Formation and crystal structures of Lewis acid adducts of Ph 3PCHP(O)Ph2; New neutral and cationic species

Article abstract of DOI:10.1002/zaac.201000092

The carbodiphosphorane C(PPh₃)₂ (1) is easily hydrolyzed from wet air to give the ylide Ph₃PCHP(O)Ph₂ (2), which forms addition compounds with various Lewis acids to give neutral or cationic compounds. According to pairs of electrons at the central carbon atom and the oxygen atom, respectively, addition compounds with coordination modes A (via oxygen), B (via carbon), and C (via carbon and oxygen) were isolated either as by-products from reactions of Lewis acids with 1 (contaminated with some 2) or directly with 2. The crystal structures and the spectroscopic properties of 2 and of the addition compounds [Ph3PCHP(OBF3)Ph2] (5), [Ph₃PCH ₂P(OBF₃)Ph₂][(μ-OH)B₂F ₆] (6), [Ph₃PCH₂P(OBI₃)Ph ₂][BI₄] (7), [Ph₃PCHP(OSnCl₂)Ph ₂] (8), and [Ph₃PCH₂P(O)Ph₂] ₂[Hg₂I₆] (9) are reported.

Full text of DOI:10.1002/zaac.201000092

ARTICLE
DOI: 10.1002/zaac.201000092
Formation and Crystal Structures of Lewis Acid Adducts of
Ph3PCHP(O)Ph2; New Neutral and Cationic Species
Wolfgang Petz,*[a] Florian Öxler,[a] Kathrin Aicher,[a] and Bernhard Neumüller*[a]
Dedicated to Professor Bernd Harbrecht on the Occasion of His 60th Birthday
Keywords: Ylides; Carbodiphosphoranes; Hydrolysis; Lewis acids; NMR spectroscopy
Abstract. The carbodiphosphorane C(PPh3)2 (1) is easily hydrolyzed were isolated either as by-products from reactions of Lewis acids with 1
from wet air to give the ylide Ph3PCHP(O)Ph2 (2), which forms addition (contaminated with some 2) or directly with 2. The crystal structures
compounds with various Lewis acids to give neutral or cationic com- and the spectroscopic properties of 2 and of the addition compounds
pounds. According to pairs of electrons at the central carbon atom and [Ph3PCHP(OBF3)Ph2] (5), [Ph3PCH2P(OBF3)Ph2][(μ-OH)B2F6] (6),
the oxygen atom, respectively, addition compounds with coordination [Ph3PCH2P(OBI3)Ph2][BI4] (7), [Ph3PCHP(OSnCl2)Ph2] (8), and
modes A (via oxygen), B (via carbon), and C (via carbon and oxygen) [Ph3PCH2P(O)Ph2]2[Hg2I6] (9) are reported.
which the P(O)Ph2 group of 2 is replaced by C(O)R and which
exhibits rich coordination chemistry [5].
1. Introduction
The carbodiphosphorane C(PPh3)2 (1) and its hydrolysis
product Ph3PCHP(O)Ph2 (2) were first described in 1961 by
Ramirez et al [1]. Whereas various addition compounds of 1
have been synthesized up to now [2], the chemistry of 2 re-
mained unexplored for many years. An earlier reported plati-
num complex with a side on bounded C(PPh3)2 ligand [3] was
Scheme 1. Coordination modes of 2. The arrows indicate potential
later identified as pure 2 [4]. Compound 2 can be seen as an
donor abilities to Lewis acids.
ylide derived from the ylide CH2PPh3 by replacing one proton
by the P(O)Ph2 group or as a derivative of the phosphane oxide
Reports on the chemistry of 2 are rare. The type A tungsten
OPPh3, in which one Ph group is replaced by the ylidic group
complex [Ph3PCHP{OW(CO)5}Ph2] (3) was described, in
CHPPh3. To the best of our knowledge, further compounds of
which 2 acts as a Lewis base coordinating with the oxygen
the type Ph3PCHP(E)Ph2 with E other than oxygen have not
atom at the electron deficient tungsten carbonyl fragment [6].
been reported so far.
The salt like complex [Ph3PCH2P(OAlBr3)Ph2][AlBr4] (4) of
Thus, the chemistry of 2 should be related to both, CH2PPh3
type C was obtained by us during the preparation of the car-
and OPPh3. In principle, 2 is endowed with two anchor points
bodiphosphorane adduct Br3Al←1 [7]. Both addition com-
for Lewis acids (LA), the free pair of electrons at the ylidic
pounds of 2 were formed as side-products from reactions of 1
carbon atom between the phosphorus atoms and a pair of elec-
trons at the oxygen atom. Therefore, 1:1 adducts with sp2 (A)
and sp3 carbon atoms (B) or 1:2 adducts with a sp3 carbon
atom (C) are expected as depicted in Scheme 1. Coordination
modes A and B represent hard and soft coordination sites, re-
spectively, of the ylide. In the coordination mode C, the ylide
2 can also act as a chelating ligand. In principle, 2 is related
to the carbonyl-stabilized ylides of the type Ph3PCHC(O)R in
with the appropriate Lewis acid. No type B compound has
been reported up to now. During our studies with 1 as complex
ligand, we frequently isolated further derivatives of 2 in small
amounts. This prompted us to explore the chemistry of 2 more
intensively in order to find out what pair of electrons is pre-
ferred upon using different kinds of Lewis acids. Herein we
report on the preparation and the crystal structure of 2 and on
the formation of further adducts of type A to C, which could
be identified and confirmed by X-ray diffraction analyses.
* Prof. Dr. W. Petz
E-Mail: petz@staff.uni-marburg.de
* Prof. Dr. B. Neumüller
Fax: +49-6421-2825653
2. Results and Discussion
Whereas the double ylide C(PPh3)2 (1) in the solid state is
not very sensitive, solutions readily react with wet air to give
2; and even if reactions with 1 were carried out in dried sol-
E-Mail: neumuell@chemie.uni-marburg.de
[a] Fachbereich Chemie
Philipps-Universität Marburg
Hans-Meerwein-Strasse
35032 Marburg, Germany
Z. Anorg. Allg. Chem. 2010, 636, 1751–1759
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W. Petz, F. Öxler, K. Aicher, B. Neumüller
ARTICLE
vents under argon protection, small amounts of 2 are always 991 cm–1. In this contribution we concentrate on the discussion
present as traced by 31P NMR spectroscopy. Thus, 2 was ob- of addition products of 2 either obtained as side-products by
tained in quantitative yields under release of benzene accord- reactions of 1 with Lewis acids or upon reaction of 2 with
ing to Equation (1), if a solution of 1 in toluene was stirred in Lewis acids, and the results are sketched in Scheme 2.
contact with wet air; the resulting 2 is soluble in toluene and
Thus, the type A compound [Ph3PCHP(OBF3)Ph2] (5)
can be precipitated by addition of n-pentane. However, direct formed when 1, containing small amounts of 2 (as shown by
addition of water to 1 is not successful; only decomposition 31P NMR spectroscopy), was allowed to react with gaseous
products were obtained.
BF3 in toluene; colorless crystals of 5 separated in low yield
from the toluene solution, and the desired adduct F3B←1 pre-
cipitated without forming crystals suitable for an X-ray analy-
sis. Upon coordination of BF3 at the oxygen atom of 2, both
doublets experienced a high field shift in the 31P NMR spec-
trum of 5. Attempts to prepare 5 directly from 2 and
F3B←OEt2 or BF3 in toluene gave a precipitate, which upon
recrystallization from CH2Cl2/n-pentane produced the type C
compound [Ph3PCH2P(OBF3)Ph2][(μ-OH)B2F6] (6) in good
yields; source for the additional proton are the solvent or impu-
rities in [F3B(OEt2)].
The 31P NMR spectrum of 2 exhibits two characteristic dou-
blets with coupling constants 2J(P,P) = 19 Hz indicating chem-
ically different phosphorus atoms; the low field signal can be
attributed to the PO group. A strong solvent dependency of the
shifts is observed, and the shift difference Δ between the dou-
blets range between 4.4 and 7.4 ppm, depending on the nature
of the solvent. In the IR spectrum the PO stretching vibration
cannot be assigned with certainty, because in the region be-
tween 1250 and 1100 cm–1 several strong bands were re-
corded. However, a very strong band at 1171 cm–1 seems to
be reliable; the P–O vibration of Ph3PO appears at about
1190 cm–1 [8, 9].
The majority of compounds based on 2 were obtained in
small amounts as side-products during our efforts to prepare
addition compounds LA←1 between the double ylide and vari-
ous Lewis acids LA, such as compounds of group 13 elements,
and attempts to obtain crystals from the crude reaction pro-
ducts. In general, the reactions with 1 were carried out in tolu-
ene, because the use of halogenated hydrocarbons or even
THF, DME, or DMSO led to deprotonation of the solvents
with formation of the cations (HC{PPh3}2)+ or
(H2C{PPh3}2)2+. Unfortunately, the resulting adducts LA←1
were insoluble in toluene and other nonpolar solvents, prevent-
ing sufficient characterization by NMR and X-ray analyses;
however, few crystals were sporadically obtained from freshly
prepared filtered toluene solutions. In most cases the precipi-
tates from toluene are soluble in DMSO or halogenated sol-
vents, but the 31P NMR spectra show only the signal of the
cation (HC{PPh3}2)+, indicating reaction with the solvent with
proton abstraction. This is confirmed by IR spectroscopic ex-
periments, in which the spectra changed after the precipitates
had got contact to polar solvents showing the characteristic
medium intense bands of the cation at 1032, 1013, and
In the 31P NMR spectrum of 6 a doublet at 17.53 ppm
[2J(P,P) = 17.80 Hz] and a multiplet at 45.63 ppm were meas-
ured, which were assigned to PPh3 and P(OBF3)Ph2 phospho-
rus atoms, respectively. Similarly, from the reaction of 1 with
BI3 in toluene the type C complex [Ph3PCH2P(OBI3)Ph2][BI4]
(7) was obtained as the only crystalline product, and the de-
sired adduct I3B←1 could not be identified; instead, only the
salt (H2C{PPh3}2)[I3]I [10] was isolated upon attempts to re-
crystallize the crude material from acetonitrile. The HI needed
for protonation probably formed upon borylation and deproto-
nation of the appropriate solvents. The 31P NMR spectrum of
7 in DCM exhibits a doublet at 16.20 ppm [2J(P,P) =
20.35 Hz] and a multiplet at 54.55 Hz, according to PPh3 and
P(OBI3)Ph2 phosphorus atoms, respectively. Relative to the
starting compound 2, the low field signal has become more
deshielded, whereas the high field signal has experienced a
high field shift in going to the addition compounds 6 and 7.
As yet, only type C compounds were detected, in which the
Lewis acid at the carbon atom is H+, thus producing salt like
compounds. Solvent reactions with proton abstraction of addi-
tion compounds with 1 and other Lewis acids were reported
recently [11].
If 2 was allowed to react with anhydrous SnCl2 in DCM the
neutral type A addition complex [Ph3PCHP(OSnCl2)Ph2] (8)
could be prepared in high yields and characterized by X-ray
analysis. The 31P NMR spectrum of a freshly prepared sample
in DCM exhibits two doublets at 38.74 and 18.18 ppm (set A),
which disappeared within some hours in favor of doublets at
22.96 and 21.33 ppm (set B). The set B persisted and was
observed as the only signals after isolation of the product indi-
cating the formation of only one type of compounds. The ini-
tial signals of set A apparently belong to an intermediate which
could not be identified so far. The IR spectrum of 8 exhibits a
new strong band at 1018 cm–1 not found in 2, which can be
assigned to the P–OSn vibration.
A quite different reaction pathway was found upon reacting
2 with HgI2 in THF. The clear solution showed a set of two
doublets at 21.58 and 20.79 ppm [2J(P,P) = 14.35 Hz] along
with a set of two broad signals at 27.8 and 26.0 ppm in about
Scheme 2. Compounds of the coordination modes A (5, 8), B (9), and
C (6, 7).
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Lewis Acid Adducts of Ph3PCHP(O)Ph2; New Neutral and Cationic Species
1:1 ratio. Attempts to grow crystals gave colorless crystals related H[HOB2F6] adduct 6 was obtained from the reaction of
suitable for X-ray analysis and a pale yellow micro crystalline 2 with [F3B(OEt2)], and crystals of 7·C7H8 formed from a tolu-
material, which was unsuitable for X-ray analysis. The color- ene solution; the adducts are of the type C. Additionally, we
less crystals turned out to be the salt like compound have obtained crystals of the type A compound 8 and the type
[Ph3PCH2P(O)Ph2]2[Hg2I6] (9). The salt can be considered as B salt 9. The structures of 2, 5, 6, 7·C7H8, 8, and 9 are shown
the first compound of the type B containing a “free” PO group in Figure 1, Figure 2, Figure 3, Figure 4, Figure 5, and Fig-
as in 2 but a protonated ylidic carbon atom, thus being its ure 6; crystallographic data are collected in Table 1; bond
conjugated acid. An alternative pathway, the addition of HgCl2 lengths and angles are summarized in Table 2, Table 3, Ta-
at the carbon atom, as expected, could not be found. However, ble 4, Table 5, Table 6, and Table 7.
the formation of such kind of adduct as intermediate can nei-
ther be excluded nor be established; no other type of crystals
was found. It could be responsible for the unusual deprotona-
tion of the solvent. The IR spectrum of 9 exhibits a strong
band at 1184 cm–1, which probably can be assigned to the P–
O vibration.
3. Crystal Structures
For comparison and for documentation of the changes in the
parameters upon adduct formation we have also studied the
Figure 3. Molecular structure of [Ph3PCH2P(OBF3)Ph2][(μ-OH)B2F6]
crystal structure of 2; colorless crystals separated from a tolu-
(6). The two cations and two anions are connected through hydrogen
ene solution after layering with n-pentane. Crystals of 5 (ad-
bonds to a centrosymmetrical dimer. The ellipsoids are drawn at a
duct of the type A) were obtained as described above. The 40 % probability level; the phenyl groups are represented as thin lines
omitting the hydrogen atoms for clarity.
Figure 1. Molecular structure of Ph3PCHP(O)Ph2 (2) with thermal el-
lipsoids at 40 % probability, the hydrogen atoms are omitted for clarity.
Figure 4. Molecular structure of [Ph3PCH2P(OBI3)Ph2][BI4] (7). The
ellipsoids are drawn at a 40 % probability level; the phenyl groups are
represented as thin lines omitting the hydrogen atoms for clarity.
3.1 Crystal Structure of Ph3PCHP(O)Ph2 (2)
The unit cell of 2 contains two independent molecules, the
parameters of which, however, differ only slightly, and only
one molecule is depicted in Figure 1. As expected, the C–P
distances to the ylidic carbon atom are different. The C–PPh3
bond length amounts to 168.8(3) pm, whereas the C–P(O)Ph2
bond is longer with 171.7(3) pm. The short P–C bond is lo-
Figure 2. Molecular structure of [Ph3PCHP(OBF3)Ph2] (5) with thermal
ellipsoids at 40 % probability, the hydrogen atoms are omitted for clarity. cated between that of C(PPh3)2 (163.5) [12] and that of the
Z. Anorg. Allg. Chem. 2010, 1751–1759
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W. Petz, F. Öxler, K. Aicher, B. Neumüller
ARTICLE
134.5(2)° in the phosphane oxide adduct. In going from 2 to 5
the P–C–P angle opens to 131.7(3)°. The influence of the Le-
wis acid induces also changes in the P–C bonding situation.
With the C–P(O)Ph2 bond length of 168.1(4) pm and the C–
PPh3 bond length of 171.6(4) pm a reverse situation to 2 oc-
curs with a shifting of the partial double bond to the other side,
more directed to the PO group. The same effects on the P–O
bond are observed in 3, where a W(CO)5 group is bonded to
the oxygen atom instead of BF3, however, the related P–C
bond lengths are those of 2, but according to large standard
deviations in the tungsten complex, these values should be dis-
cussed with caution [6] (Table 3).
Figure 5. Molecular structure of [Ph3PCHP(OSnCl2)Ph2] (8). The el-
lipsoids are drawn at a 40 % probability level; the phenyl rings are
refined as rigid groups and are represented as thin lines omitting the
hydrogen atoms for clarity.
3.3 Crystal Structure of [Ph3PCH2P(OBF3)Ph2][(μ-OH)B2F6]
(6)
In the solid state the compound forms a centrosymmetric
dimer and the two units are linked by H···F bridges. A further
H···F bridge exists between H(2) and F(4) of the anion with a
C(1)–H(2)···F(4) distance of 326.1(4) pm. The complex can be
seen as a protonation product upon addition of the hypothetical
acid H[HOB2F6] at the Lewis base 5, and the crystal structure
of the dimer unit is shown in Figure 3. The unusual and as yet
unique anion [HOB2F6]– was described earlier with a carben-
oid counter cation [20]. The bonding situation around the P–
C–P group changed dramatically upon conversion of the cen-
tral sp2 carbon atom into a sp3 carbon atom on protonation to
give a type C salt. According to a missing back donation, the
P–C bond lengths increased to 181.3(3) and 179.9(3) pm and
correspond to normal single bonds. The P–O bond length
amounts to 152.9(2) pm and is in between that of 2 and 5.
Relative to 5 the B–O bond length increased by about 5 pm to
154.2(4) pm, whereas the P–O–B angle remained unchanged.
The P–C–P angle moved into the direction of that of an sp3
carbon atom but with 119.9(2)° remains still large, probably
according to steric repulsion between the phenyl groups. The
other angles in the distorted tetrahedral environment of the car-
bon atom range between 100° (H–C–H) and 111° (P–C–H)
(Table 4).
Figure 6. Molecular structure of [Ph3PCH2P(O)Ph2]2[Hg2I6] (9). The
ellipsoids are drawn at a 40 % probability level; the phenyl groups are
represented as thin lines omitting the hydrogen atoms for clarity.
cation (HC{PPh3}2)+ (mean value of 169.9 pm from about 10
compounds) [7], indicating a decreasing P–C double bond
character down the row C(PPh3)2
> 2 (C–PPh3) >
(HC{PPh3}2)+ > 2 [C–P(O)Ph2] arising from variable back-
bonding of the occupied p orbital at the ylidic carbon atom
into P–CPh σ* orbitals [13]. The P–O distance amounts to
148.9(2) pm and is close to that in OPPh3 [148.3(2) pm] [14].
With 127.5(2)° the P–C–P angle is not far away from that of
an sp2 carbon atom and more acute than the related angle in
the cation (HC{PPh3}2)+, probably an effect of the missing
phenyl group in 2, which is responsible for steric repulsion in
the cation and related adducts of C(PPh3)2 (Table 2).
3.4 Crystal Structure of [Ph3PCH2P(OBI3)Ph2][BI4] (7·C7H8)
The compound crystallizes with one disordered toluene mol-
ecule without contacts to the salt-like compound and the mo-
lecular structure of 7 is shown in Figure 4. The replacement
of the BF3 group by the BI3 group has no dramatic effect on
3.2 Crystal Structure of [Ph3PCHP(OBF3)Ph2] (5)
The molecular structure of 5 is shown in Figure 2. The coor- the parameters of the cation; only the B–O bond is about 5 pm
dination of a BF3 molecule at the oxygen atom of 2 leads to shorter and close to that of 5, which is due to the stronger
an elongation of the P–O bond length by about 8 pm to Lewis acidity of BI3 relative to BF3. The P–C bond lengths
157.3(3) pm indicating a dramatic loss of π character; this is show the same trend as reported for the cation of 6. Weak
less operative in [(Ph3PO)BF3], where the elongation amounts hydrogen bridges between H(2) of the cation and I(4) of the
to 4 pm only [18]. A similar elongation is found in the com- anion exist [C(1)–H(2)···I(4) = 399(1) pm], which leads to a
pounds [(Ph3PO)AlX3] (X = Cl, Br) [19]. As counterweight, long B(2)–I(4) distance of 228(1) pm relative to the three oth-
the B–O bond length in 5 of 148.8(6) pm is appreciably shorter ers with a mean B–I distance of 223 pm; all B–I distances are
than that in [(Ph3PO)BF3] [151.6(6) pm]. The P–O–B angles about 10 pm longer than those in the planar BI3 molecule [21]
in both compounds are close together with 133.4(3)° in 5 and (Table 5).
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Lewis Acid Adducts of Ph3PCHP(O)Ph2; New Neutral and Cationic Species
Table 1. Crystal data and structure refinement details for the compounds 2, 5, 6, 7·C7H8, 8, and 9.
2
5
6
7·C7H8
8
9
Formula
Mw /g·mol–1
a /pm
b /pm
c /pm
α /°
C31H26OP2
476.49
C31H26BF3OP2
544.30
C31H28B3F9O2P2
697.92
C38H35B2I7OP2
1479.56
1108.0(1)
1476.5(2)
1444.4(2)
90
C31H26Cl2OP2Sn
666.05
C62H45Hg2I6O2P4
2117.51
1194.0(1)
1094.2(1)
2552.1(2)
90
1004.8(1)
1476.5(2)
1832.9(3)
107.93(1)
98.55(1)
1151.7(2)
1392.1(2)
1653.8(3)
90
97.63(1)
90
988.6(2)
1496.9(2)
2061.0(3)
1825.0(2)
90
90
90
1059.4(2)
1722.5(2)
79.46(2)
78.46(2)
65.68(2)
β /°
106.50(1)
90
100.36(1)
90
γ /°
101.09(1)
Crystal size /mm 0.32 × 0.14 × 0.08 0.17 × 0.17 × 0.04 0.14 × 0.06 × 0.05 0.24 × 0.09 × 0.05 0.13 × 0.12 × 0.04 0.18 × 0.11 × 0.09
Volume /
pm3 × 106
Z
2475.2(6)
2628.0(8)
1600.5(5)
2265.7(5)
5630(1)
3279.9(5)
4
4
2
2
8
2
dcalc /g·cm–3
1.279
1.376
1.448
triclinic
2.169
1.571
2.144
Crystal system triclinic
monoclinic
P21/n (No. 14)
IPDS II (Stoe)
Mo-Kα
100
monoclinic
P21 (No. 4)
IPDS II (Stoe)
Mo-Kα
173
orthorhombic
Pbca (No. 61)
IPDS II (Stoe)
Mo-Kα
monoclinic
P21/n (No. 14)
IPDS I (Stoe)
Mo-Kα
¯
¯
Space group
Diffractometer IPDS I (Stoe)
Radiation Mo-Kα
P1 (No. 2)
P1 (No. 2)
IPDS I (Stoe)
Mo-Kα
193
Temperature /K 193
100
193
μ /cm–1
2.1
52.34
2.1
52.10
2.2
55.22
48.9
52.12
12.35
76.36
2θmax/°
52.10
52.42
Index range
–12 ≤ h ≤ 12, –17 ≤ –14 ≤ h ≤ 14, –17 ≤ –12 ≤ h ≤ 12, –13 ≤ –13 ≤ h ≤ 13, –17 ≤ –15 ≤ h ≤ 18, –25 ≤ –14 ≤ h ≤ 12, –13 ≤
k ≤ 17, –22 ≤ l ≤ 22 k ≤ 17, –20 ≤ l ≤ 20 k ≤ 13, –19 ≤ l ≤ 19 k ≤ 18, –17 ≤ l ≤ 17 k ≤ 25, –21 ≤ l ≤ 22 k ≤ 13, –31 ≤ l ≤ 31
Number of rflns 23300
collected
36597
15732
16018
34625
15021
Number of indep. 9087 (0.0739)
5138 (0.1984)
2389
5835 (0.0863)
2360
8017 (0.065)
5058
5513 (0.5512)
1579
6169 (0.0578)
3410
rflns (Rint
)
Number of ob- 4091
served rflns with
Fo > 4σ(Fo)
Parameters
622
348
numerical
437
numerical
438
numerical
205
numerical
350
numerical
Absorption correc-numerical
tion
Structure solution direct methods
direct methods SIR- direct methods SIR- direct methods
direct methods SIR- direct methods
SHELXS-97 [15] 92 [16] SHELXS-97 [15]
SHELXS-97 [15] 92 [16]
92 [16]
Refinement
against F2
Flack-Parameter
SHELXL-97 [17] SHELXL-97 [17] SHELXL-97 [17] SHELXL-97 [17] SHELXS-97 [15] SHELXL-97 [17]
–
–
–
–0.05(3)
–
–
hydrogen atoms calculated positions calculated positions calculated positions calculated positions calculated positions calculated positions
with common dis- with common dis- with common dis- with common dis- with common dis- with common dis-
placement parame- placement parameter placement parame- placement parameter placement parameter placement parame-
ter, H(1) was refined
ter, H(1), H(2), H(3)
were refined free
0.0364
ter, H(1), H(2) were
refined free
0.0367
free
R1
0.0361
0.0651
max. electron den-0.25
sity °left /
0.0608
0.1299
0.68
0.0411
0.0611
0.72
0.0872
0.2199
1.007
wR2 (all data)
0.0595
0.0834
0.13
1.413
e·pm–3 × 10–6
3.5 Crystal Structure of [Ph3PCHP(OSnCl2)Ph2] (8)
pounds with the simple Cl2SnO core have not been reported
so far. The two Sn–Cl bond lengths in 8 are not equal and
differ by about 3 pm (Table 6). For the tin atom a typical tetra-
hedral environment is achieved, where one coordination site is
occupied by a free pair of electrons. Together with the (CO)5W
adduct 3, the compounds 5 and 8 represent the only type A
compounds existing as yet.
Similar to the BF3 adduct 5, the tin derivative 8 can be con-
sidered as type A compound; the molecular structure is de-
picted in Figure 5. Thus, the relevant bond lengths P(1)–O,
P(1)–C(1), and P(2)–C(1), which are influenced by the coordi-
nation of the tin atom, show the same trend in shifting of the
partial double bond more directed to the PO bond relative to
the starting compound 2. The Sn–O bond length amounts to
212(1) pm, which is shorter than that in the comparable com-
plex [Cl2Sn(OC(O)C{PPh3}2)] [214.3(4) pm] described by us
recently [22]. Similar Sn–O bond lengths in SnCl2 addition
3.6 Crystal Structure of [Ph3PCH2P(O)Ph2]2[Hg2I6] (9)
The protonation of 2 produces the cation of 9, its conjugated
compounds vary between 252 pm in the dioxane adduct [23] acid and a change in rehybridization of the carbon atom from
and 230 pm in the dihydrate [24]; the structures of other com- planar sp2 to tetrahedral sp3 occurred with interruption of the
Z. Anorg. Allg. Chem. 2010, 1751–1759
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1755

W. Petz, F. Öxler, K. Aicher, B. Neumüller
ARTICLE
Table 2. Selected bond lengths /pm and angles /° in one of the two Table 4. Selected bond lengths /pm and angles /° in 6.
independent molecules of 2.
P(1)–O(1)
P(1)–C(2)
P(2)–C(1)
P(2)–C(20)
F(1)–B(1)
F(3)–B(1)
C(1)–H(1)
F(4)–B(2)
F(6)–B(2)
F(8)–B(3)
O(2)–B(2)
O(2)–H(3)
152.9(2)
178.5(3)
181.3(3)
177.7(3)
138.8(4)
133.6(4)
87(3)
P(1)–C(1)
P(1)–C(8)
P(2)–C(14)
P(2)–C(26)
F(2)–B(1)
O(1)–B(1)
C(1)–H(2)
F(5)–B(2)
F(7)–B(3)
F(9)–B(3)
O(2)–B(3)
179.9(3)
177.3(3)
178.6(3)
178.2(3)
134.2(4)
154.2(4)
97(3)
137.8(4)
141.6(4)
137.1(4)
147.6(4)
P(1)–O(1)
P(1)–C(2)
P(2)–C(1)
P(2)–C(20)
C(1)–H(1)
148.9(2)
181.2(3)
168.8(3)
180.7(2)
0.85(3)
P(1)–C(1)
P(1)–C(8)
P(2)–C(14)
P(2)–C(26)
171.7(3)
182.2(3)
182.0(3)
181.9(3)
O(1)–P(1)–C(1)
O(1)–P(1)–C(8)
C(1)–P(1)–C(8)
C(1)–P(2)–C(14)
C(1)–P(2)–C(26)
C(14)–P(2)–C(26)
P(1)–C(1)–P(2)
P(2)–C(1)–H(1)
114.1(1)
112.1(1)
107.8(1)
116.3(1)
116.9(2)
103.6(1)
127.5(2)
116(2)
O(1)–P(1)–C(2)
C(1)–P(1)–C(2)
C(2)–P(1)–C(8)
C(1)–P(2)–C(20)
C(14)–P(2)–C(20)
C(20)–P(2)–C(26)
P(1)–C(1)–H(1)
111.2(1)
109.4(2)
101.4(1)
105.3(2)
106.9(1)
107.2(1)
116(2)
137.8(4)
135.3(4)
136.5(4)
151.9(4)
86(4)
O(1)–P(1)–C(1)
O(1)–P(1)–C(8)
C(1)–P(1)–C(8)
106.7(2)
111.6(1)
106.5(2)
O(1)–P(1)–C(2)
C(1)–P(1)–C(2)
C(1)–P(2)–C(26)
C(1)–P(2)–C(20)
P(1)–C(1)–P(2)
F(1)–B(1)–F(3)
F(2)–B(1)–F(3)
F(3)–B(1)–O(1)
P(1)–C(1)–H(2)
P(2)–C(1)–H(2)
B(2)–O(1)–B(3)
F(4)–B(2)–F(6)
F(5)–B(2)–F(6)
F(6)–B(2)–O(2)
F(7)–B(3)–F(9)
F(8)–B(3)–F(9)
F(9)–B(3)–O(2)
B(3)–O(2)–H(3)
111.2(1)
108.5(2)
106.2(2)
113.6(2)
119.9(2)
110.8(4)
114.9(4)
105.7(3)
107(2)
C(1)–P(2)–C(14) 109.6(2)
P(1)–O(1)–B(1)
F(1)–B(1)–F(2)
F(1)–B(1)–O(1)
F(2)–B(1)–O(1)
P(1)–C(1)–H(1)
P(2)–C(1)–H(1)
H(1)–C(1)–H(2)
F(4)–B(2)–F(5)
F(4)–B(2)–O(2)
F(5)–B(2)–O(2)
F(7)–B(3)–F(8)
F(7)–B(3)–O(2)
F(8)–B(3)–O(2)
B(2)–O(2)–H(3)
133.4(2)
110.4(3)
106.9(3)
107.4(4)
110(2)
107(2)
100(3)
111.7(3)
107.3(3)
105.3(3)
109.9(3)
108.8(3)
109.5(3)
102(2)
Table 3. Selected bond lengths /pm and angles /° in 5.
P(1)–O(1)
P(1)–C(2)
P(2)–C(1)
P(2)–C(20)
F(1)–B(1)
F(3)–B(1)
C(1)–H(1)
157.3(3)
179.7(4)
171.6(4)
180.7(4)
137.6(6)
135.9(5)
93(4)
P(1)–C(1)
P(1)–C(8)
P(2)–C(14)
P(2)–C(26)
F(2)–B(1)
O(1)–B(1)
168.1(4)
179.7(4)
180.3(4)
179.6(4)
140.2(5)
148.8(6)
111(2)
127.6(3)
110.8(3)
111.4(4)
110.1(3)
108.0(3)
112.2(4)
108.2(3)
124(2)
O(1)–P(1)–C(1)
O(1)–P(1)–C(8)
C(1)–P(1)–C(8)
C(1)–P(2)–C(14)
C(1)–P(2)–C(26)
C(14)–P(2)–C(26)
P(1)–O(1)–B(1)
F(1)–B(1)–F(2)
F(1)–B(1)–O(1)
F(2)–B(1)–O(1)
P(1)–C(1)–H(1)
118.9(2)
101.4(2)
114.4(2)
113.5(2)
112.0(2)
107.2(2)
133.4(3)
109.7(4)
110.0(4)
106.9(3)
114(2)
O(1)–P(1)–C(2)
C(1)–P(1)–C(2)
C(2)–P(1)–C(8)
C(1)–P(2)–C(20)
C(14)–P(2)–C(20)
C(20)–P(2)–C(26)
P(1)–C(1)–P(2)
F(1)–B(1)–F(3)
F(2)–B(1)–F(3)
F(3)–B(1)–O(1)
P(2)–C(1)–H(1)
108.9(2)
107.3(2)
105.1(2)
110.7(2)
104.8(2)
108.2(2)
131.7(3)
111.1(4)
110.2(4)
108.8(4)
112(2)
Table 5. Selected bond lengths /pm and angles /° in 7·C7H8.
I(1)–B(1)
I(3)–B(1)
P(1)–C(2)
P(1)–C(14)
P(2)–C(1)
P(2)–C(26)
C(1)–H(1)
I(4)–B(2)
I(6)–B(2)
221(1)
229(1)
177.0(9)
176(1)
180.4(8)
178(1)
99
I(2)–B(1)
P(1)–C(1)
P(1)–C(8)
P(2)–O(1)
P(2)–C(20)
O(1)–B(1)
C(1)–H(2)
I(5)–B(2)
I(7)–B(2)
222(1)
180(1)
179(1)
154.5(1)
175(1)
148(1)
99
π conjugation in the P–C–P–O spine. The molecular structure
is shown in Figure 6. Upon protonation, both P–C bond
lengths have increased by about 10 pm with respect to com-
228(1)
224(2)
222(2)
222(1)
pound 2 being now in the range of a normal P–C single bond; C(1)–P(1)–C(2)
107.1(5)
C(1)–P(1)–C(8)
O(1)–P(2)–C(1)
O(1)–P(2)–C(26)
C(1)–P(2)–C(26)
P(1)–C(1)–P(2)
I(1)–B(1)–I(3)
I(2)–B(1)–O(1)
P(1)–C(1)–H(1)
P(2)–C(1)–H(1)
H(1)–C(1)–H(2)
110.9(5)
104.7(4)
111.0(5)
108.0(4)
120.9(6)
109.9(5)
112.9(7)
107
C(1)–P(1)–C(14) 110.3(5)
O(1)–P(2)–C(20) 116.3(4)
C(1)–P(2)–C(20) 106.8(5)
P(2)–O(1)–B(1)
I(1)–B(1)–I(2)
I(1)–B(1)–O(1)
I(3)–B(1)–O(1)
P(1)–C(1)–H(2)
P(2)–C(1)–H(2)
however, the prevailing C–P(O) bond lengths in 2 and 9 are
about 2 to 3 pm longer. The P–O bond length remains nearly
unchanged (Table 7). The addition of a further Lewis acid at
the oxygen atom as in 6 or 7 leads to an increase of the P–O
bond by about 5 pm. In the crystals of 9 ion triples are present,
held together by H···I bridges [C(1)···I(2) = 388.6(8) pm],
which are stacked along H···H–O bridges as shown in Fig-
ure 7. The dianion is located around an inversion center caus-
ing the four-membered Hg–I–Hg–I ring to be completely pla-
nar, and both mercury atoms are in a distorted tetrahedral
environment.
139.0(7)
109.6(4)
107.3(7)
108.1(6)
107
107
106
107
not as a result of specific syntheses. Although 2 was only
present in trace amounts in the starting material the adducts
preferentially crystallized. It turned out that these are more sol-
uble, less sensitive to polar solvents, and show better crystalli-
4. Conclusion
The majority of the compounds presented herein are side- zation properties than those with 1. In part, this was also the
products, which were obtained with low yields during various case during the reaction of AlBr3 with 1 in toluene, where a
runs for preparing addition compounds of the type LA←1 and couple of colorless crystals of the adduct Br3Al←1 grew from
1756
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© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 1751–1759

Lewis Acid Adducts of Ph3PCHP(O)Ph2; New Neutral and Cationic Species
Table 6. Selected bond lengths /pm and angles /° in 8.
no crystals of the appropriate addition compounds have been
obtained from the saturated solutions as yet and attempts to
get crystals have failed according to the properties mentioned
above.
P(1)–O(1)
P(1)–C(2)
P(2)–C(1)
P(2)–C(20)
O(1)–Sn(1)
Cl(2)–Sn(1)
156(1)
182.0(3)
172(2)
183
212(1)
247.0(5)
P(1)–C(1)
P(1)–C(8)
P(2)–C(14)
P(2)–C(26)
Cl(1)–Sn(1)
C(1)–H(11)
168(2)
183
181
180
250.0(5)
95
Herein we could show that the neutral compound
Ph3PCHP(O)Ph2 (2) has a free pair of electrons at the carbon
atom and can be protonated; the results of attempted alkylation
will be reported elsewhere. Other Lewis acids such as group
13 or group 14 electron deficient compounds prefer the PO
oxygen atom. Thus, adducts of the type A, B, and C of
Scheme 1 could be realized with Lewis acids at the oxygen
atom, the carbon atom, and at both atoms, respectively. In ad-
dition to the results reported, compound 2 is assumed to act as
a chelating ligand with formation of a four-membered MCPO
ring; however, no such compound could be isolated so far.
Those compounds would have a constrained arrangement and
may act as catalysts for olefin polymerization [25].
O(1)–Sn(1)–Cl(2) 90.9(3)
Cl(2)–Sn(1)–Cl(1) 92.5(2)
P(1)–C(1)–H(11) 115.9
P(1)–O(1)–Sn(1) 138.1(6)
O(1)–Sn(1)–Cl(1)
P(1)–C(1)–P(2)
P(2)–C(1)–H(11)
O(1)–P(1)–C(1)
C(1)–P(1)–C(2)
C(1)–P(1)–C(8)
C(1)–P(2)–C(14)
C(26)–P(2)–C(14)
C(26)–P(2)–C(20)
88.3(3)
128(1)
115.9
119.2(7)
108.1(5)
111.1(5)
115.5(5)
105.5
O(1)–P(1)–C(2)
O(1)–P(1)–C(8)
C(2)–P(1)–C(8)
105.6(4)
105.4(4)
106.7
C(1)–P(2)–C(26) 108.8(5)
C(1)–P(2)–C(20) 112.0(6)
C(14)–P(2)–C(20) 106.0
108.6
Table 7. Selected bond lengths /pm and angles /° in 9.
Hg(1)–I(3)
Hg(1)–I(1)A
P(1)–O(1)
P(1)–C(2)
P(2)–C(1)
P(2)–C(20)
C(1)–H(1)
267.01(8)
280.51(7)
147.9(6)
179.2(8)
179.7(8)
179.1(9)
101(8)
Hg(1)–I(2)
Hg(1)–I(1)
P(1)–C(1)
P(1)–C(8)
P(2)–C(14)
P(2)–C(26)
C(1)–H(2)
270.35(6)
300.77(8)
182.2(8)
180.6(7)
178.5(7)
179.5(8)
93(9)
In addition, the proton at the carbon atom of 2 may also be
replaced with strong Lewis bases to produce a double ylide-
like anion [Equation (2) left side] such as in complexes with
the dianion [Ph2(E)P–C–P(E)Ph2]2– (E = NR, S) [26], but as
yet, the acidity of this proton and the assumed amphoteric
character of 2 is still unexplored. Further studies on the chem-
istry of 2 are currently in progress.
I(3)–Hg(1)–I(2)
120.81(2)
I(3)–Hg(1)–I(1)A
I(3)–Hg(1)–I(1)
I(1)A–Hg(1)–I(1)
P(1)–C(1)–P(2)
P(1)–C(1)–H(1)
P(1)–C(1)–H(2)
O(1)–P(1)–C(2)
C(2)–P(1)–C(8)
C(2)–P(1)–C(1)
C(14)–P(2)–C(1)
C(26)–P(2)–C(1)
118.50(3)
107.94(2)
94.52(2)
118.2(4)
115(5)
I(2)–Hg(1)–I(1)A 108.32(2)
I(2)–Hg(1)–I(1)
102.01(2)
Hg(1)A–I(1)–Hg(1) 85.48(2)
P(2)–C(1)–H(1)
P(2)–C(1)–H(2)
H(1)–C(1)–H(2)
O(1)–P(1)–C(8)
O(1)–P(1)–C(1)
C(8)–P(1)–C(1)
102(6)
116(6)
105(6)
5. Experimental Section
101(7)
112.3(3)
109.6(4)
102.3(3)
110.1(4)
112.0(4)
113.0(3)
112.5(4)
106.4(4)
All operations were carried out in an argon atmosphere in dried and
degassed solvents using Schlenk techniques. The solvents were thor-
oughly dried and freshly distilled prior to use. The IR spectra were run
with a Nicolet 510 spectrometer in Nujol mull. For the 31P NMR spec-
tra we used the instrument Bruker AC 200. Elemental analyses were
performed by the analytical service of the Fachbereich Chemie at the
Philipps Universität Marburg, Germany. The carbodiphosphorane
C(PPh3)2 (1) was prepared according to a modified literature procedure
[27]. [BF3(OEt2)] was commercially obtained and used without further
purification. BI3 was obtained according to the procedure described in
[28].
C(20)–P(2)–C(1) 108.3(4)
Ph3PCHP(O)Ph2 (2): A suspension of 1 (2.3 g, 4.3 mmol) in toluene
(40 mL) was stirred in a 100 mL flask. The neck was closed by glass
wool to allow a slow admission of moist air. After about 2 h, the
yellow color of 1 had disappeared and a colorless suspension was ob-
tained. The solution was filtered from small amounts of an insoluble
material. From the clear solution compound 1 precipitated as colorless
crystals by layering with n-pentane. Yield 1.9 g (4.0 mmol, 95 %). 31P
NMR (CH2Cl2, 200 MHz, 298 K): δ = 25.8 (d, PO), 19.2 [d, PPh3),
2J(P,P) = 19.7 Hz, Δ = 6.66 ppm]; similar values were obtained in
CHCl3 [25.3, 18.6 ppm, 2J(P,P) = 19.1 Hz, Δ = 7.39 ppm], THF [26.7,
21.5 ppm, 2J(P,P) = 19.1 Hz, Δ = 4.15 ppm], DMSO [25.2, 19.0 ppm,
2J(P,P) = 20.4 Hz, Δ = 6.15 ppm], and toluene [25.3, 20.6 ppm,
2J(P,P) = 19.7 Hz, Δ = 4.65 ppm] solutions. Remarkable is the shift
difference Δ between the two doublets in the respective solvents. IR
Figure 7. Crystal packing diagram of compound 9 viewed along the b
axis; hydrogen contacts are indicated by dashed lines.
a saturated toluene solution overnight and among them were
very few yellow crystals of 4 [7]. However, in the majority of
(Nujol mull): ν = 1479 s, 1435 vs, 1306 w, 1198 s, 1184 sh, 1171 vs,
˜
reactions with C(PPh3)2 and Lewis acids in toluene or benzene 1165 s, 1150 s, 1113 vs, 1100 vs, 1069 m, 1028m, 995 sh, 984 s, 964
Z. Anorg. Allg. Chem. 2010, 1751–1759
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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1757

W. Petz, F. Öxler, K. Aicher, B. Neumüller
ARTICLE
s, 806 w, 789 w, 764 m, 750 s, 743 s, 714 vs, 694 vs, 569 m, 536 vs,
2J(P,P) = 14.3 Hz] in DCM and δ = 23.32. 21.79 [d's, 2J(P,P) =
518 s, 500 s, 444 w cm–1.
14.3 Hz] in DMSO. IR (Nujol mull): ν = 1481 m, 1447 s, 1194 m,
˜
1181 m, 1157 w, 1117 s, 1107 s, 1030 s, 1018 s, 997 s, 972 s, 806 m,
758 m, 747 s, 737 s, 723 s, 718 m, 702 m, 692 s, 596 m, 527 s, 515
s, 494 m, 480 m, 467 w, 467 w, 434 w cm–1. C31H26Cl2OP2Sn (MW
666.07): found C 54.7, H 4.1 %; calcd. C 55.90, H 3.94 %.
Formation of [Ph3PCHP(OBF3)Ph2] (5): A solution of 1 (0.59 g,
1.1 mmol) containing small amounts of 2 (identified by 31P NMR
spectroscopy) in toluene (20 mL) was admitted to an atmosphere of
gaseous BF3 for about 1 hour and the mixture was stirred mechanically.
A colorless precipitate formed immediately. After several days of
standing, colorless whiskers of 5 had grown from the filtered solution.
31P NMR (CH2Cl2, 200 MHz, 298 K): δ = 21.02, 19.38, 2J(P,P) =
[Ph3PCH2P(O)Ph2]2[Hg2I6] (9): To
a solution of 2 (0.07 g,
0.15 mmol) in THF (3 mL) HgI2 (0.09 g, 0.2 mmol) was added and a
clear solution was obtained. The 31P NMR spectrum of the solution
showed two doublets at 21.79, 21.07 ppm [d's, 2J(P,P) = 12.51 Hz]
along with two broad bands at 27.1 and 26.3 ppm. Layering of the
solution with n-pentane gave colorless crystals overnight, which turned
12.71 Hz. IR (Nujol mull): ν = 1613 m, 1588 w, 1487 w, 1441 st,
˜
1358 m, 1196 st, 1154 st, 1113 st, 997 m, 922 w, 903 w, 862 m, 883
st, 797 st, 739 st, 710 w, 685 st, 660 w, 579 m, 564 w, 507 m, 501 m,
488 m cm–1. C31H36BF3OP2: found C 67.4, H 5.1 %; calcd. C 68.4, H
4.8 %. The main product, probably the adduct F3B←1, dissolves in
DMSO, and the 31P NMR shows a signal at 20.8 ppm, which indicates
the formation of the cation (HC{PPh3}2)+ via proton abstraction from
the solvent. Similar behavior was observed with other polar solvents
such as DCM, DCE, and THF, therefore the structure of the precipitate
could not be identified as yet.
out to be the salt 9. 31P NMR (DMSO, 300 MHz, 298 K): δ = 23.34,
2
21.92 [d's, J(P,P) = 14.3 Hz]. IR (Nujol mull): ν = 1588 m, 1484 m,
˜
1437 s, 1375 m, 1334 m, 1185 s, 1118 s, 1071 m, 998 m, 799 s, 783
s, 743 m 743 s, 729 s, 712 s, 689 s, 556 m, 503 s, 484 m cm–1.
C31H27HgI3OP2 (MW 1058.77): found C 35.05, H 2.63 %; calcd. C
35.17, H 2.57 %.
Crystallographic data for the structures have been deposited with the
Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge
CB21EZ, UK. Copies of the data can be obtained on quoting the de-
pository numbers CCDC-757261 (2), -757262 (5), -757263 (6),
-757264 (7·C7H8), -757265 (8), and -757266 (9) (Fax: +44-1223-336-
033; E-Mail: deposit@ccdc.cam.ac.uk).
Formation of [Ph3PCH2P(OBF3)Ph2][HOB2F6] (6): From 2 and
[BF3(OEt2)]: [BF3(OEt2)] (0.1 mL, 0.8 mmol) was layered in a
Schlenk tube with toluene (2 mL). This mixture was layered with a
solution of 2 (0.05 g, 0.11 mmol) in toluene (1 mL) and allowed to
stand overnight. Colorless crystals of 6 separated. 31P NMR (CH2Cl2,
200 MHz, 298 K): δ = 45.63 (m, PO), 17.54 (d, PPh3), 2J(P,P) =
17.80 Hz. IR (Nujol mull): ν = 2723 m, br [ν(OH)], 1589 w, 1485, w,
˜
1439 s, 1406 w, 1367 m, 1341 w, 1173 to 1117 vs. [ν(BF)], 1034 m,
999 m, 856 s, 847 s, 801 s, 781 s, 743 vs, 731 s, 689 s, 600 w, 579
w, 557 w, 505 m, 490 m cm–1. Compound 6 was also obtained from
2 and BF3: A solution of 2 (0.20 g, 0.42 mmol) in toluene (20 mL)
was contacted with a bulb containing gaseous BF3. After some days,
crystals of 6 formed at the surface of the solution. The precipitate was
filtered and dried in vacuo. 31P NMR (CD2Cl2, 200 MHz, 298 K): δ =
45.69 (m, PO), 17.55 (d, PPh3), 2J(P,P) = 17.80 Hz. Another set of
two doublets at 23.54 and 18.75 ppm (2J(P,P) = 13.99 Hz) belongs to
5.
Acknowledgement
We thank the Deutsche Forschungsgemeinschaft for financial support.
W.P. is also grateful to the Max-Planck-Society, Munich, Germany, for
supporting this research project.
References
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Formation
of
[Ph3PCH2P(OBI3)Ph2][BI4]
(7)
and
(H2C{PPh3}2)[I3]I: Solutions of 1 (0.24 g, 0.45 mmol) and of BI3
(0.84 g, 2.14 mmol), in toluene (each about 10 mL), were combined
at room temperature. The resulting precipitate was filtered. In the fil-
trate small yellow crystals had formed after several days which turned
out to be 7·C7H8. 31P NMR (CH2Cl2, 200 MHz, 298 K): δ = 54.55
(m, PO), 16.20 (d, PPh3), 2J(P,P) = 16.35 Hz. IR (Nujol mull): ν =
˜
1558 m, 1480 m, 1439 s, 1339 w, 1312 w, 1213 m, 1181 s, 1161 m,
1099 w, 1074 w, 1028 w, 997 w, 963 m, 745 m, 735 m, 721 s, 710 w,
696 m, 687 m, 648 w, 536 s, 509 s cm–1. Part of the precipitate was
dissolved in MeCN. After five days needle-like orange red crystals
separated which turned out to be the salt (H2C{PPh3}2)[I3]I. 31P NMR
(MeCN): δ = 18.30.
[4] W. Petz, C. Kutschera, B. Neumüller, Organometallics 2005, 24,
5038.
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Khaasi, Polyhedron 2008, 27, 1963, and literature cited therein.
[6] S. Z. Goldberg, K. N. Raymond, Inorg. Chem. 1973, 12, 2923.
[Ph3PCHP(OSnCl2)Ph2] (8): To a solution of 2 (0.21 g, 0.44 mmol)
in DCM (4 mL) anhydrous SnCl2 (0.27 g, 0.88 mmol) was added and [7] W. Petz, C. Kutschera, S. Tschan, F. Weller, B. Neumüller, Z.
Anorg. Allg. Chem. 2003, 629, 1235.
the mixture was treated for 30 min in an ultrasonic bath at room tem-
perature. The resulting suspension was filtered from some insoluble
material. The 31P NMR spectrum of the solution showed two doublets
at 38.74 and 18.18 ppm [2J(P,P) = 19.67 Hz]. After about 24 h the
signals had disappeared in favor of two new doublets at 22.96, 21.33
ppm [2J(P,P) = 12.52 Hz]. Layering of the solution with n-pentane
gave colorless crystals after about three days which turned out to be
the addition compound 8; the product was filtered and dried in vacuo;
the yield was not determined. 31P NMR: δ = 23.01, 21.40 [d's,
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Int. Ed. 2006, 45, 8038.
1758
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Received: February 16, 2010
Published Online: June 2, 2010
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Z. Anorg. Allg. Chem. 2010, 1751–1759
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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