Synthesis of cationic R2P5+ cages and subsequent chalcogenation reactions

Article abstract of DOI:10.1002/chem.201204337

Cationic R₂P₅⁺ cage compounds (1 ⁺) have been synthesized by the stoichiometric reaction of R ₂PCl, GaCl₃ and P₄. The reaction conditions depend on the substituent R. Alkyl-substituted derivatives (1 a-1 d[GaCl ₄]) are best synthesized under solvent-free conditions, whereas aryl-substituted derivatives (1 e-1 h[GaCl₄]) are formed in C ₆H₅F. All compounds have been prepared on a multi-gram scale in good to excellent yields and have been fully characterized with an emphasis on ³¹P NMR spectroscopy in solution and single-crystal structure determination. Subsequent chalcogenation reactions of cations R ₂P₅⁺ (1 a⁺, 1 e⁺) and trication Ph₆P₇³⁺ (3³⁺) with elemental sulfur (α-S₈) or grey selenium (Se_grey) yielded a series of unique polyphosphorus-chalcogen cations (4 a⁺, 4 e⁺, 5 a⁺, 6²⁺ and 7²⁺ Copyright

Full text of DOI:10.1002/chem.201204337

FULL PAPER
DOI: 10.1002/chem.201204337
+
Synthesis of Cationic R2P5 Cages and Subsequent Chalcogenation Reactions
Michael H. Holthausen,[a] Alexander Hepp,[a] and Jan J. Weigand*[a, b]
Dedicated to Professor Werner Uhl on the occasion of his 60th birthday
+
Abstract: Cationic R2P5 cage com-
pounds (1+) have been synthesized by
the stoichiometric reaction of R2PCl,
GaCl3 and P4. The reaction conditions
depend on the substituent R. Alkyl-
characterized with an emphasis on
31P NMR spectroscopy in solution and
single-crystal structure determination.
Subsequent chalcogenation reactions of
a series of unique polyphosphorus–
chalcogen cations (4a+, 4e+, 5a+, 62+
and 72+), possessing nortricyclane-type
molecular structures. An in-depth
study of the 31P{1H} and 77Se NMR
spectroscopic parameters is presented,
and correlations between the substitu-
tion pattern and the observed structur-
al features have been investigated in
detail.
+
cations R2P5 (1a+, 1e+) and trication
(33+
) with elemental sulfur
3+
substituted derivatives (1a–1d
are best synthesized under solvent-free
conditions, whereas aryl-substituted de-
[GaCl4])
Ph6P7
(a-S8) or grey selenium (Segrey) yielded
rivatives (1e–1hACHTUNGTRENNUNG[GaCl4]) are formed in
Keywords: cations · chalcogens ·
main group elements · NMR spec-
troscopy · phosphorus
C6H5F. All compounds have been pre-
pared on a multi-gram scale in good to
excellent yields and have been fully
Introduction
insertion steps led to the formation of the larger cages
2+
3+
Ph4P6 (22+) and Ph6P7 (33+; Figure 1).[7]
Cationic species containing a polyphosphorus framework
are interesting synthetic targets. Catenated and cyclic poly-
phosphanylphosphonium ions are the most extensively stud-
ied cations featuring such frameworks.[1] Only recently, cat-
The facile insertion of up to two additional Ph2P+ moiet-
+
À
ies into the P P bonds of 1e led us to speculate as to
whether this reactivity might be exploited for the prepara-
tion of other cationic phosphorus–element cages. Of special
interest is the insertion of chalcogen atoms for the targeted
synthesis of polyphosphorus–chalcogen cations. To the best
of our knowledge, only five examples of such cations have
hitherto been reported. Two distinct reactions for their prep-
aration have been described (Scheme 1).
ACHTUNGTRENNUNGionic polyphosphorus cages have been synthesized by the re-
action of P4 with appropriate phosphenium ion precursors,
which was inspired by intriguing reactions involving P4 and
low-coordinated main group element compounds.[2] The first
+
examples were the binary cationic P5X2 cages (X=Cl, Br,
I), which were obtained by insertion of an in situ formed
Firstly, P4S3 was reported to react with in situ generated
+
[3]
+
PX2 ion into a P P bond of the P4 tetrahedron. A series
of differently substituted P5 cage compounds was prepared
PI2 phosphenium ions to give cation 8+, which dispropor-
À
tionates to cations 9+ and 10+ and one equivalent of the re-
+
by following a similar approach and applying various sour-
ces of phosphenium ions.[4] Chloro- and organo-substituted
P5+-cage compounds, for example, were obtained from mix-
tures of dichlorophosphanes RPCl2, ECl3 (E=Al, Ga) and
active iodophosphinidene [PI] (Scheme 1I).[8] The second
+
P4 in fluorobenzene.[5] The preparation of cation Ph2P5
(1e+), however, required the reaction of Ph2PCl, GaCl3 and
P4 in a solvent-free melt.[6] Furthermore, additional Ph2P+
[a] Dr. M. H. Holthausen, Dr. A. Hepp, Prof. Dr. J. J. Weigand
Institut fꢀr Anorganische und Analytische Chemie
Westfꢁlische Wilhelms-Universitꢁt Mꢀnster
Corrensstrasse 30, 48149 Mꢀnster (Germany)
[b] Prof. Dr. J. J. Weigand
Professur fꢀr Anorganische Koordinationschemie
TU Dresden, 01062 Dresden (Germany)
Fax : (+49)351-83-33126
Figure 1. Cationic polyphosphorus cages 1a+–1h+, 22+ and 33+ obtained
from the insertion of R2P+ phosphenium ions into P P bonds of white
E-mail: jan.weigand@tu-dresden.de
À
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201204337.
phosphorus (P4) and cationic polyphosphorus–chalcogen cages 4a+, 4e+,
5a+, 5e+, 62+ and 72+
.
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The addition of GaCl3 to P4 suspended in R2PCl (R=Cy,
iPr, Et, Me) initiates a highly exothermic reaction yielding
brown to yellow biphasic melts. These melts are composed
of immiscible phases of liquid P4 (upper phase) and mixtures
of GaCl3 and the corresponding chlorophosphane (lower
phase). The progress of the reactions can be conveniently
monitored by observing the consumption of the P4 phase.
Ultimately, homogeneous yellow to brown melts are ob-
tained. With increasing steric bulk of the substituents R, ex-
tended reaction times and higher temperatures are required
(R=Cy: 3 h, 1508C vs. R=Me: 1 h, 1008C) to achieve
Scheme 1. I) Reaction of P4S3 with in situ generated phosphenium ion
PI2+; a)+Ag[X], +PI3, ÀAgI, CH2Cl2, À808C, 16 h; b) À[PI], CH2Cl2,
À788C, 2 weeks, 9[X]: 41%; II) reaction of a-P4S3I2 with Ag[X];
a)+Ag[X], ÀAgI, CH2Cl2, À808C, 2 d; b) +a-P4S3I2, À[PI], CH2Cl2,
+
quantitative conversion to the corresponding R2P5 cations.
The melts were cooled to ambient temperature and dis-
solved in CH2Cl2. A small amount of orange residue was re-
moved by filtration. Repeated recrystallization steps were
needed to convert the melts into yellow or brown microcrys-
talline solids, which reduced the isolated yields to some
À308C, 7 d, 12[X]: 16%; X=Al{OC
ACHTNUGTERN(NUGN CF3)3}4.
approach is based on halide abstraction from a-P4S3I2 with
the Krossing silver salt Ag[Al{OC
(CF3)3}4][9] giving inter-
extent (1a–1d
substituted compounds, the aryl-substituted derivatives 1e–
1h[GaCl4] were conveniently prepared in C6H5F at ambient
ACHTUNGRTENN[UNG GaCl4]: 71–78%). In contrast to the alkyl-
AHCTUNGTRENNUNG
temperature (Scheme 2).
+
of organo-substituted R2P5 cages by the reaction of R2PCl,
The addition of GaCl3 to P4 suspended in a solution of
R2PCl in C6H5F yielded yellow (R=Ph) or red to purple
(R=C6F5, Mes, Dipp) reaction mixtures. In the last three
cases, the colour faded upon completion of the reactions.
The reaction times decreased significantly with increasing
steric demand of the substituent R (Ph: 14 d, C6F5: 2 d,
Mes: 2 h, Dipp: 12 h). In the case of Ph2PCl, the reaction
was conducted in the dark to prevent light-induced decom-
position of P4 due to the long reaction time. In all cases,
workup involved the addition of n-hexane to the reaction
mixture followed by filtration to isolate the precipitated
GaCl3 and P4. The reaction conditions strongly depend on
the nature of the chlorophosphane R2PCl. Thus, a solvent-
free protocol is required for dialkylchlorophosphanes,
whereas the reactions are performed in C6H5F for diaryl-
ACHTUNGTRENNUNGchloroACHTUNGTRENNUNGphosACHTUNGTRENNUNGphanes. Subsequently, we investigated chalcoge-
+
3+
nation reactions of R2P5 and Ph6P7 cages with elemental
sulfur (a-S8) or grey selenium (Segrey) and developed two
synthetic approaches for the synthesis of cationic polyphos-
phorus–chalcogen cages. These protocols are based on
À
either the insertion of chalcogen atoms into the P P bonds
+
of R2P5 cages or the substitution of Ph2P+ fragments of
compounds in high yields (1e–1hACTHNGUTERNNU[G GaCl4]: 80–90%).
3+
+
Ph6P7
(33+). The obtained polyphosphorus–chalcogen
The R2P5 cages were obtained by the formal insertion of
À
cages possess nortricyclane-type molecular structures, and
an in-depth discussion of 31P{1H}/77Se{1H} NMR parameters
and the correlation thereof with the features of these struc-
tural motifs is presented.
R2P+ phosphenium ions into a P P bond of P4. However,
this is an oversimplified explanation since free phosphenium
ions cannot be observed in mixtures of most alkyl- and aryl-
substituted chlorophosphanes and GaCl3 in solution.[11] The
+
formation of R2P5 cages can be rationalized in terms of
Equations (A–C) (Scheme 3).
Results and Discussion
It is known that mixtures of chlorophosphanes and GaCl3
commonly form Lewis acid/base adducts of type 13. Adduct
13 reacts with R2PCl to give the phosphanylphosphonium
The solvent-free reaction of alkyl-substituted phosphanes
R2PCl with GaCl3 and P4 in a 1:1:1 stoichiometry proceeds
according to a previously reported melt approach[7] and
species 14
ACHTUNGTRENNUNG
tion of 13 and 14AHCTUNGTRENNUNG
yields R2P5 cations 1a+–1d+ as [GaCl4]À salts (Scheme 2).
melts.[6,7] Phosphanylphosphonium ions of type 14+ are sus-
ceptible to nucleophilic substitution of the phosphoniumyl
moiety by R2PCl, as illustrated in Equation (B). Similar re-
activity has previously been reported for related reactions.[12]
In the present context, this is best regarded as the transfer
of a phosphenium ion between two phosphanes. Similarly,
the phosphenium ion may also be transferred onto P4
+
+
+
Scheme 2. R2P5 cage compounds prepared in solvent-free melts: 1a-
[Equation (C)], ultimately yielding an R2P5 cage. A related
transfer of an RPCl+ moiety has also been suggested for the
reaction of P4, RPCl2 and GaCl3 (R=alkyl, aryl) on the
basis of quantum chemical calculations.[5] The different reac-
tivities of alkyl- and aryl-substituted phosphanes in the syn-
G
A
U
ACHTUNGERTN[NUNG GaCl4]
A
ACHTUNGTRENNUNG
G
ACHTUNGTRENNUNG
trimethylphenyl, Dipp=2,6-diisopropylphenyl; a) details are given in the
Experimental Section.
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Synthesis and Reactivity of R2P5 Cages
FULL PAPER
d(PM)=À19.5 ppm, 1c+: d(PM)=1.6 ppm, 1d+: d(PX)=
28.7 ppm). This characteristic trend has previously been ob-
served in 13C and 31P NMR spectroscopic investigations and
was termed the g-effect.[15] The resonances of the tetra-coor-
+
dinated P atoms in alkyl-substituted R2P5 cages exhibit a
gradual shift to higher field with increasing number of hy-
drogen atoms at the a-carbon atom of the substituent (1a+:
d(PX)=35.4 ppm, 1c+: d(PX)=32.0 ppm, 1d+: d(PM)=
12.5 ppm). This observation is counterintuitive considering
the inductive effects of the respective substituents. However,
it constitutes a characteristic feature of phosphonium moiet-
ies and was termed the a-effect.[16] The resonances of the PM
+
atoms in aryl-substituted R2P5 cages are shifted to higher
field compared to those of the corresponding P atoms in the
alkyl-substituted cages. This may be rationalized in terms of
a positive mesomeric effect, namely the donation of p-elec-
tron density from the aryl substituents into the lobes of anti-
Scheme 3. Equilibrium reactions: A) Lewis acid/base adduct 13 reacts
with R2PCl to afford phosphanylphosphonium salt 14
tution of a phosphoniumyl moiety in 14
[GaCl4] by R2PCl2 (R1 =R2);
C) formation of R2P5A
[GaCl4] by transfer of an R2P+ moiety from 14-
[GaCl4] to P4 according to mechanistic considerations in ref. [5].
ACHTUNGRTEN[NGNU GaCl4]; B) substi-
AHCTUNGTRENNUNG
CHTUNGTRENNUNG
[16a]
À
bonding s*
N
ACHTUNGTRENNUNG
+
thesis of R2P5 cage compounds can be rationalized
in terms of the different Lewis acidities of the cor-
responding phosphenium ions, which are reflected
by their fluoride ion affinities (e.g., Me2P+: FIA=
959 kJmolÀ1, Ph2P+: FIA=828 kJmolÀ1).[13] This ne-
cessitates a more Lewis acidic environment for the
transfer of an alkyl-substituted phosphenium ion,
which is realized in a solvent-free medium.
+
The 31P{1H} NMR spectra of the R2P5 cage com-
pounds dissolved in CD2Cl2 are depicted in Figure 2
and the corresponding spectroscopic parameters are
summarized in Table 1. A2M2X spin systems are ob-
served for cations 1a+–1c+ and A2MX2 spin systems
for 1d+–1h+. Both spin systems are in accordance
with a C2v-symmetric molecular structure of the
+
R2P5 cages in solution. The A parts of the spin sys-
tems (ranging from d(PA)=À301.4 ppm for 1b+ to
d(PA)=À264.0 ppm for 1 f+) are assigned to the P
atoms opposite to the phosphonium moieties. The
observed resonances are in the typical range of the
two bridgehead
tetraphosphabicyclo
P
ACHTUNGTRENNUNG
atoms in butterfly-shaped
[1.1.0]butane derivatives.[14] For
1a+–1c+ the M part of the A2M2X spin system and
for 1d+–1h+ the X part of the A2MX2 spin system
corresponds to the P atoms adjacent to the phos-
phonium moiety. Consequently, the X part of the
A2M2X spin system of 1a+–1c+ and the M part of
the A2MX2 spin system of 1d+–1h+ are assigned to
the tetra-coordinated P atoms.
The observation of two different spin systems for
+
R2P5 cages may be explained in terms of the dis-
tinct steric and electronic influences of the alkyl
and aryl substituents R. The resonances of the P
atoms adjacent to phosphonium moieties in alkyl-
+
substituted R2P5 cages reveal a stepwise shift to
Figure 2. 31P{1H} NMR spectra of compounds 1a–1d
(CD2Cl2, RT); resonances from small amounts of unidentified side products are
ACHUTGTNERN[NGU GaCl4] and 1 f–1hACHTUNGTRENNUNG[GaCl4]
lower field with decreasing number of alkyl groups
at the g-position relative to these atoms (1a+: marked with asterisks.
Chem. Eur. J. 2013, 00, 0 – 0
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J. J. Weigand et al.
+
Table 1. 31P{1H} NMR parameters of R2P5 cages 1a+–1h+.
31P
1a+
(R=Cy)
1b+
(R=iPr)
1c+
(R=Et)
31P
1d+
(R=Me)
1e+
(R=Ph)
1 f+
(R=C6F5)
1g+
(R=Mes)
1h+
ACHTUNGTRENNUNG
G
E
G
E
G
N
N
[a]
spin system
d(PA)
d(PM)
A2M2X
À301.0
À19.5
35.4
À135.4
À209.1
6.0
A2M2X
À301.4
À19.3
44.7
À135.2
À212.5
5.9
A2M2X
À286.7
1.6
spin system
d(PA)
d(PM)
A2MX2
A2MX2
A2MX2
A2MX2
À273.1
À292.0
À264.0
À35.7
25.5
À138.0
À270.3
13.2
À270.5
À15.5
50.2
À151.6
À207.2
7.1
À274.8
À26.3
52.2
À153.7
À201.2
6.4
12.5
À5.4
d(PX)
32.0
d(PX)
28.7
19.7
1J
1J
2J
N
À135.0
À208.0
7.7
1J
1J
2J
N
À137.0
À203.2
9.4
À139.7
À212.2
8.3
[a] 31P{1H} NMR parameters are taken from ref. [7].
This positive mesomeric effect is enhanced by alkyl groups
at the ortho- and para-positions of the aryl substituents.
Thus, a successive shift to higher field is observed in the
order of 1e+ (d(PM)=À5.4 ppm), 1g+ (d(PM)=À15.5 ppm)
and 1h+ (d(PM)=À26.3 ppm). The 31P{1H} NMR spectrum
of 1 fACHTUNGTRENNUNG[GaCl4] shows an additional coupling of the ortho-
fluoro substituents of the C6F5 group to the PM and PX
4
atoms (3J
of the
3J
(PMF) coupling constant indicates a through-space cou-
pling path.[5,17]
Single crystals of compounds 1a–1d
and 1h[GaCl4] suitable for X-ray structure determination
N
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHUTNGREN[NUG GaCl4], 1gACHTUNTGNER[NUGN GaCl4]
ACHTUNGTRENNUNG
were obtained by slow diffusion of n-hexane into solutions
of the respective compounds in CH2Cl2 or C6H4F2. The mo-
lecular structures of the cations are depicted in Figure 3.
Table 2 lists selected structural parameters of the cations.
+
À
The P P bond lengths and angles in the R2P5 frameworks
of compounds 1a–1h
[GaCl4] are very similar to one anoth-
er. Therefore, general trends with respect to the structural
parameters of the compounds are discussed. For all cages,
À
two distinct sets of P P bond lengths are observed, which is
a typical feature of the structural motif of an R2P5
+
cage.[4–6,8] The P P bonds involving the tetra-coordinated P
À
À
À
atoms are shorter (av. P1 P2/P1 P3 bond lengths:
2.1844(7) ꢃ) than that of the P4 tetrahedron (P4: 2.21 ꢃ).[18]
À
Short P P bonds are also observed between the two P
atoms opposite the phosphonium moiety (ranging from 1d+:
2.1611(8) ꢃ to 1g+: 2.185(4) ꢃ). This is a characteristic fea-
ture of bridgehead
P
atoms in butterfly-shaped
tetraphosphabicycloACHTUNGTRENNUNG
[1.1.0]butane derivatives[19] or related
Figure 3. Molecular structures of cations 1a+–1d+, 1g+ and 1h+ of the
corresponding gallate salts (hydrogen atoms and solvate molecules are
omitted for clarity and thermal ellipsoids are displayed at 50% probabili-
ty).
EP4 cages (E=Ga,[20] Si,[21] PX2 (X=Br, I,[3] Ph[7])). All
À
other P P bonds (ranging from 2.2542(7) ꢃ to 2.2260(7) ꢃ)
are slightly longer than those in P4.[18] The P1 atoms exhibit
highly distorted tetrahedral environments with acute P-P-P
angles (av. P-P-P: 88.12(3)8). Interestingly, the C-P-C angles
widen successively with increasing steric demand of the sub-
stituents (from 1d+: 106.2(1)8 to 1h+: 116.44(8)8), whereas
the P-P-P angles involving the P1 atom decrease slightly
(1d+: 89.05(3)8 to 1h+: 85.94(3)8). In the same sequence, a
nounced folding (P2···P3 1g+: 3.006(3) ꢃ, 1h+: 3.000(1) ꢃ)
+
than that of R2P5 cages bearing alkyl substituents R (aver-
age P2···P3: 3.052(4) ꢃ). The distances of the P1 atoms to
the bonds between the bridgehead P atoms are also differ-
ent (shortest distances between P1 and a line through P4
À
stepwise elongation of P P bonds involving the P1 atom is
+
observed (compare 1d+ P1 P2: 2.1696(7) ꢃ and P1 P3:
and P5, 1g+: 2.826(1) ꢃ, 1h+: 2.851(1) ꢃ, average (Ralkyl)2P5
À
À
2.1761(7) ꢃ with 1h+ P1 P2: 2.1987(7) ꢃ and P1 P3:
: 2.799(3) ꢃ).
À
À
+
2.2026(7) ꢃ). As a consequence, the tetraphosphabicyclo-
All presented R2P5 cage compounds were conveniently
[1.1.0]butane moieties of 1g+ and 1h+ display a more pro-
prepared on a multi-gram scale in good to excellent yields.
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Synthesis and Reactivity of R2P5 Cages
FULL PAPER
+
Table 2. Selected bond lengths [ꢃ] and angles [8] of R2P5 cations 1a+–1d+, 1g+ and
nificantly lower the melting point of the reaction
1h+.
mixture (m.p. 1a
ACHTUNGERTN[NUNG GaCl4]=106.2–107.98C). A mix-
1a+
(R=Cy)
1b+
(R=iPr)
1c+
(R=Et)[b]
1d+
(R=Me)
1g+
(R=Mes)
1h+
(R=Dipp)
ture of 1a[GaCl4], GaCl3 and two equivalents of
AHCTUNGTRENNUNG
A
E
U
N
E
ACHTUNGTRENNUNG
Segrey yielded a yellow melt containing suspended
Segrey at around 658C. After 1 h, the viscosity of the
melt increased rapidly and solidification was pre-
vented by increasing the reaction temperature to
1408C for a further 2 h. The melt was cooled to am-
bient temperature and the obtained solid was dis-
solved in C6H4F2. 31P{1H} NMR spectroscopic analy-
sis of the solution revealed 84% conversion of 1a+
to 4a+ (Figure 4A). However, isolation was ham-
pered by the presence of the additional equivalent
of GaCl3, leading to the separation of a yellow oil
upon addition of n-hexane. Repeated dissolution of
the obtained oil in 1,2-C6H4F2 and slow diffusion of
n-hexane into the solution at À358C yielded 4a-
À
P1 C1
À
P1 Cn
1.815(3) 1.839(2)
1.813(3) 1.818(2)
1.806(2)
1.806(2)
1.804(2)
1.794(2)
1.820(3)
1.816(3)
1.831(2)
1.835(2)
2.1987(7)
2.2026(7)
2.2329(8)
2.2260(7)
2.2264(8)
2.2425(8)
2.1836(8)
116.44(8)
85.94(3)
118.84(7)
119.22(7)
87.49(3)
86.84(3)
58.64(3)
60.38(3)
84.35(3)
61.12(3)
[a]
À
P1 P2
2.183(1) 2.1734(8) 2.1796(6)
2.184(1) 2.1844(8) 2.1796(6)
2.242(1) 2.2312(8) 2.2542(7)
2.250(1) 2.2450(7) 2.2386(7)
2.240(1) 2.2434(8) 2.2386(7)
2.242(1) 2.2451(8) 2.2542(7)
2.166(1) 2.1673(8) 2.178(1)
2.1696(7) 2.189(1)
2.1761(7) 2.195(1)
2.2423(8) 2.235(1)
2.2462(8) 2.225(1)
2.2361(8) 2.226(1)
2.2492(8) 2.233(1)
2.1611(8) 2.185(1)
106.2(1)
89.05(3)
115.30(7) 107.35(9)
115.12(7) 112.47(9)
85.00(3)
85.76(3)
57.56(3)
61.13(3)
85.36(3)
61.50(3)
À
P1 P3
À
P2 P4
À
P2 P5
À
P3 P4
À
P3 P5
À
P4 P5
C1-P1-Cn[a] 108.3(1) 109.2(1)
108.5(1)
89.36(3)
110.01(1)
86.58(4)
P2-P1-P3
P2-P1-C1
P3-P1-Cn[a]
P1-P2-P5
P1-P2-P4
P5-P2-P4
P4-P5-P2
P2-P5-P3
P5-P4-P3
88.87(4) 88.00(3)
114.0(1) 114.47(8) 113.63(6)
114.5(1) 113.21(8) 113.63(6)
85.06(4) 86.09(3)
85.45(4) 86.46(3)
57.75(4) 57.92(3)
61.24(4) 60.72(3)
85.69(4) 84.78(2)
61.37(4) 61.16(3)
84.62(2)
85.00(2)
57.99(3)
61.36(2)
86.03(3)
60.65(2)
87.78(4)
86.84(3)
58.67(4)
60.89(4)
84.82(4)
60.44(4)
AHCTUNGTRENNUNG
AHCTUNGRTENN[GUN GaCl4] and
[a] 1a+: n=7, 1b+: n=4, 1c+: n=1i, 1d+: n=2, 1g+: n=10, 1h+: n=13; [b] P3=P2i,
Segrey was heated to 1108C, resulting in the forma-
tion of a yellow melt containing suspended Segrey
P4=P3, P5=P3i; i=Àx+1, Àx+y+1, Àz+5= .
3
(m.p. 1eACTHNURGTNEUNG[GaCl4]=60.0–61.58C). After 1 h, the vis-
They appear to be indefinitely stable in the solid state
(under Ar or N2 atmosphere) at ambient temperature. All
derivatives are poorly soluble in C6H4F2 and C6H5F, and rea-
sonably soluble in CH2Cl2. However, their solubility can be
drastically improved by the addition of a small amount of
GaCl3.
cosity of the melt increased and solidification was prevented
by heating to 1508C for a further 16 h. The condensation of
some P4 on colder parts of the reaction vessel was observed.
The 31P{1H} NMR spectrum of the melt dissolved in CH2Cl2
revealed only moderate conversion to 4e+ (46%, Fig-
ure 5A).
Chalcogenation reactions employing elemental sulfur
A singlet resonance of low intensity (d(P)=117.1 ppm) in
(a-S8) and grey selenium (Segrey) were investigated with the
the 31P{1H} NMR spectrum of the reaction mixture contain-
+
R2P5 cage compounds 1a
[GaCl4] and 1e
N
ing 1aACHTNUGRETN[NUG GaCl4] could be assigned to Cy2P(Se)Cl·GaCl3 (15a)
tion was observed for suspensions of grey selenium in solu-
tions of 1a[GaCl4] or 1e[GaCl4] in C6H5F. However, a sol-
vent-free approach led to the formation of 4a[GaCl4] and
4e[GaCl4] (Scheme 4).
by comparison with the spectrum of related iPr2P(Se)Cl
G
ACHTUNGTRENNUNG
(d(PA)=125.3 ppm).[22] The singlet is superimposed by the
E
doublet of the isotopomer Cy2P
854 Hz; for example, iPr2P
(77Se)Cl: J
(77Se)Cl·GaCl3 (1J
ACHUTGTNRENNUG ACHTUNGTRENNUNG
1
G
A
N
A
second singlet of low intensity (d(P)=75.3 ppm) can be as-
signed to Cy2PClH+ (16a+) and is split into a doublet in the
31P NMR spectrum (1J(PH)=526 Hz).[24] The formation of
16a+ is the result of a previously reported GaCl3-induced
solvent activation.[7] The 31P{1H} NMR spectrum of the reac-
tion mixture containing 1eACHTNUTRGENNG[U GaCl4] displayed several com-
plex multiplet resonances of low intensity. Attempts to iso-
late 4e+ as a gallate salt were unsuccessful. The formation
of 4a+ and 4e+ proceeds by the insertion of two Se atoms
À
into two P P bonds adjacent to the phosphonium moieties
of 1a+ and 1e+. Their structural motif resembles that of
nortricyclane, with three P atoms forming the basal three-
membered ring, the phosphonium moiety and two Se atoms
occupying the bridging positions, and one P atom defining
the apex of the cage. This is in accordance with the observed
AM2OX spin system of the CS-symmetric, 77Se-free iso-
topomers of 4a+ and 4e+ (Figures 4 and 5). The corre-
sponding 31P{1H} NMR parameters were iteratively fitted
and are summarized in Table 3.
Scheme 4. I) Solvent-free reaction of 1aACTHUNGTRENNUNG
equivalents of Segrey; a) 708C, 1 h, 1408C, 2 h, ÀGaCl3, 4a
ACHTUNGTRENNUNG
II) Solvent-free reaction of 1e
b) 1108C, 1 h, 1508C, 16 h.
A
;
A mixture of 1aACHTUNGTRENNUNG[GaCl4] and Segrey in 1:2 stoichiometry
forms a melt at 1108C; however, it solidifies within approxi-
mately 20 min even at temperatures up to 1608C. Therefore,
the addition of one equivalent of GaCl3 was required to sig-
The resonances of the AM2OX spin system are superim-
posed by the AMNOXZ spin system of the C1-symmetric
Chem. Eur. J. 2013, 00, 0 – 0
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J. J. Weigand et al.
Figure 4. A) 31P{1H} NMR spectrum of 4a
ACHTNUGTRNENUG[GaCl4] (CD2Cl2, RT); resonances from small amounts of unidentified side products are marked by asterisks;
the enlargements in C show the experimental (upwards) and simulated spectra (downwards); the enlargements in D (downwards) show the fitted spec-
trum of the 77Se-free isotopomers of 4a+ (AM2OX spin system); the enlargements in E (downwards) show the simulated spectrum of the isotopomer
with one 77Se nucleus (AMNOXZ spin system); B) experimental 77Se{1H} NMR spectrum of 4a
ACHTUNGTRENUNG[GaCl4] (CD2Cl2, RT, 8678 scans, upwards) and iteratively
fitted spectrum (downwards).
2
1
2
responding J
(PASeZ), J
E
E
stants of 4a+. Determination of the 1J
(SeZPM), 2J
1
and J
(PMPN) coupling constants was difficult due to the 77Se
isotope effect and, as a result, the higher order M and N
part of the spin system. However, the 77Se isotope effect on
the 31P{1H} NMR chemical shift of a directly bonded P atom
is only approximately 5 ppb.[25] Thus, the chemical shifts of
the M and N part were set as d(PM)=d(PN). Similar adjust-
ments have previously been made to determine the
ACTHNUTRGNEUNG
nJ(31P77Se) coupling constants in P4SenS3Àn cage compounds
(n=1–3).[26] The values obtained from the assignment itera-
tion of the 77Se{1H} NMR spectrum were subsequently ap-
plied in the simulation of the higher order resonance of the
M and N part of the AMNOXZ spin system, resulting in a
multiplet of 44 lines (Figure 4E, third enlargement from the
left). Twenty of the more intense central lines of the simula-
tion are in very good agreement with the experimental spec-
trum, whereas eight of the remaining intense lines are not
visible due to overlap with the resonances of the M2 part of
the AM2OX spin system. The remaining sixteen lines are of
very low intensity and cannot be observed in the experimen-
tal spectrum.
Figure 5. A) 31P{1H} NMR spectrum of 4e
ACHTNUGTRNE[UNG GaCl4] (CD2Cl2, RT); resonan-
ces from unidentified side products are marked by asterisks; the enlarge-
ments in B show the experimental (upwards) and simulated spectrum
(downwards).
Analogous assumptions were made in the simulation of
the spin systems of both isotopomers of 4e+ (Figure 5B).
The A, M and N parts of the spin systems of 4a+ and 4e+
can be assigned to the P atoms of the basal three-membered
rings on the basis of the characteristic chemical shifts at
high field and the relatively small absolute values of their
mutual coupling constants.[7,28] The O parts are assigned to
isotopomer incorporating one 77Se nucleus. Given the natu-
ral abundance of 77Se (7.63%), the probability of a single
77Se nucleus being present in any one of the two bridging
positions is 14.1%. The AMNOXZ spin system was simulat-
ed by using the obtained 31P{1H} NMR data from the fitting
of the AM2OX spin system (Figure 4D). Simulation of the
approximately first-order A, O and X parts yielded the cor-
2
the apical P atoms on the basis of two different J(PP) cou-
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+
Synthesis and Reactivity of R2P5 Cages
FULL PAPER
Table 3. 31P{1H} and 77Se{1H} NMR parameters of cations 4a+, 4e+, 5a+, 62+ and 72+
.
31P{1H}
4a+
Cy2P5Se2
4e+
Ph2P5Se2
5a+
Cy2P5S2
31P{1H}
62+
72+
+
+
+
Ph4P6Se2+
Ph4P6S2+
isotopomer
spin system
d(PA)
d(PM)=d(PN)
d(PO)
77Se-free
AM2OX
1ꢄ77Se
AMNOXZ
À260.6
À56.8
À38.8
225.3
77Se-free
AM2OXZ
1ꢄ77Se
AMNOXZ
À254.5
À56.6
–
isotopomer
spin system
both
AA’MOXX’(Z)
À195.5
À91.1
À56.5
155.9
–
AA’MOXX’
À203.4
À81.0
À34.0
151.9
–
À193.0
À202.2
À426.1
À313.9
3.4
AM2OX
À291.6
À43.3
À9.4
À260.6
À254.5
d(PA)=d
d(PM)
ACHTUGNRTEN(NUGN PA’)
À56.8
À56.6
À38.8
À26.3
À26.3
d(PO)
d(PX)
225.3
192.7
192.7
207.8
–
d(PX)=d
(77SeZ)
(PAPA’)
(PAPO)=1J
(PAPX)=1J
(PA’PX’)
(PMPX)=1J
(PMPX’)
(PAPM)=2J
(PA’PM)
(PA’PX)=2J
(PAPX’)
(POPM)
(POPX)=2J
(PXPX’)
(PMSeZ)
(POSeZ)
(PA/A’SeZ)/2J
ACHTUGNRTEN(NUGN PX’)
[a]
d
N
–
565.5
–
–
d
A
292.6
1J
1J
1J
1J
2J
2J
2J
2J
1J
2J
1J
2J
N
(PAPN)
À178.2
À178.2
À471.6
À175.8
À348.5
1.2
À176.3
À176.3
À477.5
À176[b]
À332.9
7.4
À172.8
1J
1J
1J
1J
2J
2J
2J
2J
2J
1J
1J
2J
N
À208.6
À200.9
À432.9
À315.7
0.5
3.3
60.6
4.3
35.0
À471.6
À477.5
À469.2
ACHTNUGRTEN(NGNU PA’PO)
–
–
ACHTUNGTRENNUNG
À348.5
À332.9
À341.3
ACHTUNGTRENNUNG
1.2
70.3
6.7
–
7.4
71.1
5.9
–
4.3
73.3
6.3
–
ACHTUNGTRENNUNG
A
70.3
6.7
71.1
T
0.1
70.8
3.0
43.1
–
–
–
A
5.9
À8.4
À8[b]
A
–
–
–
–
À209.0
7.4
–
–
–
–
À209[b]
–
–
–
–
8[b]
À318.5
À104.7
15.8/21.1
À281.6
À293[b]
39[b]
42.9
A
[a] Not measured. [b] Decimal places of the coupling constants are not reported due to insufficient accuracy of the simulation caused by the high com-
plexity of the experimental 31P{1H} NMR spectrum and low intensities of the relevant lines of the resonances.
pling constants to the basal three-membered rings. The large
P3 bond connecting the tetra-coordinated P atom with the
three-membered phosphorus ring is rather short (4e[GaCl4]:
2.187(1) ꢃ, 4a[GaCl4]: 2.186(1) ꢃ) and comparable to bond
2
2
2
values of J
G
E
ACHTUNGTRENNUNG
coupling through bridging chalcogen atoms,[25,28] whereas the
ACHTUNGTRENNUNG
small values of J
ed P atom (33+: J(PP)=0 Hz).[7] The X parts are assigned
to the tetra-coordinated P atoms in 4a+ and 4e+ and are sig-
nificantly shifted to lower field compared to the correspond-
ing resonances of related R2P5 cages 1a+ and 1e+. The
values of the J(PP) coupling constants between the PX and
PO atoms are of typical magnitude for one-bond couplings
between tetra- and tri-coordinated
P
atoms (e.g.,
[Ph3PPPh2]
ACHTUNGTRENNUNG
1
values of the J(PP) coupling constants involving the PX and
PA atoms are remarkably large. This seems to be a charac-
teristic feature of nortricyclane-type polyphosphorus com-
pounds and has previously been observed for cations 33+
(1J(PP)=À397 Hz)[7] and 9+ (1J(PP)=À368.2 Hz).[8] The iso-
topomer of 4a+ with one 77Se nucleus exhibits a resonance
at dACHTUNGTRENNUNG
(SeZ)=565.5 ppm in the 77Se{1H} NMR spectrum, which
ACTHNUTRGNEUNG
is comparable to values reported for P4Se277Se (d(77Se)=
Figure 6. Molecular structures of cations 4a+ and 4e+ in 4a
4e[GaCl4] (hydrogen atoms are omitted for clarity and thermal ellipsoids
are displayed at 50% probability); selected bond lengths [ꢃ] and angles
ACHTUNGRTENN[UNG GaCl4] and
540.6 ppm) and P4Se77SeS (d(Se)=596.7 ppm).[25] All ob-
AHCTUNGTRENNUNG
n
served J
N
[8]: 4a+: P1 C1 1.835(4), P1 C7 1.836(4), P1 P2 2.201(1), P1 P3
À
À
À
À
with the corresponding parameters of previously published
À
À
À
À
2.186(1), P2 Se1 2.248(1), P2 Se2 2.236(1), P3 P4 2.218(2), P3 P5
1
compounds,[25] with the exception of J
comparatively small absolute value.
Single crystals of 4a[GaCl4] and 4eACHTNUGTRENNUNG
ACHTUNGTRENNUNG
À
À
À
2.213(3), P4 P5 2.268(4), P4 Se1 2.271(1), P5 Se2 2.237(3); C1-P1-C2
108.4(2), P3-P1-P2 109.86(6), P1-P2-Se1 92.99(5), P1-P2-Se2 95.07(5),
Se1-P2-Se2 101.01(5), P2-Se1-P4 100.94(5), P2-Se2-P5 102.19(8), Se2-P5-
P4 104.4(1), Se2-P5-P3 108.5(1), Se1-P4-P3 106.85(6), Se1-P4-P5
G
X-ray structure determination were obtained by diffusion of
n-hexane into solutions of the respective compounds at
À358C. The molecular structures of the cations are depicted
106.24(9), P1-P3-P4 99.15(6), P1-P3-P5 99.2(1), P3-P4-P5 59.1(1), P4-P5-
+
À
À
À
P3 59.3(1), P5-P3-P4 61.6(1); 4e : P1 C1 1.799(3), P1 C7 1.802(3), P1
À
À
À
À
P2 2.200(1), P1 P3 2.187(1), P2 Se1 2.2224(9), P2 Se2 2.2324(9), P3 P4
À
À
À
À
À
2.236(1), P3 P5 2.235(1), P4 P5 2.206(1), P4 Se1 2.2664(9), P5 Se2
2.2673(9); C1-P1-C2 110.6(2), P3-P1-P2 110.32(5), P1-P2-Se1 93.41(4),
P1-P2-Se2 93.97(4), Se1-P2-Se2 102.14(3), P2-Se1-P4 101.32(3), P2-Se2-
P5 101.35(3), Se2-P5-P4 105.37(4), Se2-P5-P3 107.43(4), Se1-P4-P3
106.17(4), Se1-P4-P5 106.87(4), P1-P3-P4 99.05(4), P1-P3-P5 98.56(4), P3-
P4-P5 60.42(4), P4-P5-P3 60.45(4), P5-P3-P4 59.12(4).
in Figure 6. Both compounds display comparable P P bond
lengths and angles in the R2P5Se2 frameworks and, thus,
+
À
are jointly discussed. The P P bonds within the basal three-
À
membered rings as well as the P1 P2 bonds in both com-
[18]
À
À
pounds exhibit typical P P single-bond lengths. The P1
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J. J. Weigand et al.
+
lengths involving the tetra-coordinated P atom in R2P5
À
cages (see above). The P Se bond lengths are similar to
those observed in binary phosphorus selenides.[29] The P1
atoms are in an almost perfect tetrahedral environment, in
+
contrast to the strained phosphonium moieties in R2P5
cages, which might account for the differences in the chemi-
cal shifts of the corresponding resonances (see above).
Solvent-free reactions of 1aACHTNUTRGENNUG[GaCl4] and 1eACHTUNGTERN[NUGN GaCl4] with
= a-S8 were performed in analogy to the reactions involving
2
8
Segrey. The reaction involving 1a+ yielded 5a+, which is the
lighter congener of 4a+ (Scheme 5). A phenyl-substituted
derivative 5e+ was not observed. In both reactions, the con-
densation of a large amount of P4 on colder parts of the re-
action vessel was observed.
Figure 8. Molecular structure of adduct 17a (hydrogen atoms are omitted
for clarity and thermal ellipsoids are displayed at 50% probability); se-
À
À
lected bond lengths [ꢃ] and angles [8]: P1 C1 1.815(2), P1 C7 1.815(2),
À
À
À
P1 Cl1 2.0003(7), P1 S1 2.0142(7), S1 Ga1 2.3182(5); C1-P1-C7
113.7(9), C1-P1-Cl1 104.38(7), C7-P1-Cl1 104.66(7), C1-P1-S1 113.26(7),
C7-P1-S1 108.67(7), Cl1-P1-S1 111.82(7), P1-S1-Ga1 105.56(2).
Single crystals of 17a suitable for X-ray structure determi-
nation were obtained by diffusion of n-hexane into the fil-
tered reaction mixture at À358C. The molecular structure is
depicted in Figure 8 and reveals coordination of the GaCl3
to the sulfur atom. Similar coordination modes have been
Scheme 5. Solvent-free reactions of 1a
G
ACHTUNGERTN[NUNG GaCl4]
2
(R=Ph) with = a-S8; n + m=1; a) 1a
N
ACHTUNGTRENNUNG
8
1108C, 1.5 h.
reported for related compounds.[31] The S1 Ga1 bond length
À
(2.3182(5) ꢃ) is in the typical range[32] for such an interac-
The 31P{1H} NMR spectra of the melts dissolved in
CH2Cl2 are depicted in Figure 7. In both, prominent reso-
tion and the S1 P1 bond length (2.0142(7) ꢃ) is very similar
À
to those in (iPr2N)2P(S)Cl·AlCl3 (2.017(6) ꢃ) or Ph3PS·AlCl3
nances of an AX3 spin system (d(PA)=À128.2 ppm, d(PX)=
(2.028(2) ꢃ).[33] The 31P{1H} NMR spectrum of the reaction
2
63.2 ppm, J
N
mixture containing 1eACTHNGUTERN[NUG GaCl4] also shows a prominent sin-
reaction involving 1a
[GaCl4],
a
singlet resonance of
glet resonance, which can be assigned to 17e (d(P)=
CyP(S)Cl·GaCl3 (17a, d(P)=122.1 ppm) was observed.[30]
86.6 ppm).[34] The formation of P4S3 and 17a/17e may be ra-
tionalized in terms of dissociation of 1a/1eACTHNURGTNEUNG[GaCl4] yielding
P4 and R2PCl·GaCl3 (R=Cy, Ph). Such dissociations of
+
R2P5 cage compounds are commonly observed in coordi-
nating solvents[7] and might also be initiated by nucleophilic
S8 in the melts. Subsequently, P4S3 and 17a/17e are obtained
by the reaction of P4 and R2PCl·GaCl3 with a-S8. No other
binary P4Sn compounds (n=1, 2; n>3) were observed by
means of 31P{1H} NMR spectroscopy. Only the spectrum of
the reaction mixture containing 1aACTHNUTRGNENUG[GaCl4] (Figure 7A) dis-
played the resonances of an AM2OX spin system at low in-
tensity (24% conversion), which could be assigned to cation
5a+. In comparison with the selenium congener 4a+, the res-
onance of the PO atom is shifted to lower field (5a+: d(PO)=
À9.4 ppm; 4a+: d(PO)=À38.8 ppm). This can be rational-
ized in terms of different inductive effects of the chalcogen
atoms, which is the dominant factor that influences the
chemical shifts of apical P atoms in the series P4Se3, P4Se2S,
P4SeS2 and P4S3.[35] The resonances of basal P atoms shift to
lower field with increasing exocyclic angles involving the
basal ring.[25] This is attributed to a decreased s-orbital con-
tribution to the lone pairs of electrons and, consequently, a
decreased shielding of these P atoms. Thus, the downfield
shift of the M part of the spin system of 5a+ (d(PM)=
À43.3 ppm) compared to the M and N parts in the case of
4a+ (d(PM)=d(PN)=À56.8 ppm) indicates a more acute
Figure 7. 31P{1H} NMR spectra of the reactions of A) 1a
N
2
RT) and B) 1e
G
8
tal (upwards) and fitted spectra (downwards) of the AM2OX spin system
of 5a+; resonances from unidentified side products are marked by aster-
isks.
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+
Synthesis and Reactivity of R2P5 Cages
FULL PAPER
exocyclic angle in the latter. This observation is consistent
with similar angles observed in P4S3 and P4Se3.[36] The high-
field shift of the A part for 5a+ (d(PA)=À291.6 ppm; 4a+:
d(PA)=À260.6 ppm) can be explained by similar arguments.
To gain a detailed understanding of the intermediates in-
volved in the formation of 4a+/4e+, the reactions of 1a/1e-
ACHTUNGTRENNUNG[GaCl4] with Segrey in a 1:1 stoichiometry were investigated.
À
The insertion of one Se atom into a P P bond of the respec-
+
tive R2P5 cages is assumed to yield cations 18a+/18e+
(Scheme 6).
Figure 9. A) 31P{1H} NMR spectrum of the dissolved reaction mixture of
1eACTHNUTRGNEU[GN GaCl4] and Segrey in a 1:1 stoichiometry (CH2Cl2, C6D6 capillary, RT);
resonances from unidentified side products are indicated by asterisks;
B) enlargements showing the experimental (upwards) and fitted spectra
(downwards) of the resonances of dication 62+
.
nated P atoms. The AA’ part (d(PA)=d
(PA’)=À195.5 ppm)
and the O part (d(PO)=À56.5 ppm) are assigned to the
basal P3 ring by comparison with the spectra of related neu-
tral nortricyclane-type compounds.[37] As discussed for cat-
Scheme 6. Suggested stepwise formation of 4a+/4e+ and 62+
.
AHCTUNGTRENNUNG
ions 4a+/4e+, the 1J(PP) coupling constant between the
basal three-membered ring and the tetra-coordinated P
atoms (d(PX)=d(PX’)=155.9 ppm) has large absolute
value (1J(PAPX)=1J
(PA’PX’)=À432.9 Hz). The M part of the
G
a
The melt of 1a
E
G
ACHTUNGTRENNUNG
to prevent solidification and was heated to 1508C for 2 h.
After cooling, it was dissolved in CH2Cl2 and investigated
by means of 31P{1H} NMR spectroscopy. The spectrum indi-
cated approximately 50% conversion of the starting materi-
al 1a+ to 4a+. An intermediate species of type 18a+, how-
ever, was not observed. This suggests that the insertion of
the first selenium atom into a bond adjacent to the phospho-
nium moiety is the rate-determining step in the formation of
AA’MOXX’ spin system (d(PM)=À91.0 ppm) is assigned to
the apical P atom and is shifted to higher field compared to
the related resonances of cations 4a+/4e+. Prolonged heat-
ing of the melt to 1208C for 18 h resulted in the formation
of some 4e+ according to 31P{1H} NMR spectroscopic inves-
tigations. The reaction of 1e+ with Segrey is assumed to pro-
ceed as follows. The initially formed intermediate 18e+
reacts in the second step to afford dication 62+ through the
incorporation of a Ph2P+ fragment (Scheme 6). This may be
understood in terms of a transfer of a Ph2P+ moiety from
1e+ to intermediate 18e+. This step is accompanied by the
stoichiometric formation of P4, sublimation of which was
typically observed in all chalcogenation reactions involving
1e+. Dication 62+ subsequently reacts to produce 4e+ if
longer reaction times are applied. This proceeds through the
exchange of a Ph2P+ moiety by an Se atom. The low conver-
sion of cation 1e+ to 4e+ observed in the 1:2 reaction of 1e+
and Segrey (see above) may be attributed to the intermediate
formation of 62+, which consumes one equivalent of 1e+.
Moreover, the removal of P4 from the reaction mixture ini-
tiates side reactions of the formally remaining Ph2P+ cation.
4a+. The melt containing 1e
ACHTUNRGTNEUNG[GaCl4] and Segrey was heated
to 1108C for 1 h, during which time some P4 condensed on
colder areas of the reaction vessel.
A portion of the melt was dissolved in CH2Cl2 and investi-
gated by means of 31P{1H} NMR spectroscopy (Figure 9A).
The spectrum featured resonances of the cation 1e+
(ꢀ50%) and some of lower intensity corresponding to
Ph2P(Se)Cl·GaCl3 (15e), Ph2PClH+ (16e+) and phosphanyl-
phosphonium ion Ph2(Cl)PPPh2 (19+).[7] Resonances corre-
sponding to 18e+ were not observed. Most prominent was
an AA’MOXX’ spin system, attributable to the 77Se-free iso-
topomer of dication 62+. These resonances were superim-
posed by the AA’MOXX’Z spin system of the isotopomer
with one 77Se nucleus (Figure 9B). Dication 62+ possesses a
CS-symmetric, nortricyclane-type structure. The bridging po-
sitions are occupied by one Se atom and two tetra-coordi-
Accordingly, the reaction of 1e
stoichiometry yields 6[GaCl4]2 and P4 (Scheme 7). Upon
heating the reaction mixture to 1208C for 12 h, condensa-
ACHTUNGNERTN[UGN GaCl4] with Segrey in a 2:1
AHCTUNGTRENNUNG
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Scheme 7. Solvent-free reaction of 1e
ometry; a) ÀP4, 1208C, 12 h.
ACHTUNGNERTN[NUG GaCl4] with Segrey in a 2:1 stoichi-
tion of P4 on colder areas of the reaction vessel was ob-
served. The 31P{1H} NMR spectrum of the reaction mixture
Figure 11. Molecular structure of cation 62+ in 6
ACTHUNRGTNNEUG[GaCl4]2·0.5ACHTUGNTERN(NUGN CH2Cl2) (hy-
drogen atoms and solvate molecule are omitted for clarity and thermal
ellipsoids are displayed at 50% probability); selected bond lengths [ꢃ]
dissolved in CD2Cl2 showed 6
ACHTUGNRTEN[NUGN GaCl4]2 as the main product
in an approximate purity of 80% (Figure 10A).
À
À
À
À
and angles [8]: P1 C1 1.791(7), P1 C7 1.799(7), P6 C13 1.790(7), P6
À
À
À
À
C19 1.797(7), P1 P2 2.209(2), P1 P3 2.201(1), P6 P2 2.192(2), P6 P3
À
À
À
À
2.198(2), P2 Se1 2.217(2), P4 Se1 2.303(2), P3 P4 2.241(3), P3 P5
2.214(2), P4 P5 2.224(3); C1-P1-C2 109.0(3), C13-P6-C19 113.1(3), P3-
À
P1-P2 110.5(1), P5-P6-P2 110.5(1), P1-P2-Se1 94.69(8), P6-P2-Se1
95.34(8), P1-P2-P6 91.67(9), P2-Se1-P4 101.70(7), P4-P3-P1 99.0(1), P5-
P3-P1 101.7(1), P3-P5-P6 103.10(9), P4-P5-P6 98.39(9), P3-P4-Se1
106.88(9), P5-P4-Se1 108.08(8), P3-P4-P5 59.46(8), P4-P5-P3 60.65(8), P5-
P3-P4 59.89(9).
atoms that show the coupling constant of larger absolute
value in the 31P{1H} NMR spectrum (1J
G
1
vs. J
N
As presented in Scheme 6, dication 62+ reacts with Segrey
to give 4e+ through the formal exchange of a phosphonium
moiety by a Se atom. This prompted us to speculate as to
whether this remarkable reactivity might be exploited to
prepare dications of type 62+ by the reaction of 33+ with
a-S8 or Segrey. The reaction with sulfur is of particular inter-
Figure 10. A) 31P{1H} NMR spectrum of dissolved
from the reaction of 1e[GaCl4] and Segrey in a 2:1 stoichiometry (CD2Cl2,
RT); resonances from unidentified side products are marked by asterisks;
B) experimental 77Se{1H} NMR spectrum of 6
[GaCl4]2 (upwards, CD2Cl2,
RT, 13182 scans) and simulated spectrum (downwards).
6ACHTUNGRETNNU[G GaCl4]2 obtained
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
est since the related S derivative (72+) is not otherwise ac-
cessible. Thus, the reactions of 3
N
Attempts to isolate analytically pure 6
[GaCl4]2 were un-
Segrey in 1:1 and 1:4 stoichiometries were investigated
(Scheme 8). All obtained melts were dissolved in CH2Cl2
successful. However, in contrast to the previously obtained
mixtures, the material was of sufficient purity to record a
77Se{1H} NMR spectrum (Figure 10B). The 77Se resonance
displayed a broad ddtt splitting at d
resonance is remarkably shifted to higher field compared to
the resonances of 4a+ (d(SeZ)=565.5 ppm) and P4Se277Se
(d(Se)=540.6 ppm).[25] The absolute value of the J
coupling constant involving the apical P atom is larger
(1J
(PMSeZ)=À318.5 Hz) than that involving the basal P
atom (1J
(POSeZ)=À104.7 Hz). similar but less pro-
nounced trend was observed in the series P4SenS3Àn (n=1–
ACHTUNGTREN(NNUG SeZ)=292.6 ppm. This
AHCTUNGTRENNUNG
1
AHCTUNGTRENNUNG
(31P77Se)
ACHTUNGTRENNUNG
G
A
1
Scheme 8. Solvent-free reactions of 3
G
8
and 1:4 stoichiometries; a)+1= a-S8, 1108C, 12 h; b)+4= a-S8, 1108C,
48 h; c)+1 Segrey, 1108C, 12 h; d)+4 Segrey, 1108C, 24 h.
8
3)[25] and for cations 4a+/4e+ (e.g., 4a+: 1J
ACHTUNGTRENNUNG
À281.6 Hz, 1J
ACHTUNGTRENNUNG
CH2Cl2 solvate of 6ACHTUNGTRENNUNG
termination were obtained by slow diffusion of n-hexane
into a solution in CH2Cl2 at À358C. Unfortunately, the crys-
tals were covered with a copious amount of a yellow oil,
and analysed by means of 31P{1H} NMR spectroscopy. For
reactions involving Segrey, the formation of 62+ was observed.
In the case of a-S8, prominent resonances of an AA’MOXX’
spin system could be assigned to 72+ by analogy with 62+
(Figure 12).
which prevented the isolation of pure 6ACHTUNRTGENUNG[GaCl4]2. The molec-
ular structure of dication 62+ is depicted in Figure 11. The
À
P Se bond involving the apical P atom is distinctly shorter
As byproducts, GaCl3 and Ph2PCl were released in the re-
action mixtures. These formed either phosphanylphosphoni-
um ion 19+[7] or adduct 15e (17e). Both compounds were
À
À
than that to the basal P atom (P2 Se1: 2.217(2) ꢃ, P4 Se1:
2.303(2) ꢃ). Interestingly, the shorter bond involves those
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Synthesis and Reactivity of R2P5 Cages
FULL PAPER
the features that influence these parameters. Figure 13B and
C shows the dependence of the chemical shifts of 33+, 62+
,
72+, 4a+, 4e+, 5a+, P4Se3 and P4S3 on the number of chalco-
gen atoms in the corresponding molecules.
In general, the stepwise exchange of tetra-coordinated P
atoms in 33+ by Se or S atoms leads to a high-field shift of
the resonances of the P atoms of the basal three-membered
ring. This is illustrated for P atoms bonded to a tetra-coordi-
nated P atom in the sequence 33+ (d(PA)=À163.7 ppm),[7]
62+ (d(PA)=À195.4 ppm) and 4e+ (d(PA)=À260.6 ppm). A
similar but less pronounced trend is observed for the P
atoms bonded to the chalcogen bridges (e.g., 72+: d(PO)=
À34.0 ppm, 5a+: d(PM)=À43.3 ppm, P4S3:
dACHTUNGTRENNUNG(Pbasal)=
À120.1 ppm;[25] 4a+: d(PM)=À56.8 ppm and P4Se3:
d(Pbasal)=À104.5 ppm[25]). The resonances of basal P atoms
in related compounds have been reported to shift to higher
field with decreasing exocyclic angles.[25] An analogous trend
is observed in the solid state for exocyclic angles involving
tetra-coordinated P atoms (av. P-P-P angle 33+: 102.5(2)8,[7]
6
2+: 100.6(4)8 and 4e+: 98.81(4)8) and Se atoms (av. P-P-Se
angle 62+: 107.5(2)8, 4e+: 106.4(6)8, P4Se3: 104.5(2)8[35]). The
resonances of the apical phosphorus atoms exhibit the
widest range of chemical shifts and show a stepwise down-
field shift upon the substitution of tetra-coordinated P
atoms by chalcogen atoms. This is illustrated in the sequence
33+ (d(PM)=À157.1 ppm),[7] 62+ (d(PM)=À91.0 ppm), 4e+
Figure 12. 31P{1H} NMR spectra of the dissolved reaction mixtures of 3-
ACHTUNGTRENNUNG[Ga2Cl7]3 and a-S8 in stoichiometries of A) 1:1 (CH2Cl2, C6D6 capillary,
RT) and B) 1:4 (CH2Cl2, C6D6 capillary, RT); the enlargements in C
show the experimental (upwards) and fitted spectra (downwards) of the
AA’MOXX’ spin system of 72+; resonances from unidentified side prod-
ucts are marked by asterisks.
(d(PO)=À26.3 ppm) and P4Se3 (d
(Papical)=53.3 ppm)[25] and
ACHTUNGTRENNUNG
is consistent with the different electronegativities of directly
bonded phosphorus or chalcogen atoms. Moreover, apical P
atoms in nortricyclane-type arrangements[27] commonly
show a high dependency of the chemical shift on elongation
or compression of the framework.[38] Elongation is accompa-
nied by a decrease in the P-P-P angles at the apical P atom.
Thus, the s-orbital contribution to the lone pair of electrons
increases and leads to an upfield shift of the corresponding
resonance in the 31P{1H} NMR spectrum.[39] On this basis,
observed in the reactions of 1:1 stoichiometry, whereas only
the latter was formed in reactions of 1:4 stoichiometry.
All presented cationic polyphosphorus–chalcogen cages
were formally derived by stepwise isolobal exchange of [Se]
or [S] by [R2P]+ units in the bridging positions of the nortri-
cyclane-type structures of P4Se3 and P4S3 (Figure 13A). This
enables an in-depth study of the 31P{1H} NMR characteris-
tics of the whole series of compounds and an evaluation of
Figure 13. A) The series of cationic polyphosphorus–chalcogen cages formally derived from stepwise isolobal substitution of [Ch] by [R2P]+ units in
P4Se3 or P4S3; B) 31P{1H} NMR shifts of 33+, 62+, 72+, 4a+, 4e+, 5a+, P4S3 and P4Se3 versus the number of chalcogen atoms (n); C) frame displays the as-
signment of P or Ch atoms to the positions of a nortricyclane-type cage; Ch=S, Se.
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J. J. Weigand et al.
in the case of R=Me solidification was observed. The melts were dis-
solved in either CH2Cl2 (R=Cy, iPr) or C6H4F2 (R=Et). After removal
of a small amount of orange residue by filtration, n-hexane was added,
which yielded brown to yellow oils. Brownish to yellowish microcrystal-
line solids were obtained by repeated dissolution of the oils in CH2Cl2
and addition of n-hexane. The workup procedure for compound
1d[GaCl4] involved mechanical crushing of the melt and washing of the
powder with C6H5F (3ꢄ20 mL). After removal of all volatiles in vacuo,
the observed stepwise downfield shift indicates a stepwise
elongation of the nortricyclane-type framework. This is also
reflected in the molecular structures of the respective com-
pounds. The distance between the centroid of the basal ring
and the apical P atom increases in the sequence P4Se3
(3.182(3) ꢃ), 4e+ (3.268(1) ꢃ), 62+ (3.34(2) ꢃ) and 33+
(3.397(1) ꢃ), and the P-P-P angles at the apical P atoms
become more acute (angular sums P4Se3: 298.6(3)8,[25] 4e+:
289.1(1)8, 62+: 281.7(3)8 and 33+: 275.0(3)8[7]).
1d
7.98 g; 1b
71%, 2.82 g. In the case of 1d
N
ACHTUNGTRENNUNG
C
U
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
coordinating solvents such as C6H5F, C6H4F2 and CH2Cl2 was observed.
The solubility was significantly enhanced in the presence of GaCl3.
Therefore, one equivalent of GaCl3 was added to a solution of 1dACHTUNGTRENNUNG[GaCl4]
Conclusion
in CD2Cl2 to obtain sufficiently resolved NMR spectra. Single crystals
suitable for X-ray structure determination were obtained by diffusion of
n-hexane into a solution of the respective gallate salt in CH2Cl2 at
+
A series of R2P5 cages (R=alkyl, aryl) has been conven-
iently synthesized by the reaction of R2PCl, GaCl3 and P4 on
a multi-gram scale and fully characterized. Depending on
the substituent R, solvent-free melt approaches (R=alkyl)
or solutions in C6H5F (R=aryl) are required. The
31P{1H} NMR parameters in solution and the molecular
structures in the solid state have been studied in detail.
À358C; characterization data for compounds 1a–1d
ACHTUNGRTEN[NNUG GaCl4] are provided
in the Supporting Information.
Preparation of 1e–1hACHTUNGRTNEUNG[GaCl4]: P4 (1.0 equiv) was added to a solution of
GaCl3 (1.0 equiv) and R2PCl (1 equiv; R=Ph: 662 mg, 3.00 mmol; R=
C6F5: 8.011 g, 20.00 mmol; R=Mes: 305 mg, 1.00 mmol; R=Dipp:
389 mg, 1.00 mmol) in C6H5F (5–30 mL). The addition of GaCl3 to solu-
tions of R2PCl (R=C6F5, Mes, Dipp) yielded intensely red to purple re-
action mixtures. In the course of the dissolution of P4, a colour change to
yellow was observed. The resulting suspensions were stirred in the dark
at ambient temperature (R=Ph: 14 d; R=C6F5: 2 d; R=Mes: 2 h; R=
Dipp: 12 h). Thereafter, n-hexane (10 mL) was added to complete the
precipitation. The supernatants were removed and the yellow to colour-
less microcrystalline solids were washed with n-hexane. All volatiles were
removed in vacuo, yielding analytically pure compounds; yields:
+
Moreover, the R2P5 cages have been utilized in chalcoge-
nation reactions with a-S8 or Segrey in a solvent-free melt ap-
proach, yielding unique polyphosphorus–chalcogen cations
that are difficult to prepare by other methods. The chalcoge-
nation proceeds by selective insertion of selenium or sulfur
+
À
atoms into P P bonds of the cationic R2P5 cages. In a com-
1e[GaCl4]: 90%, 1.40 g; 1 f
ACHTUTGNRENNGU[GaCl4]: 80%, 11.14 g; 1gACHTUNTGREN[NUGN GaCl4]·0.5C6H5F:
plementary approach, such cations were synthesized by the
substitution of phosphonium moieties in the tricationic cage
Ph6P73+. Utilizing both approaches gave access to an intrigu-
ing series of nortricyclane-type polyphosphorus–chalcogen
cations. These adopt structures that are formally derived by
stepwise isolobal exchange of chalcogen moieties [Ch]
86%, 563 mg; 1h[GaCl4]: 82% 367 mg. Single crystals of
AHCTUNGTRENNUNG
1g[GaCl4]·0.5C6H4F2 suitable for X-ray structure determination were ob-
tained by layering a solution in C6H4F2 with pentane at À358C. Single
crystals of 1h
tion of 1h
pounds 1 f–1h
Preparation of 4a
Segrey (158 mg, 2.00 mmol, 2.0 equiv) were added to 1aAHCTUNGTRENNUNG
ACHTUNGRTEN[NGNU GaCl4] were obtained by diffusion of n-hexane into a solu-
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
(Ch=Se, S) in P4S3 and P4Se3 by [R2P]+ moieties, thus re-
AHCTUNGTRENNUNG
3+
sulting in structures of the types R6P7
, ,
R4P6Ch2+
1.00 mmol, 1.0 equiv). The mixture was stirred and heated to 708C for
1 h to afford a suspension of Segrey in a yellow melt. When the mixture
started to solidify, the temperature was incrementally increased to 1408C
and the mixture was stirred for a further 2 h. In the course of the reac-
tion, the Segrey was consumed and a brown melt was formed. After cool-
ing to ambient temperature, C6H4F2 (20 mL) was added to afford a
yellow supernatant and a small amount of yellow residue, which was re-
moved by filtration. The solution was investigated by 31P{1H} NMR spec-
troscopy. Addition of n-hexane (10 mL) to the filtered solution yielded a
yellow oil. Extensive washing of this oil with n-hexane (5ꢄ5 mL) resulted
in a yellow sludge. This material was dissolved in C6H4F2 (10 mL) and
the clear solution was layered with n-hexane at À358C. After 4 d, com-
R2P5Ch2 and P4Ch3. In depth 31P{1H} and 77Se NMR spec-
troscopic studies in solution are presented and the chemical
shifts are correlated with the observed structural features in
the solid state.
+
Experimental Section
General: General information on materials and methods is given in the
Supporting Information. Experimental details regarding the reactions of
2
pound 4aACHTUNRGTNE[UGN GaCl4] was obtained as a yellow, crystalline material in approx-
1a
G
G
8
imately 95% purity (27%, 185 mg), which was suitable for X-ray single-
crystal structure determination; characterization data for compound
4a[GaCl4] are provided in the Supporting Information.
action of 1e
G
1
3[Ga2Cl7]3 with Segrey or = a-S8 in 1:2 and 1:4 stoichiometries are provid-
ed in the Supporting Information.
Preparation of 4e
CATHNUGTREN[NUNG GaCl4]: Segrey (111 mg, 1.40 mmol, 2.0 equiv) was
Preparation of 1a–1dACHTUNGTRENNUNG[GaCl4]: GaCl3 (1.0 equiv) was carefully added to a
added to 1e[GaCl4] (364 mg, 0.70 mmol, 1.0 equiv) and the mixture was
AHCTUNGTRENNUNG
mixture of P4 (1.0 equiv) and R2PCl (1 equiv; R=Cy: 4.65 g, 20.00 mmol;
R=iPr: 1.53 g, 10.00 mmol; R=Et: 335 mg, 2.70 mmol; R=Me: 965 mg,
10.00 mmol). The exothermic reactions led to the formation of yellow to
brown biphasic melts, of which the upper phases were composed of
liquid P4 and the immiscible lower phases of R2PCl and GaCl3. The melts
were vigorously stirred for 3 h at 1508C (R=Cy); 2.5 h at 1308C (R=
iPr); 1 h at 1208C (R=Et); or 1 h at 1008C (R=Me). In the case of R=
Cy or iPr, the condensation of a large amount of P4 on colder parts of
the reaction vessels was observed. This could be avoided by heating the
tops of the reaction vessels with a heat gun to approximately 2008C. For
R=Et or Me, the initially yellow melt turned a deep-orange colour and
heated to 1108C for 1 h to afford a suspension of Segrey in a yellow melt.
When the mixture started to solidify, the temperature was raised to
1508C and the mixture was stirred for a further 16 h. The sublimation of
some P4 to colder parts of the reaction vessel was observed, accompanied
by the formation of a brown melt. After cooling to ambient temperature
and addition of CH2Cl2 (15 mL), a small amount of a yellowish residue
was removed by filtration. The filtered solution was investigated by
means of 31P{1H} NMR spectroscopy, identifying 4e+ as the main product.
Attempts to isolate 4e+ as a gallate salt failed. However, slow diffusion
of n-hexane into a solution of the reaction mixture in CH2Cl2 gave a
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Synthesis and Reactivity of R2P5 Cages
FULL PAPER
yellow oil and a small amount of single crystals of 4e
X-ray structure determination; characterization data for compound
4a[GaCl4] are provided in the Supporting Information.
[GaCl4] suitable for
Hoge, P. Panne, Chem. Eur. J. 2006, 12, 9025–9035; c) R. G. Miller,
A. W. Yankowsky, S. O. Grim, J. Chem. Phys. 1969, 51, 3185–3190;
d) E. Fluck, D. Wachtler, Liebigs Ann. Chem. 1979, 1125–1129.
[18] a) I. Krossing, J. Am. Chem. Soc. 2001, 123, 4603–4604; b) H. Tai, I.
Krossing, M. Seth, D. V. Deubel, Organometallics 2004, 23, 2343–
2349.
[19] a) E. Fluck, R. Riedel, H.-D. Hausen, G. Heckmann, Z. Anorg.
Allg. Chem. 1987, 551, 85–94; b) J.-P. Bezombes, P. B. Hitchcock,
M. F. Lappert, J. E. Nycz, Dalton Trans. 2004, 499–501.
[20] M. B. Power, A. R. Barron, Angew. Chem. 1991, 103, 1403–1404;
Angew. Chem. Int. Ed. Engl. 1991, 30, 1353–1354.
[21] Y. Xiong, S. Yao, M. Brym, M. Driess, Angew. Chem. 2007, 119,
4595–4597; Angew. Chem. Int. Ed. 2007, 46, 4511–4513.
[22] M. Necas, M. R. St J. Foreman, J. Marek, J. D. Wollins, J. Novosad,
New J. Chem. 2001, 25, 1256–1263.
[23] It has been reported that coordination of a Lewis acid to the Se
atom of selenophosphoryl derivatives does not have a significant in-
fluence on the chemical shift; therefore, compounds 15a and
iPr2P(Se)Cl display similar 31P{1H} NMR parameters; see: a) R.
Sevcik, M. Necas, J. Novosad, Polyhedron 2003, 22, 1585–1589; b) P.
Sekar, J. A. Ibers, Inorg. Chim. Acta 2001, 319, 117–122.
[24] J. R. Goerlich, R. Schmutzler, Phosphorus Sulfur Silicon Relat.
Elem. 1994, 88, 241–244.
Acknowledgements
We gratefully acknowledge the FCI (fellowship for M.H. Holthausen),
the European Phosphorus Science Network (PhoSciNet CM0802) and
the DFG (WE 4621/2–1). J. J.W. thanks Prof. F. Ekkehardt Hahn (WWU
Mꢀnster) for his generous support.
[1] C. A. Dyker, N. Burford, Chem. Asian J. 2008, 3, 28–36.
[2] a) V. A. Milyukov, Y. H. Budnikova, O. G. Sinyashin, Russ. Chem.
Rev. 2005, 74, 781–805; b) M. Scheer, G. Balazs, A. Seitz, Chem.
Rev. 2010, 110, 4236–4256; c) N. A. Giffin, J. D. Masuda, Coord.
Chem. Rev. 2011, 255, 1342–1359.
[3] a) I. Krossing, I. Raabe, Angew. Chem. 2001, 113, 4544–4547;
Angew. Chem. Int. Ed. 2001, 40, 4406–4409; b) M. Gonsior, I.
Krossing, L. Mꢀller, I. Raabe, M. Jansen, L. van Wꢀllen, Chem. Eur.
J. 2002, 8, 4475–4492; c) I. Krossing, J. Chem. Soc. Dalton Trans.
2002, 500–512; d) A. Bihlmeier, M. Gonsior, I. Raabe, N. Trapp, I.
Krossing, Chem. Eur. J. 2004, 10, 5041–5051.
[4] a) M. H. Holthausen, J. J. Weigand, J. Am. Chem. Soc. 2009, 131,
14210–14211; b) M. H. Holthausen, C. Richter, A. Hepp, J. J. Wei-
gand, Chem. Commun. 2010, 46, 6921–6923; c) M. H. Holthausen,
J. J. Weigand, Z. Anorg. Allg. Chem. 2012, 638, 1103–1108.
[5] M. H. Holthausen, K.-O. Feldmann, S. Schulz, A. Hepp, J. J. Wei-
gand, Inorg. Chem. 2012, 51, 3374–3387.
[6] a) J. J. Weigand, N. Burford, A. Decken, Eur. J. Inorg. Chem. 2008,
4343–4347; b) J. J. Weigand, N. Burford, M. D. Lumsden, A.
Decken, Angew. Chem. 2006, 118, 6885–6889; Angew. Chem. Int.
Ed. 2006, 45, 6733–6737.
[7] J. J. Weigand, M. H. Holthausen, R. Frçhlich, Angew. Chem. 2009,
121, 301–304; Angew. Chem. Int. Ed. 2009, 48, 295–298.
[8] M. Gonsior, I. Krossing, E. Matern, Chem. Eur. J. 2006, 12, 1703–
1714.
[9] I. Krossing, Chem. Eur. J. 2001, 7, 490.
[10] M. Gonsior, I. Krossing, E. Matern, Chem. Eur. J. 2006, 12, 1986–
1996.
[11] N. Burford, T. S. Cameron, D. J. LeBlanc, P. Losier, S. Sereda, G.
Wu, Organometallics 1997, 16, 4712–4717.
[12] a) N. Burford, T. S. Cameron, P. J. Ragogna, J. Am. Chem. Soc. 2001,
123, 7947–7948; b) N. Burford, P. J. Ragogna, R. McDonald, M. J.
Ferguson, J. Am. Chem. Soc. 2003, 125, 14404–14410.
[13] a) B. D. Ellis, P. J. Ragogna, C. L. B. McDonald, Inorg. Chem. 2004,
43, 7857–7867; b) J. M. Slattery, S. Hussein, Dalton Trans. 2012, 41,
1808–1815.
[14] a) E. Niecke, R. Rꢀger, B. Krebs, Angew. Chem. 1982, 94, 553–554;
Angew. Chem. Int. Ed. Engl. 1982, 21, 544–545; b) A. R. Fox, R. J.
Wright, E. Rivard, P. P. Power, Angew. Chem. 2005, 117, 7907–7911;
Angew. Chem. Int. Ed. 2005, 44, 7729–7733; c) M. Donath, E.
Conrad, P. Jerabek, G. Frenking, R. Frçhlich, N. Burford, J. J. Wei-
gand, Angew. Chem. 2012, 124, 3018–3021; Angew. Chem. Int. Ed.
2012, 51, 2964–2967.
[25] B. W. Tattershall, J. Chem. Soc. Dalton Trans. 1988, 2055–2057.
[26] B. W. Tattershall, R. Blachnik, H. P. Baldus, J. Chem. Soc. Dalton
Trans. 1989, 977–984.
[27] a) M. Baudler, Pure Appl. Chem. 1980, 52, 755–769; b) L. R. Smith,
J. L. Mills, J. Am. Chem. Soc. 1976, 98, 3852–3857; c) V. A. Milyu-
kov, A. V. Kataev, E. Hey-Hawkins, O. G. Sinyshin, Russ. Chem.
Bull. 2007, 56, 298–303; d) M. Baudler, A. Floruss, Z. Anorg. Allg.
Chem. 1995, 621, 207–212; e) B. W. Tattershall, N. L. Kendall, Poly-
hedron 1994, 13, 1517–1521; f) M. Baudler, U. M. Krause, Z. Natur-
forsch. B 1979, 34, 1690–1692; g) F. Kraus, N. Korber, Chem. Eur. J.
2005, 11, 5945–5959.
[28] R. Blachnik, A. Hepp, P. Lçnnecke, J. A. Donkin, B. W. Tattershall,
Z. Anorg. Allg. Chem. 1994, 620, 1925–1931.
[29] a) G. J. Penney, G. M. Sheldrick, Acta Crystallogr. B 1970, 26, 2092–
2095; b) G. J. Penney, G. M. Sheldrick, J. Chem. Soc. A 1971, 245–
248.
[30] N. Weferling, Z. Anorg. Allg. Chem. 1987, 548, 55–62.
[31] N. Burford, R. E. v. H. Spence, J. Chem. Soc. Dalton Trans. 1990,
3611–3619.
[32] a) N. Burford, S. Mason, R. E. v. H. Spence, J. M. Whalen, J. F. Ri-
chardson, R. D. Rogers, Organometallics 1992, 11, 2241–2250; b) J.-
H. Park, P. OꢅBrian, A. J. P. White, D. J. Williams, Inorg. Chem.
2001, 40, 3629–3631.
[33] N. Burford, B. W. Royan, R. E. v. H. Spence, R. D. Rogers, J. Chem.
Soc. Dalton Trans. 1990, 2111–2117.
[34] a) J. Omelanczuk, Phosphorus Sulfur Silicon Relat. Elem. 1994, 86,
93–102; b) L. Maier, Z. Anorg. Allg. Chem. 1966, 345, 29–34.
[35] R. Blachnik, U. Wickel, P. Schmidt, Z. Naturforsch. B 1984, 39,
1135–1138.
[36] R. Rollo, G. R. Burns, W. T. Robinson, R. J. H. Clark, H. M. Dawes,
M. B. Hursthouse, Inorg. Chem. 1990, 29, 2889–2894.
[37] a) B. W. Tattershall, N. L. Kendall, Polyhedron 1994, 13, 2629–2637;
b) B. W. Tattershall, R. Blachnik, A. Hepp, J. Chem. Soc. Dalton
Trans. 2000, 2551–2558; c) A. Hepp, Ph.D. Thesis, Osnabrꢀck Uni-
versity, Osnabrꢀck, 1998.
[38] W. Hçnle, H. G. v. Schnering, Z. Anorg. Allg. Chem. 1978, 440, 171–
182.
[39] M. Baudler, Angew. Chem. 1987, 99, 429–451; Angew. Chem. Int.
Ed. Engl. 1987, 26, 419–441.
[15] a) R. K. Harris, E. M. Norval, M. Fild, J. Chem. Soc. Dalton Trans.
1979, 826–831; b) J. J. Weigand, S. D. Riegel, N. Burford, A.
Decken, J. Am. Chem. Soc. 2007, 129, 7969–7976.
[16] a) S. O. Grim, W. McFarlane, E. F. Davidoff, T. J. Marks, J. Phys.
Chem. 1966, 70, 581–584; b) S. O. Grim, W. McFarlane, Can. J.
Chem. 1968, 46, 2071–2074.
Received: December 5, 2012
Revised: April 11, 2013
Published online: && &&, 0000
[17] a) A. Westenkirchner, A. Villinger, K. Karaghiosoff, R. Wustrack,
D. Michalik, A. Schulz, Inorg. Chem. 2011, 50, 2691–2702; b) B.
Chem. Eur. J. 2013, 00, 0 – 0
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
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These are not the final page numbers!

J. J. Weigand et al.
+
R2P5 Cages
M. H. Holthausen, A. Hepp,
J. J. Weigand* ................. &&&& — &&&&
+
Synthesis of Cationic R2P5 Cages and
Subsequent Chalcogenation Reactions
Phosphorus–chalcogen cations: Chal-
type structures are obtained, these
+
cogenation reactions of R2P5 and
being formally derived by stepwise iso-
lobal exchange of chalcogen moieties
in P4Ch3 by [R2P]+ moieties. In addi-
tion, synthetic protocols for the synthe-
3+
Ph6P7 cages with a-S8 or Segrey yield
a series of phosphorus–chalcogen cati-
ons (see scheme). The reactions pro-
ceed by insertion of Ch (Ch=S, Se)
+
sis of a series of R2P5 cages are pre-
À
into P P bonds or exchange of a tetra-
coordinated P moiety. Nortricyclane-
sented.
&
14
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www.chemeurj.org
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
ÝÝ
These are not the final page numbers!