s) ppm. ESI-MS (L =
1b): m/z (%) = 2636.1 (1) [L4Cu6Br5]+, 2494.5 (2) [L4Cu5Br4]+,
2350.8 (2) [L4Cu4Br3]+, 2182.3 (1) [L3Cu5Br6]+, 2030.2 (2)
[L3Cu5Br4]+, 1743.3 (10) [L3Cu4Br2]+, 1279.3 (4) [L2Cu4Br2]+,
1135.3 (3) [L2Cu2Br]+, 991.4 (19) [L2Cu]+, 568.1 (100) [LCuMe-
CN]+, 527.1 (35) [LCu]+. C150H254Br8Co6Cu8P12·CH2Cl2 (4015.44):
calcd. C 45.17, H 6.43; found C 45.55, H 6.42.
[(CpЈЈЈCo)(μ,η4:1-{PCtBu}2)Cu(μ-Cl)]2 (3a): 1H NMR (CD2Cl2/
CD3CN): δ = 0.93 [s, 18 H, C5(C4H9)3H2], 1.30 [s, 9 H, C5(C4H9)3-
H2], 1.41 [s, 18 H, C2(CCH3)2P2], 4.73 [s, 2 H, C5(C4H9)3H2] ppm.
13C{1H} NMR (CD2Cl2/CD3CN): δ = 31.3 [s, C5(CC3H9)3H2], 31.6
[s, C5(CC3H9)3H2], 31.7 {t, 3JP,C = 5.1 Hz, C2[C(CH3)3]2P2}, 32.0 [s,
[(Cu{μ3-I})4({CpЈЈЈCo}{μ3,η4:1:1-(PCiPr)2})3]n (4b): 1H NMR
3
(CD2Cl2/CD3CN):
δ
=
0.91 {d, JH,H
=
6.18 Hz, 12 H,
[PCCH(CH3)2]2}, 1.40 [s, 18 H, C5(C4H9)3H2], 1.44 [s, 9 H,
C5(C4H9)3H2], 2.47 {m, 2 H, [PCCH(CH3)2]2}, 4.64 [s, 2 H,
C5(C4H9)3H2] ppm. 31P NMR (CD2Cl2/CD3CN): δ = 26.9 (s) ppm.
31P{1H} NMR (CD2Cl2/CD3CN): δ = 26.9 (s) ppm. ESI-MS (L =
1b): m/z (%) = 2492.9 (2) [L4Cu4I3]+, 2408.4 (3) [L3Cu6I5]+, 2218.7
(4) [L3Cu5I4]+, 2027.0 (5) [L3Cu4I3]+, 1837.2 (14) [L3Cu3I2]+, 1647
(18) [L3Cu2I]+, 1373.3 (22) [L2Cu3I2]+, 1181.4 (20) [L2Cu2I]+, 991.4
(100) [L2Cu]+.
[(Cu{μ3-I})4({CpЈЈЈCo}{μ3,η4:1:1-(PCtBu)2})3]n (4c): 1H NMR
(CD2Cl2/CD3CN): δ = 1.06 (s, 36 H), 1.41 (s, 18 H), 1.52 (s, 36 H),
4.8 (s, 4 H) ppm. 13C{1H} NMR (CD2Cl2/CD3CN): δ = 31.4 [s,
2
C5(CC3H9)3H2], 34.21 [s, C5(CC3H9)3H2], 34.24 {t, JP,C = 5.8 Hz,
C2[C(CH3)3]2P2}, 76.7 [s, C5(CC3H9)3H2], 111.1 [s, C5(CC3H9)3H2],
113.5 [s, C5(CC3H9)3H2] ppm. 31P{1H} NMR (CD2Cl2/CD3CN): δ
= 14.1 (s), 30.9 (s) ppm. 31P{1H} NMR (C6D6): δ = 9.9 (s), 26.7
1
(s) ppm. 31P{1H} MAS NMR: δ = –2.01, 28.72 (q, JCu,P
=
1850 Hz) ppm. ESI-MS (CH2Cl2/CH3CN): m/z (%) = 1245.3 (1)
[CpЈЈЈ2Co2(P2C2tBu2)2Cu3Cl2]+, 1147.5 (1) [CpЈЈЈ2Co2(P2C2tBu2)2-
Cu2Cl]+, 1047.5 (1) [CpЈЈЈ2Co2(P2C2tBu2)2Cu]+, 696.1 (3)
[CpЈЈЈCo(P2C2tBu2)Cu2Cl
[CpЈЈЈCo(P2C2tBu2)Cu
+
CH3CN]+,
596.2
(100)
+
CH3CN]+.
C54H94Cl2Co2Cu2P4
(1183.08): calcd. C 54.82, H 8.01; found C 54.96, H 7.84.
3
C5(CC3H9)3H2], 31.6 [t, C5(CC3H9)3H2], 32.1 {t, JP,C = 5.1 Hz,
C2[C(CH3)3]2P2}, 32.2 [s, C5(CC3H9)3H2], 34.5 [s, C5(CC3H9)3H2,
t, JP,C = 6.6 Hz, C2(CCH3)2P2], 76.7 [s, C5(CC3H9)3H2], 111.1 [s,
[(CpЈЈЈCo)(μ,η4:1-{PCtBu}2)Cu(μ-Br)]2 (3b): 31P{1H} NMR
(CD2Cl2/CD3CN): δ = 8.2 (s), 24.8 (s) ppm. 31P{1H} MAS NMR:
2
1
1
C5(CC3H9)3H2], 113.5 [s, C5(CC3H9)3H2] ppm. 31P{1H} NMR
(CD2Cl2/CD3CN): δ = 15.4 (s), 33.3 (s) ppm. 31P{1H} NMR
(C6D6): δ = 13.3 (s), 31.2 (s) ppm. 31P{1H} MAS NMR: δ = 2.13
(s), –0.32 (q, 1JCu,P = 1600 Hz), 12.08 (q, 1JCu,P = 1600 Hz), 6.40 (q,
1JCu,P = 1800 Hz) ppm. ESI-MS (CH2Cl2/CH3CN): m/z (%) =
δ = 14.4 (s), 17.8 (q, JCu,P = 1900 Hz), –1.5 (s), 5.8 (q, JCu,P
=
1950 Hz) ppm. ESI-MS (CH2Cl2/CH3CN): m/z (%) = 1335.4 (4)
[CpЈЈЈ2Co2(C2tBu2P2)2Cu4Br2]+, 1191.5 (2) [CpЈЈЈ2Co2(C2tBu2P2)2-
Cu2Br]+, 1047.5 (4) [CpЈЈЈ2Co2(C2tBu2P2)2Cu]+, 740.2 (5)
[CpЈЈЈCo(C2tBu2P2)Cu2Br
[CpЈЈЈCo(C2tBu2P2)Cu
+
CH3CN]+,
CH3CN]+.
C54H94Br2Co2Cu2P4
596.2
(100)
2111.0
(1)
[CpЈЈЈ3Co3(C2tBu2P2)3Cu4I3]+,
1921.2
(2)
+
[CpЈЈЈ3Co3(C2tBu2P2)3Cu3I2]+, 1429.4 (3) [CpЈЈЈ2Co2(C2tBu2P2)2-
Cu3I2]+, 1239.4 (4) [CpЈЈЈ2Co2(C2tBu2P2)2Cu2I]+, 1047 (25)
[CpЈЈЈ2Co2(C2tBu2P2)2Cu]+, 596.1 (100) [CpЈЈЈCo(C2tBu2P2)Cu +
CH3CN]+, 555.0 (2) [CpЈЈЈCo(C2tBu2P2)Cu]+. C81H141Co3Cu4I4P6·
2CH2Cl2 (2409.30): calcd. C 41.38, H 6.07; found C 41.68, H 6.01.
[({CpЈЈЈCo}{μ3,η4:1:1-(PCtBu)2})(Cu{μ3-I})4(MeCN)2]n (5): A Solu-
tion of 1a (46 mg, 0.093 mmol) in CH2Cl2 (5 mL) was layered with
(1271.99): calcd. C 50.99, H 7.45; found C 51.22, H 7.34.
[(CpЈЈЈCo)(μ,η4:1-{PCtBu}2)Cu(μ-I)]2 (3c): 1H NMR (CD2Cl2/
CD3CN): δ = 0.98 [s, 18 H, C5(C4H9)3H2], 1.33 [s, 9 H, C5(C4H9)3-
H2], 1.44 [s, 18 H, C2(CCH3)2P2], 4.72 [s, 2 H, C5(C4H9)3H2] ppm.
13C{1H} NMR (CD2Cl2/CD3CN): δ = 31.4 [s, C5(CC3H9)3H2], 31.6
3
[t, C5(CC3H9)3H2], 32 {t, JP,C = 5.1 Hz, C2[C(CH3)3]2P2}, 32.2 [s,
2
C5(CC3H9)3H2], 34.5 [s, C5(CC3H9)3H2], 34.5 {t, JP,C = 6.2 Hz,
C2[C(CH3)3]2P2}, 76.7 [s, C5(CC3H9)3H2], 111.2 [s, C5(CC3H9)3H2], a solution of CuI (36 mg, 0.189 mmol) in CH3CN (5 mL). After
113.6 [s, C5(CC3H9)3H2] ppm. 31P{1H} NMR (CD2Cl2/CD3CN): δ complete diffusion, the reaction mixture was shaken twice, filtered
= 14.4 (s), 32.4 (s) ppm. 31P{1H} NMR (C6D6): δ = 13.1 (s), 31.0 (s) through a Teflon® capillary and layered with n-hexane (10 mL).
Eur. J. Inorg. Chem. 2014, 1625–1637
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© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
After three weeks, compound 5 crystallized as yellow needles (crys-
talline yield: 32 mg, 27%). 1H NMR (CD2Cl2/CD3CN): δ = 0.97
(s, 18 H), 1.33 (s, 9 H), 1.44 (s, 18 H), 4.72 (s, 2 H) ppm. 31P{1H}
(q, 1JCu,P = 2000 Hz), –3.91 (q, 1JCu,P = 2000 Hz), –11.22 (q, 1JCu,P
1
= 2000 Hz), –73.19 (q, JCu,P = 2000 Hz) ppm. ESI-MS (CH2Cl2/
CH3CN): m/z (%) = 1937.8 (1) [CpЈЈЈ3Co3(C2tBu2P2)3Cu5Cl4]+,
NMR (CD2Cl2/CD3CN): δ = 12.3 (s), 30.2 (s) ppm. 31P{1H} NMR 1838.1
(1)
[CpЈЈЈ3Co3(C2tBu2P2)3Cu4Cl3]+,
1739.8
(2)
(C6D6): δ = 10.6 (s), 28.8 (s) ppm. 13C{1H} NMR (CD2Cl2/
[CpЈЈЈ3Co3(C2tBu2P2)3Cu3Cl2]+, 1345.4 (2) [CpЈЈЈ2Co2(C2tBu2P2)2-
Cu4Cl3]+, 1245.5 (5) [CpЈЈЈ2Co2(C2tBu2P2)2Cu3Cl2]+, 11.47.5 (9)
CD3CN): δ = 31.4 [s, C5(CC3H9)3H2], 31.6 [t, C5(CC3H9)3H2], 32.0
3
{t, JP,C = 5.1 Hz, C2[C(CH3)3]2P2}, 32.2 [s, C5(CC3H9)3H2], 34.5 [CpЈЈЈ2Co2(C2tBu2P2)2Cu2Cl]+, 1047.6 (9) [CpЈЈЈ2Co2(C2tBu2P2)2-
[s, C5(CC3H9)3H2, t, 2JP,C = 6.6 Hz, C2(CCH3)2P2], 76.7 [s, C5(CC3- Cu]+, 794.0 (8) [CpЈЈЈCo(C2tBu2P2)Cu3Cl2 + CH3CN]+, 753 (7)
H9)3H2], 111.0 [s, C5(CC3H9)3H2], 113.5 [s, C5(CC3H9)3H2] ppm.
[CpЈЈЈCo(C2tBu2P2)Cu3Cl2]+, 696.1 (26) [CpЈЈЈCo(C2tBu2P2)Cu2Cl
1
31P{1H} MAS NMR: δ = 5.44 (q, JCu,P = 1400 Hz), –13.07 (q, + CH3CN]+, 596.1 (100) [CpЈЈЈCo(C2tBu2P2)Cu + CH3CN]+.
1
1
1JCu,P = 1400 Hz), 0.15 (q, JCu,P = 1450 Hz), –20.54 (q, JCu,P
=
[({CpЈЈЈCo}{μ3,η4:1:1-(PCtBu)2})2(Cu{μ3-Br})4]n (6b): 1H NMR
(CD2Cl2/CD3CN): δ = 0.99 (s, 36 H), 1.34 (s, 18 H), 1.44 (s, 36 H),
4.75 (s, 4 H) ppm. 13C{1H} NMR (CD2Cl2/CD3CN): δ = 20.8 [s,
1500 Hz) ppm. ESI-MS (CH2Cl2/CH3CN): m/z (%) = 1618.8 (1)
[CpЈЈЈ2Co2(C2tBu2P2)2Cu4I3]+, 1429.3 (3) [CpЈЈЈ2Co2(C2tBu2P2)2-
Cu3I2]+, 1239.4 (0.8) [CpЈЈЈ2Co2(C2tBu2P2)2Cu2I]+, 1047.5 (2)
[CpЈЈЈ2Co2(C2tBu2P2)2Cu]+, 936.8 (6) [CpЈЈЈCo(C2tBu2P2)Cu3I2]+,
786.0 (20) [CpЈЈЈCo(C2tBu2P2)Cu2I + CH3CN]+, 596.1 (100)
[CpЈЈЈCo(C2tBu2P2)Cu + CH3CN]+, 555.0 (3) [CpЈЈЈCo(C2tBu2P2)-
Cu]+.
[({CpЈЈЈCo}{μ3,η4:1:1-(PCtBu)2})2(Cu{μ3-X})4]n (6a: X = Cl, 6b: X =
Br, 6c: X = I): A solution of 1a (40 mg, 0.081 mmol) in CH2Cl2
(5 mL) was layered with a solution of CuCl (80 mg, 0.808 mmol)
in CH3CN (5 mL), a solution of 1a (23 mg, 0.047 mmol) in CH2Cl2
(5 mL) was layered with a solution of CuBr (67 mg, 0.467 mmol)
in CH3CN (5 mL), and a solution of 1a (27 mg, 0.055 mmol) in
CH2Cl2 (5 mL) was layered with a solution of CuI (92 mg,
0.483 mmol) in CH3CN (5 mL). After complete diffusion, the
orange solutions were filtered through a Teflon® capillary and con-
centrated to 5 mL. Within a week, crystals of 6a–6c suitable for X-
ray structure determination formed. The crystals were washed with
n-hexane and dried in vacuo (crystalline yield: 6a: 36 mg, 64%; 6b:
23 mg, 63%, 6c: 31 mg, 65%).
3
C5(CC3H9)3H2], 31.6 [s, C5(CC3H9)3H2], 31.9 {t, JP,C = 4.8 Hz,
C2[C(CH3)3]2P2}, 32.2 [s, C5(CC3H9)3H2], 34.4 [s, C5(CC3H9)3H2],
76.8 [s, C5(CC3H9)3H2], 125.2 [s, C5(CC3H9)3H2], 128.2 [s,
C5(CC3H9)3H2] ppm. 31P{1H} NMR (CD2Cl2/CD3CN): δ = 2.3 (s),
18.6 (s) ppm. 31P{1H} NMR (C6D6): δ = 6.0 (s), 22.4 (s) ppm.
1
31P{1H} MAS NMR: δ = –13.89 (q, JCu,P = 1850 Hz), –5.71 (q,
1
1
1JCu,P = 1800 Hz), 3.42 (q, JCu,P = 1900 Hz), 7.72 (q, JCu,P
=
1850 Hz) ppm. ESI-MS (CH2Cl2/CH3CN): m/z (%) = 1479.1 (1)
[CpЈЈЈ2Co2(C2tBu2P2)2Cu4Br3]+, 1335.3 (6) [CpЈЈЈ2Co2(C2tBu2P2)2-
Cu4br2]+, 1191.3 (2) [CpЈЈЈ2Co2(C2tBu2P2)2Cu2Br]+, 740.0 (16)
[CpЈЈЈCo(C2tBu2P2)Cu2Br + CH3CN]+, 699.1 (1) [CpЈЈЈCo-
(C2tBu2P2)Cu2Br]+, 596.1 (100) [CpЈЈЈCo(C2tBu2P2)Cu + CH3-
CN]+. C54H94Br4Co2Cu4P4 (1558.89): calcd. C 41.61, H 6.08; found
C 41.45, H 5.95.
[({CpЈЈЈCo}{μ3,η4:1:1-(PCtBu)2})2(Cu{μ3-I})4]n (6c): 1H NMR
(CD2Cl2/CD3CN): δ = 1.04 (s, 36 H), 1.38 (s, 18 H), 1.49 (s, 36 H),
4.78 (s, 4 H) ppm. 31P{1H} NMR (CD2Cl2/CD3CN): δ = 8.6 (s),
26.6 (s) ppm. 31P{1H} NMR (C6D6): δ = 3.0 (s), 20.7 (s) ppm.
13C{1H} NMR (CD2Cl2/CD3CN): δ = 32.2 [s, C5(CC3H9)3H2], 32.6
[({CpЈЈЈCo}{μ3,η4:1:1-(PCtBu)2})2(Cu{μ3-Cl})4]n (6a): 1H NMR
(CD2Cl2/CD3CN): δ = 0.95 (s, 36 H), 1.32 (s, 18 H), 1.42 (s, 36 H),
{t, 3JP,C = 4.9 Hz, C2[C(CH3)3]2P2}, 32.8 [s, C5(CC3H9)3H2], 77.3 [s,
4.73 (s, 4 H) ppm. 13C{1H} NMR (CD2Cl2/CD3CN): δ = 31.4 [t, C5(CC3H9)3H2] ppm. 31P{1H} MAS NMR: δ = –16.22 (q, JCu,P
=
1
3
1
1
C5(CC3H9)3H2], 31.8 {t, JP,C = 5.1 Hz, C2[C(CH3)3]2P2}, 32.1 [s, 1600 Hz), –5.68 (q, JCu,P = 2000 Hz), –4.42 (q, JCu,P = 1600 Hz),
1
C5(CC3H9)3H2], 34.3 [s, C5(CC3H9)3H2], 76.8 [s, C5(CC3H9)3H2], 3.25 (q, JCu,P = 1400 Hz) ppm. ESI-MS (CH2Cl2/CH3CN): m/z
111.3 [s, C5(CC3H9)3H2], 113.8 [s, C5(CC3H9)3H2] ppm. 31P{1H}
(%) =
1619.4 (1) [CpЈЈЈ2Co2(C2tBu2P2)2Cu4I3]+, 1429.2 (4)
NMR (CD2Cl2/CD3CN): δ = 12.7 (s), 29.4 (s) ppm. 31P{1H} NMR [CpЈЈЈ2Co2(C2tBu2P2)2Cu3I2]+, 1239.3 (1) [CpЈЈЈ2Co2(C2tBu2P2)2-
(C6D6): δ = –0.4 (s), 13.9 (s) ppm. 31P{1H} MAS NMR: δ = 4.85
Cu2I]+, 936.8 (3) [CpЈЈЈCo(C2tBu2P2)Cu3I2]+, 786.0 (17)
Table 4. X-ray crystallographic data for 1–2.
1a
1b
2
Formula
Molecular weight
C27H47CoP2
492.52
C25H43CoP2
464.46
C54H86Co2O4P4W
1224.81
Crystal dimensions /mm
Crystal system
Space group (No.)
a /Å
b /Å
c /Å
α /°
0.26ϫ0.09ϫ0.07
monoclinic
P21/c (14)
9.7326(13)
11.9298(3)
23.731(3)
90
0.14ϫ0.06ϫ0.03
monoclinic
C2/c (15)
25.757(5)
13.9201(9)
18.509(6)
90
0.20ϫ0.13ϫ0.06
monoclinic
C2/c (15)
34.0031(6)
11.7250(2)
15.1391(3)
90
β /°
93.130(13)
90
2751.3(5)
4
129.32(3)
90
5134(3)
8
109.821(2)
90
5678.17(19)
4
γ /°
V /Å3
Z
Tmeas /K
123(1)
1.189
6.051
123(1)
1.202
6.457
123(1)
1.433
9.563
ρcalcd. /gcm–3
μ /mm–1
Reflections collected
Unique reflections (Rint
R1 [IϾ2σ(I)]
11003
4776 (0.0274)
0.0367
8212
4888 (0.0521)
0.0490
17774
5877 (0.0483)
0.0449
)
wR2 (all data)
0.0952
1.077
0.1232
0.906
0.1199
1.063
GooF S (on F2)
Eur. J. Inorg. Chem. 2014, 1625–1637
1635
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
[CpЈЈЈCo(C2tBu2P2)Cu2I
+
CH3CN]+,
596.1
(100)
drogen atoms were located in idealized positions and refined iso-
tropically according to the riding model. The crystals of 4a were
twinned. Hence, the model was refined against HKLF5 data, which
revealed a ratio of the second component of 37.4(8)%. Further-
more, for the refinement of the disordered parts of the structure
and the modeling of the solvent molecule at the special position,
several restraints were applied. The figures of the solid-state struc-
tures were prepared with SCHAKAL-99.[20] The X-ray structure
details are summarized in Tables 4–6.
[CpЈЈЈCo(C2tBu2P2)Cu + CH3CN]+.
Crystal Structure Determination
X-ray crystal structure analyses were performed by using an Oxford
Gemini R Ultra CCD diffractometer with Cu-Kα radiation (λ =
1.54178 Å; for 1a, 3a, 5, 6b) or Mo-Kα radiation (λ = 0.71073 Å;
for 3b and 6a) or an Oxford Diffraction SuperNova diffractometer
with Cu-Kα radiation (λ = 1.54178 Å) and a CCD-Atlas detector
(for 1b, 2, 4a–c, 6c). Structure solution and refinement were ac-
complished by using SIR-92,[16] SHELXL-97,[17] and WinGX. Af-
ter measurement, analytical[18] or semi-empirical[19] absorption cor-
rection was performed.
CCDC-963884 (for 1a), -963885 (for 1b), -963886 (for 2), -963887
(for 3a), -963888 (for 3b), -963889 (for 4a), -963890 (for 4b),
-963891 (for 4c), -963892 (for 5), -963893 (for 6a), -963894 (for 6b),
and -963895 (for 6c) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via www.ccdc.cam.
ac.uk/data_request/cif.
The structures were solved with the program SIR-92; full-matrix
least-squares refinement on F2 in SHELXL-97 was performed with
anisotropic displacement parameters for all non-H atoms. The hy-
Table 5. X-ray crystallographic data for 3–4.
3a
3b
4a·CH2Cl2
4b·CH2Cl2
4c·2CH2Cl2
Formula
C54H94Cl2Co2Cu2P4 C54H94Br2Co2Cu2P4 C151H260Cl2Co6Cu8Br8P12 C151H260Cl2Co6Cu8I8P12 C83H145Cl4Co3Cu4I4P6
Molecular weight
Crystal dimensions /mm 0.06ϫ0.17ϫ0.27
Crystal system
Space group (No.)
a /Å
b /Å
c /Å
α /°
β /°
1183.03
1271.93
4019.32
4395.32
2408.01
0.60ϫ0.02ϫ0.02
monoclinic
P21/c (14)
28.0318(6)
18.6628(5)
19.5745(4)
90
92.765(2)
90
10228.5(4)
4
0.07ϫ0.28ϫ0.43
triclinic
0.14ϫ0.10ϫ0.08
triclinic
0.14ϫ0.06ϫ0.03
triclinic
triclinic
¯
¯
¯
¯
P1 (2)
P1 (2)
P1 (2)
P1 (2)
9.4604(5)
9.9873(4)
16.1126(6)
87.243(3)
88.236(4)
73.823(4)
1460.22(11)
1
11.8836(2)
15.3364(3)
16.4031(3)
97.589(2)
96.1870(10)
96.560(2)
2921.97(9)
2
10.0219(2)
18.2410(5)
24.6742(6)
87.197(2)
79.893(2)
76.820(2)
4323.52(19)
2
10.0637(3)
18.4268(5)
24.8861(6)
87.472(2)
79.921(2)
76.492(2)
4418.0(2)
2
γ /°
V /Å3
Z
Tmeas /K
123(1)
1.345
0.662
123(1)
1.446
2.786
123(1)
1.544
9.237
123(1)
1.652
17.894
123(1)
1.564
16.216
ρcalcd. /gcm–3
μ /mm–1
Reflections collected
Unique reflections (Rint
R1 [IϾ2σ(I)]
wR2 (all data)
GooF S (on F2)
18242
4933 (0.0293)
0.0298
0.0813
1.072
30699
13743 (0.0253)
0.0244
0.0594
0.937
21459
15896 (0.0537)
0.0616
0.1768
0.983
15178
13976 (0.0477)
0.0343
0.0922
1.071
37108
20532 (0.0603)
0.0711
0.2079
1.036
)
Table 6. X-ray crystallographic data for 5–6.
5·0.33C6H14
6a
6b
6c·0.45CH2Cl2·CH3CN
Formula
Molecular weight
Crystal dimensions /mm
Crystal system
Space group (No.)
a /Å
b /Å
c /Å
C33H45.67CoCu4I4N2P2
1365.11
C54H94Cl4Co2Cu4P4
1381.04
C54H94Br4Co2Cu4P4
1558.84
C46.46H97.9Cl0.9Co2Cu4I4P4N
1826.06
0.01ϫ0.03ϫ0.14
monoclinic
P21/c (14)
10.4101(2)
39.0133(8)
16.9658(3)
90
90.721(2)
90
6889.8(2)
4
0.06ϫ0.14ϫ0.29
triclinic
0.03ϫ0.17ϫ0.28
monoclinic
P21/c (14)
17.8397(2)
17.6833(2)
19.8197(2)
90
96.898(1)
90
6207.16(12)
4
0.17ϫ0.11ϫ0.03
monoclinic
P21/c (14)
17.9334(10)
17.8661(9)
19.9783(7)
90
96.996(5)
90
6353.4(5)
4
¯
P1 (2)
10.2467(3)
18.3693(4)
24.8239(6)
82.015(2)
78.934(2)
89.187(2)
4540.8(2)
4
α /°
β /°
γ /°
V /Å3
Z
Tmeas /K
123(2)
1.997
27.061
123(1)
1.478
2.176
123(1)
1.630
9.590
123(2)
1.760
20.548
ρcalcd. /gcm–3
μ /mm–1
Reflections collected
Unique reflections (Rint
R1 [IϾ2σ(I)]
33963
15676 (0.0447)
0.0443
65316
15113 (0.0306)
0.0274
28270
11062 (0.0242)
0.0261
40335
13617 (0.0544)
0.0383
)
wR2 (all data)
0.01275
1.064
0.0656
1.041
0.0663
0.966
0.1025
1.060
GooF S (on F2)
Eur. J. Inorg. Chem. 2014, 1625–1637
1636
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
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Acknowledgments
The authors gratefully acknowledge the financial support of the
Deutsche Forschungsgemeinschaft (DFG).
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Received: October 4, 2013
Published Online: November 22, 2014
Eur. J. Inorg. Chem. 2014, 1625–1637
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© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim