Phosphinidene reactivity toward unsaturated phosphorus heterocycles

Article abstract of DOI:10.1016/S0022-328X(00)00601-X

The transient electrophilic phosphinidene complex PhPW(CO)₅ reacts in the presence of CuCl at room temperature with phospholene 2 and phospholes 4a-c to give the corresponding W(CO)₅ complexed products 3 and 5a-c. The intermediate phosphoranylidene phosphine complexes, formed, from the addition of PhPW(CO)₅ to the phosphorus atom of the substrates, are characterized by NMR spectroscopy and by a single crystal X-ray structure determination for the one generated from phospholene 2. This intermediate 8 is a CuCl-complexed dimer, which speculatively results from dissociating the phosphole-CuCl tetramer on insertion of PhPW(CO)₅ into the P-Cu bonds. Reacting PhPW(CO)₅ with phospholene 2 at 110°C in the absence of CuCl gives besides the W(CO)₅-complexed phospholene 3 also a bisphospholene-W(CO)₄ complex 13. The formation of 13 is attributed to a ligand exchange reaction in the intermediate phosphinidene-phospholene adduct.

Full text of DOI:10.1016/S0022-328X(00)00601-X

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 617–618 (2001) 311–317
Phosphinidene reactivity toward unsaturated phosphorus
heterocycles
Mark J.M. Vlaar a, Frans J.J. de Kanter a, Marius Schakel a, Martin Lutz b,
Anthony L. Spek b, Koop Lammertsma a,*
a Department of Organic and Inorganic Chemistry, Faculty of Sciences, Vrije Uni6ersiteit, De Boelelaan 1083, NL-1081 HV,
Amsterdam, The Netherlands
b Bij6oet Center for Biomolecular Research, Department of Crystal and Structural Chemistry, Utrecht Uni6ersity, Padualaan 8,
NL-3584 CH Utrecht, The Netherlands
Received 10 July 2000; accepted 23 August 2000
Abstract
The transient electrophilic phosphinidene complex PhPW(CO)5 reacts in the presence of CuCl at room temperature with
phospholene 2 and phospholes 4a–c to give the corresponding W(CO)5 complexed products 3 and 5a–c. The intermediate
phosphoranylidene phosphine complexes, formed, from the addition of PhPW(CO)5 to the phosphorus atom of the substrates, are
characterized by NMR spectroscopy and by a single crystal X-ray structure determination for the one generated from
phospholene 2. This intermediate 8 is a CuCl-complexed dimer, which speculatively results from dissociating the phosphole–CuCl
tetramer on insertion of PhPW(CO)5 into the P–Cu bonds. Reacting PhPW(CO)5 with phospholene 2 at 110°C in the absence of
CuCl gives besides the W(CO)5-complexed phospholene 3 also a bisphospholene–W(CO)4 complex 13. The formation of 13 is
attributed to a ligand exchange reaction in the intermediate phosphinidene–phospholene adduct. © 2001 Elsevier Science B.V. All
rights reserved.
Keywords: Phosphinidene; Reactivity; Unsaturated phosphorus heterocycles
and C–H [8] bonds and even for selected C–C [9] and
C–P [10] bonds giving a broad spectrum of phosphine
derivatives. Association of the phosphinidene complex
to the P-atom of phosphines PR3 (R=alkyl, phenyl)
reportedly gives complexes of phosphoranylidene phos-
phines (R3PP(Ph)W(CO)5) [11] which can be applied as
phospha-Wittig reagents to generate PꢀC bonds [11,12].
Interested in expanding the scope of PhPW(CO)5 we
decided to study its reactivity toward unsaturated
organophosphorus compounds. Our intend was to es-
tablish whether addition to a CꢀC bond can be accom-
plished in the presence of a P-group. Here we report on
the reactions with a phospholene and with various
phospholes.
1. Introduction
Since Mathey showed that terminal phosphinidene
complexes RPM(CO)5 (M=W, Cr, Mo) can be gener-
ated in situ from phosphanorbornadienes [1], the car-
bene-like reactivity of these electrophilic species toward
various functional groups has been scrutinized [2]. 1,2-
Additions occur with simple CꢀC and CꢁC bonds. With
dienes larger five-membered ring structures result from
a subsequent 1,3-sigmatropic shift and by direct 1,4-ad-
dition [3]. Additions to CꢀN bonds, via pre-association
to the N-atom, have been reported to give heterocycles
in which two imines are incorporated [4], but the
smaller aza-phosphiranes are known too [5]. Bond in-
sertions of PhPW(CO)5 are also well established. They
have been shown to occur for O–H [1,5,6], N–H [6,7],
2. Results and discussion
* Corresponding author. Tel.: +31-20-444-7474; fax: +31-20-444-
7488.
Reaction of the complexed phosphinidene precursor
E-mail address: lammert@chem.vu.nl (K. Lammertsma).
1 with phospholene 2 at room temperature in the
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00601-X

312
M.J.M. Vlaar et al. / Journal of Organometallic Chemistry 617–618 (2001) 311–317
presence of more than one equivalent of CuCl afforded
to our surprise the W(CO)5-complexed phospholene 3
in 90% yield as the sole product. Likewise, reaction of
1 with phospholes (4a–c) resulted only in the W(CO)5-
complexed phospholes (5a–c), also in good yields.
These reactions seem perplexingly simple as the sub-
strates are merely complexed with a W(CO)5 group.
However, the addition of this transition metal group
cannot be a simple transfer from 1. We wondered about
the role of PhPW(CO)5 that must be generated from 1
under the reaction conditions. It is evident that no
addition to CꢀC bonds occur, but does association to
the P-atom take place? It also surprised us that more
than one equivalent of CuCl is needed for the reactions,
whereas only catalytic amounts are used for generating
PhPW(CO)5 from 1. We observed no reaction at room
temperature with less than one equivalent.
have 31P-NMR resonances for the phosphinidene and
phosphine phosphorus atoms of −100 to −145 and
1
31–35 ppm, respectively, with J(P–P) coupling con-
stants ranging from 430 to 444 Hz [11]. Of the more
stable complexes R3PꢀP(CO2Et)W(CO)5 (7, R=Bu,
Et) the Et derivative 7a (confirmed by a crystal struc-
ture determination) has corresponding phosphorus
chemical shifts of −97 and 38 ppm and a smaller
coupling constant of 361 Hz. These comparisons do
indeed suggest a similar association of PhPW(CO)5 to
the phospholene and phospholes of reaction 1 and 2.
To establish unequivocally the structure of the more
stable intermediate, we resorted to its single crystal
structure analysis. Surprisingly, intermediate 8 is not a
regular phosphoranylidene phospholene complex, but
rather a CuCl-complexed dimer (Fig. 1, Scheme 1). We
suggest that similar CuCl-complexed dimers (9a–c) are
formed in the reaction of complex 1 with phospholes
4a–c. The compound crystallizes with one molecule in
the asymmetric unit, which has approximately non-
crystallographic inversion symmetry. Selected bond
lengths and angles for 8 are given in the caption of Fig.
1. The organophosphorus part of the structure is as
expected. The two PP bond lengths of 2.1814(19) and
,
,
2.1751(18) A are slightly longer (ca. 0.02 A) than those
reported for 7a and the PW bonds of 2.5597(13) and
,
2.5559(13) A are correspondingly shorter. The 5–6°
larger PPW angles of 115.11(6)° and 116.09(6)° may
indicate more congestion in 8. The PCu bond lengths of
,
2.1979(14) and 2.1955(14) A between the organophos-
phorus parts and the central Cu2Cl2 ring are in line
with those reported for [Ar3PCuCl]2 complexes [13].
The bridging Cl atoms of the Cu2Cl2 ring are bound
asymmetrically, i.e. with Cu(11)Cl(11) and Cu(11)Cl-
Monitoring the reactions of 1 with 2 and with 4a,b
(not 4c) by 31P-NMR showed the formation of interme-
diates with PP bonds as evidenced by their 1J(P–P)
coupling constants. Executing the reaction of 1 with 2
for a short time (ca. 75 min), to maximize the forma-
tion of an intermediate (8), enabled its isolation and
even its purification using low temperature chromatog-
raphy on silica gel. The 31P-NMR doublets of 8 at l
−54.7 and 31.1 ppm suggest a phosphinidene–phos-
pholene complex, although it has a relatively small
1J(P–P) coupling constant of 294 Hz for a PꢀP bond.
The 31P-NMR data for the more reactive and only in
situ observed phosphinidene-phosphole complexes 9a
and 9b are similar.
,
(12) bond lengths of 2.2661(14) and 2.3518(14) A,
respectively, which is in line with related studies on
[(cyclohexyl)3PCuCl]2 and [(o-tolyl)3PCuCl]2 [13]. The
Cu atoms are in distorted trigonal planar environments,
ꢀ angles of 360.0° and 359.9°, with obtuse ClCuCl
angles of 99.13(5)° and 99.14(5)°; the angles at the
chlorines are acute, i.e. 80.94(4)° and 80.83(4)°. The
,
Cu···Cu distance of 2.9954(9) A is of similar length as
those of related [R3P2Cu2Cl2] systems [13]. In analogy
with these earlier studies we consider this distance to be
too long to represent a formal metal–metal bond.
It is informative to compare these spectroscopic data
with those of phosphoranylidenephosphines. Mathey
reported the very reactive, and difficult to purify
Bu3PꢀPRW(CO)5 (6, R=Ph, Me, allyl) complexes to
Scheme 1. Molecular structure of 8 in the crystal.

M.J.M. Vlaar et al. / Journal of Organometallic Chemistry 617–618 (2001) 311–317
313
,
Fig. 1. Displacement ellipsoid plot of 8 drawn at the 50% probability level. Hydrogen atoms are omitted for clarity. Selected bond lengths (A)
and angles (°): W11–P11 2.5597(13), W12–P12 2.5559(13), Cu11–P11 2.1979(14), Cu12–P12 2.1955(14), P11–P21 2.1814(19), P12–P22
2.1751(18), P11–C131 1.826(5), P12–C132 1.841(4), Cu11–Cl11 2.2661(14), Cu12–Cl12 2.2672(13), Cu11–Cl12 2.3518(14), Cl11–Cu12
2.3501(14); P21–P11–W11 115.11(6), P22–P12–W12 116.09(6), Cu11–P11–W11 119.94(6), Cu12–P12–W12 119.11(5), C131–P11–W11
114.34(16), C132–P12–W12 114.20(16), Cl11–Cu11–Cl12 99.13(5), Cl12–Cu12–Cl11 99.14(5), Cu11–Cl11–Cu12 80.89(4), Cu12–Cl12–Cu11
80.83(4).
The presence of CuCl in the crystal structure of 8 may
explain why more than one equivalent is needed in the
reactions. Reportedly, 6 and 7 are formed at 25–40°C in
THF as solvent without the use of CuCl. No transfer of
the W(CO)5 group from the phosphinidene to the phos-
phine phosphorus was observed in these systems [11].
Interestingly, reaction of complex 1 with tributylphos-
phine in the presence of more than one equivalent of
CuCl does give the W(CO)5 complexed tributylphos-
phine (11). The 1J(P–P) coupling constant for the
intermediate 10 of 286 Hz is 158 Hz smaller than that
for 6a. This relatively small coupling constant, which is
of this structure has a C2-distorted cubic form. With
bulkier ligands dimers [13,16] and monomers [17] were
found. We speculate that reaction of 1 occurs with the
[LCuCl]4 tetramer (12) of the phospholene (2), phospho-
les (4a–c), and Bu3P with insertion of PhPW(CO)5 into
the PCu coordinating bonds to result in the [L%CuCl]2
dimers 8 or 9a–c, or 10, respectively. We attribute the
cleavage of the tetramer to the more congested nature of
the R2P(Ph)ꢀPPhW(CO)5 ligand.
similar to those of 8 and 9a–c, is attributed to the
complexation of the phosphoranylidene phosphine com-
plexes to CuCl. We suggest that the W(CO)5 transfer in
8 and 9a–c to generate 3 and 5, respectively, proceeds
via a p-complex with concurrent elimination of rapidly
oligomerizing (Cu-complexed) PhP; p-complexes be-
tween transition metal groups and PꢀP bonds are well
established [14].
Why is CuCl present in the crystal structure of 8? It
is likely that CuCl coordinates with phospholene 2, the
phospholes 4a–c, and Bu3P. In fact, Nelson et al. showed
Cu(I) halides to coordinate to 1-phenyl-3,4-
dimethylphosphole (L) to form various complexes of the
type [LnCuX]m (n=1, 2, 3; m=4, 2, 1). They reported a
crystal structure for the tetramer [15]. The P4Cu4I4 core
To further inspect the impact of CuCl on the course
of the reactions we conducted experiments without this
catalyst. Reaction of 1 with phospholene 2 in toluene at
110°C gave again complex 3, but also bisphospholene
complex 13 in a 1:1 ratio (Scheme 2). The formation of
3 illustrates that the W(CO)5-shift in intermediate 8 is
independent of CuCl. However, CuCl may facilitate the
elimination of PhP and the concurrent transfer of
W(CO)5. Because of its rather complicated 13C-NMR
spectrum, due to the higher order couplings, we used a
single crystal X-ray structure determination (Fig. 2) to
establish with confidence the identity of 13 (l(31P)=1.8
ppm). Whereas formation of 13 may be rationalized by
a simple thermally induced ligand exchange of 3, heating

314
M.J.M. Vlaar et al. / Journal of Organometallic Chemistry 617–618 (2001) 311–317
W(CO)5 adds to the phosphorus center of phospholenes
(2) and phospholes (4a–c) instead of reacting with their
olefinic bonds. The resulting intermediates convert to
the corresponding W(CO)5-complexed products 3 and
5a–c with transfer of the transition metal group and
expulsion of PPh. The intermediate phosphoranylidene-
phosphine complexes are identified by NMR spec-
troscopy. A crystal structure of the one generated from
phospholene 2 showed it to be a CuCl-complexed dimer
(8). Generating PhPW(CO)5 in the absence of CuCl and
reacting it with phospholene 2 gives besides 3 also
bisphospholene complex 13.
Scheme 2.
4. Experimental
All experiments were performed under an atmo-
sphere of dry nitrogen. Solids were dried in vacuum
and liquids were distilled (under N2) prior to use.
Solvents were used as purchased except for toluene,
which was distilled over sodium, and CHCl3, which was
dried over molecular sieves. NMR spectra were
recorded on Bruker AC 200 (1H, 13C) and WM 250
spectrometers (31P) using SiMe4 (1H, 13C) and 85%
H3PO4 (31P) as external standards, IR spectra on a
Mattson-6030 Galaxy FTIR spectrophotometer, and
high-resolution mass spectra (HRMS) on a Finnigan
Mat 90 spectrometer. 1-Phenyl-3,4-dimethylphos-
pholene (2) [18], 1-phenyl-3,4-dimethylphosphole (4a)
[19], 1,3,4-trimethylphosphole (4b) [19] and 1,2,5-
triphenylphosphole (4c) [20] were prepared according to
literature procedures.
Fig. 2. Displacement ellipsoid plot of 13 drawn at the 50% probability
level. Hydrogen atoms are omitted for clarity. Selected bond lengths
,
(A) and angles (°): W–P1 2.4962(10), W–P2 2.5138(11), P1–C7
1.817(4), P2–C19 1.821(4), P1–C1 1.843(5), P2–C13 1.845(4), P1–C4
1.844(4), P2–C16 1.833(4), C2–C3 1.308(9), C14–C15 1.343(6), C1–
C2 1.508(7), C13–C14 1.525(6), C3–C4 1.508(7), C15–C16 1.518(6);
P1–W–P2 95.23(3), C7–P1–W 113.49(13), C19–P2–W 115.69(14),
C25–W–P1 86.63(12), C26–W–P2 88.04(13), C27–W–P1 88.10(11),
C27–W–P2 86.63(13), C28–W–P1 87.74(12), C28–W–P2 91.28(13),
C1–P1–C4 92.5(2), C16–P2–C13 92.3(2).
4.1. Reaction of 1 with 1-phenyl-3,4-dimethyl-
phospholene (2)
of this compound together with phospholene 2 at 110°C
for several hours does not give any 13. It seems then
more plausible that ligand exchange occurs in the inter-
mediate phosphinidene–phosphole complex. Indeed,
heating a mixture of isolated 8 and 2 at 110°C does
result in a mixture of bisphospholene complex 13 and 3.
Phosphoranylidene-phosphines can be considered
phospha-Wittig reagents. In fact, 6, but not the more
stable 7, are known to react with aldehydes only to
form incipient phosphaalkenes, which can subsequently
be trapped with, for example, methanol [11,12]. How-
ever, we did not observe a reaction of 8 with benzalde-
hyde nor with isobutyraldehyde, but obtained only 3.
The formal phosphinidene O–H insertion product
[(MeO)PHPh]W(CO)5 results in the presence of
methanol as trapping reagent.
4.1.1. Formation of
[(Me)2C4H4P(Ph)ꢀPPhW(CO)5CuCl]2 (8)
A mixture of complex 1 (0.62 g, 0.95 mmol), 2 (0.18
g, 0.95 mmol) and CuCl (0.11 g, 1.10 mmol) in 5 ml of
CHCl3 was stirred at room temperature (r.t.) for 75
min. Chromatography on activated silica at −15°C
with pentane–CH2Cl2 (2:1) as eluent and crystallization
from a hexane–CH2Cl2 mixture gave 0.33 g (47.4%
(based on 1) of complex 8 as yellow crystals: 31P-NMR
(CDCl3) l=31.1 (d, 1J(P–P)=294 Hz, P–P–W),
−54.7 (d, 1J(P–P)=294 Hz, P–P–W); 1H-NMR
(CDCl3) l=1.72 (d, 4J(P–H)=5.0 Hz, 12H, CH3),
3.0–3.5 (m, 8H, CH2), 7.3–7.7 (m, 20H, Ph); 13C-NMR
2
(CDCl3) l=199.7 (d, J(P–C)=16.1 Hz, trans-CO),
2
1
197.2 (d, J(P–C)=3.9 Hz, J(P–W)=125.4 Hz, cis-
3
2
CO), 137.5 (dd, J(P–C)=5.1 Hz, J(P–C)=13.7 Hz,
o-Ph), 133.1 (d, 4J(P–C)=3.0 Hz, p-Ph), 131.8 (d,
3J(P–C)=8.6 Hz, m-Ph), 130.4 (d, J(P–C)=11.1 Hz,
1
3. Conclusions
4
ipso-Ph), 130.2 (d, J(P–C)=3.0 Hz, p-Ph), 129.4 (d,
Transient electrophilic phosphinidene complex PhP-
3J(P–C)=11.5 Hz, m-Ph), 128.8 (dd, 3J(P–C)=3.5

M.J.M. Vlaar et al. / Journal of Organometallic Chemistry 617–618 (2001) 311–317
315
2
2
Hz, J(P–C)=7.6 Hz, o-Ph), 128.6 (d, J(P–C)=4.5
showed the formation of intermediate 9b: 31P-NMR
l=36.9 (d, 1J(P–P)=294 Hz, P–P–W), −72.6 (d,
1J(P–P)=294 Hz, P–P–W).
Hz, CꢀC), 124.9 (d, 1J(P–C)=59.7 Hz, ipso-Ph), 36.5 (d,
1J(P–C)=42.9 Hz, CH2), 16.7 (dd, 3J(P–C)=11.4 Hz,
4J(P–C)=3.5 Hz, CH3). IR (CH2Cl2, cm−1): w(CO)=
1934 (s), 2067 (w).
4.2.3. Reaction of 1 with 1,2,5-triphenylphosphole (4c)
A solution of complex 1 (0.29 g, 0.45 mmol), 4c (0.14
g, 0.45 mmol) and CuCl in toluene was heated at 55°C
for 2 h. Filtration, evaporation to dryness and chro-
matography on silica with pentane–toluene (1:1) gave
0.17 g (61%) of 5c as a yellow solid. Spectroscopic data
for 5c were identical to an authentic sample [24].
4.1.2. Formation of [1-phenyl-3,4-dimethylphos-
pholene](pentacarbonyl)tungsten (3)
A mixture of complex 1 (0.17 g, 0.25 mmol), 2 (44 mg,
0.23 mmol) and CuCl in CHCl3 was stirred overnight at
r.t. Evaporation to dryness and chromatography on silica
with pentane–toluene (3:1) gave 117 mg (90%) of 3 as
colorless crystals. Spectroscopic data for 3 are in accord
with literature data [21].
4.3. Reaction of 1 with tributylphosphine
A solution of complex 1 (0.14 mg, 0.21 mmol),
tributylphosphine (53 ml, 0.21 mmol) and CuCl (22 mg,
0.22 mmol) in 3 ml of CHCl3 was stirred at r.t. for 4.5
h. Evaporation to dryness and chromatography on silica
with pentane–dichloromethane (4:1) gave 61 mg of 11 as
a light yellow oil. Spectroscopic data for 11 are in accord
with literature data [25]. Monitoring the reaction by
31P-NMR showed the formation of intermediate 10:
31P-NMR l=23.2 (d, 1J(P–P)=286 Hz, P–P–W),
4.1.3. Formation of 3 and cis-bis-[1-phenyl-3,4-
dimethylphospholene]-(pentacarbonyl)tungsten (13)
A solution of complex 1 (0.29 g, 0.45 mmol) and 2 (0.26
g, 1.3 mmol) in 4 ml of toluene was heated at 110°C for
2 h. Evaporation to dryness and chromatography on
silica with pentane–toluene (4:1), gave 86 mg (37%) of
3 and 99 mg (32%) of 13. Colorless crystals of 13 were
obtained after recrystallization from pentane–CH2Cl2:
m.p. 96–97°C; 31P-NMR (CDCl3) l=1.8 (1J(31P–
1
−79.7 (d, J(P–P)=286 Hz, P–P–W).
1
183W)=224.7 Hz); H-NMR (CDCl3) l=1.54 (s, 6H,
4.4. Attempted reaction of 8 with aldehydes
CH3), 2.6–2.9 (m, 4H, CH2), 7.17–7.24 (m, 10H, phenyl);
13C-NMR (CDCl3) l=206.0 (m, trans-CO), 202.2 (t,
2J(P–C)=7.7 Hz, cis-CO), 138.9 (m, 1+3J(PꢂC)=30.8
Hz, ipso-Ar), 129.6–128.0 (Ar), 129.6 (s, CꢀC), 44.6 (m,
1+3J(PꢂC)=27.7 Hz, CH2), 16.0 (s, CH3). IR (KBr,
cm−1): w(CO)=2062 (s), 2089 (w); HRMS. Calc. for
C28H30P2WO4: 676.11293; Found: 676.11279.
4.4.1. Reaction in the presence of methanol
A solution of complex 1 (0.24 g, 0.37 mmol), 2 (64 mg,
0.34 mmol) and CuCl in 5 ml of CHCl3 was stirred at
r.t. When the conversion of 1 to 8 was complete (as
monitored by 31P-NMR), one equivalent of benzalde-
hyde or isobutyraldehyde was added. After 5 min, 0.16
ml (4.0 mmol) of MeOH was added and stirring was
continued for 45 min. Evaporation to dryness and
chromatography on silica with pentane–toluene (4:1)
afforded 0.10–0.12 g (76–88%) of [(MeO)PHPh]-
W(CO)5 as a white solid. Spectroscopic data for
[(MeO)PHPh]W(CO)5 are in accord with literature data
[1].
4.2. Reaction of 1 with phospholes 4a–c
4.2.1. Reaction of 1 with
1-phenyl-3,4-dimethylphosphole (4a)
A solution of complex 1 (0.28 g, 0.42 mmol), 4a (0.20
g, 1.1 mmol) and CuCl in 5 ml of CHCl3 was stirred
overnight at r.t. Filtration, evaporation to dryness and
chromatography on silica with pentane–toluene (4:1)
gave 0.16 g (74%) of 5a as a yellow solid. Spectroscopic
data for 5a are in accord with literature data [22].
Monitoring the reaction by 31P-NMR showed the forma-
4.4.2. Reaction without methanol
Complex 8 was synthesized in situ as described above.
Addition of five equivalents of benzaldehyde or isobu-
tyraldehyde and stirring overnight at r.t. yielded quanti-
tatively complex 3 as indicated by 31P-NMR.
tion of intermediate 9a: 31P-NMR l=40.5 (d, J(P–
1
1
P)=316 Hz, P–P–W), −53.3 (d, J(P–P)=316 Hz,
P–P–W).
4.5. X-ray crystallography
4.2.2. Reaction of 1 with 1,3,4-trimethylphosphole (4b)
A solution of complex 1 (0.89 g, 1.35 mmol), 4b (0.17
g, 1.35 mmol) and CuCl (0.17 g, 0.17 mmol) in CHCl3
was stirred overnight at r.t. Filtration, evaporation to
dryness and chromatography on silica with pentane–tol-
uene (4:1) gave 0.25 g (41%) of 5b as a yellow oil.
Spectroscopic data for 5b were identical to an authentic
sample [23]. Monitoring the reaction by 31P-NMR
4.5.1. Crystal structure determination of complex 8
C46H40Cl2Cu2O10P4W2+solvent, Fw=1442.341, yel-
3
(
low block, 0.36×0.27×0.09 mm , triclinic, P1 (no. 2),
,
a=10.7136(8), b=15.9667(13), c=20.2435(14) A, h=
93.161(4), i=103.032(3), k=93.428(3)°, V=3359.2(4)
1 Derived values do not contain the contribution of the disordered
solvent.

316
3
M.J.M. Vlaar et al. / Journal of Organometallic Chemistry 617–618 (2001) 311–317
A , Z=2, z=1.426 g cm−3.1 A total of 29 905 reflec-
,
5. Supplementary material
tions were measured on a Nonius KappaCCD diffrac-
Crystallographic data for the structures reported in
this paper have been deposited with the Cambridge
Crystallographic Data Centre, CCDC no. 146323 for
compound 8 and CCDC no. 146324 for compound
13. Copies of this information may be obtained free
of charge from the Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK (fax: +44-1223-336-033;
e-mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.
cam.ac.uk).
,
tometer with rotating anode (u=0.71073 A) at a
temperature of 100(2) K. A total of 14 786 reflections
were unique (Rint=0.051). The absorption correction
was based on multiple measured reflections (program
PLATON [26], routine MULABS, v=4.25 mm−1,1 0.54–
0.73 transmission). The structure was solved with Pat-
terson methods (DIRDIF-97 [27]) and refined with
SHELXL-97 [28] against F2 of all reflections. Non-hy-
drogen atoms were refined freely with anisotropic dis-
placement parameters. Hydrogen atoms were refined
as rigid groups. The crystal structure contains large
3
Acknowledgements
,
voids (1087 A /unit cell) filled with disordered
dichloromethane and hexane molecules. Their contri-
bution to the structure factors was secured by back-
Fourier transformation (program PLATON [26], CALC
SQUEEZE, 344 e−/unit cell). 599 refined parameters, no
restraints. R values [I\2|(I)]: R1=0.0449, wR2=
0.1027. R values [all reflections]: R1=0.0681, wR2=
0.1086. GoF=1.070. Rest electron density between
Acknowledgment is made to the Netherlands Orga-
nization for Scientific Research (NWO/CW) for sup-
port of this research. We thank Dr. H. Zappey for
the HRMS measurements.
References
−2.29 and 2.21 e A−3. Molecular illustration, struc-
,
ture checking and calculations were performed with
the PLATON package [26].
[1] F. Mathey, A. Marinetti, J. Am. Chem. Soc. 104 (1982) 4484.
[2] (a) F. Mathey, Angew. Chem. 99 (1987) 285; Angew. Chem. Int.
Ed. Engl. 26 (1987) 275. (b) K.B. Dillon, F. Mathey, J.F. Nixon,
Phosphorus: The Carbon Copy, Wiley, Chichester,1998, pp.
19–39.
[3] (a) J.T. Hung, K. Lammertsma, J. Org. Chem. 58 (1993) 1800.
(b) K. Lammertsma, J.-T. Hung, P. Chand, G.M. Gray, J. Org.
Chem. 57 (1992) 6557. (c) A. Marinetti, F. Mathey,
Organometallics 3 (1984) 456. (d) M.J. van Eis, F.J.J. de Kanter,
W.H. de Wolf, K. Lammertsma, F. Bickelhaupt, M. Lutz, A.L.
Spek, Tetrahedron, 56 (2000) 129.
4.5.2. Crystal structure determination of complex 13
C28H30O4P2W+solvent, Fw=676.311, colourless
3
(
block, 0.50×0.25×0.13 mm , triclinic, P1 (no. 2),
,
a=8.2135(6), b=9.7430(6), c=18.8082(11) A, h=
95.296(5),
i=96.453(6),
k=108.070(6)°,
V=
1408.87(16) A , Z=2, z=1.594 g cm−3.1 A total of
12 483 reflections were measured on an Enraf-Nonius
CAD4T diffractometer with rotating anode (u=
3
,
[4] N.H.T. Huy, L. Ricard, F. Mathey, Heteroatom. Chem. 9 (1998)
597.
[5] R. Streubel, A. Ostrowski, H. Wilkens, F. Ruthe, J. Jeske, P.G.
Jones, Angew. Chem. 109 (1997) 409; Angew. Chem. Int. Ed.
Engl. 36 (1997) 378.
[6] A. Marinetti, F. Mathey, Organometallics 1 (1982) 1488.
[7] B. Deschamps, L. Ricard, F. Mathey, Polyhedron 8 (1989) 2671.
[8] J. Svara, F. Mathey, Organometallics 5 (1986) 1159.
[9] Y. Inubushi, N.H.T. Huy, F. Mathey, J. Chem. Soc. Chem.
Commun. (1996) 1903.
[10] (a) N.H.T. Huy, L. Ricard, F. Mathey, Organometallics 16
(1997) 4501. (b) B. Wang, K.A. Nguyen, G.N. Srinivas, C.L.
Watkins, S. Menzer, A.L. Spek, K. Lammertsma, Organometal-
lics 18 (1999) 796.
[11] P. Le Floch, A. Marinetti, L. Ricard, F. Mathey, J. Am. Chem.
Soc. 112 (1990) 2407–2410.
,
0.71073 A) at a temperature of 150(2) K. A total of
6478 reflections were unique (Rint=0.084). The ab-
sorption correction was based on psi-scans (program
PLATON [26], routine ABSP, v=4.24 mm−1 1
, 0.82–
0.98 transmission). The structure was solved with Pat-
terson methods (DIRDIF-97 [27]) and refined with
SHELXL-97 [28] against F2 of all reflections. Non-
hydrogen atoms were refined freely with anisotropic
displacement parameters. Hydrogen atoms were
refined as rigid groups. The crystal structure contains
3
,
a
void (92 A /unit cell) filled with disordered
dichloromethane and hexane molecules. Their contri-
bution to the structure factors was secured by back-
Fourier transformation (program PLATON [26], CALC
SQUEEZE, 29 e−/unit cell). 320 refined parameters, no
restraints. R values [I\2|(I)]: R1=0.0280, wR2=
0.0724. R values [all reflections]: R1=0.0324, wR2=
0.0751. GoF=1.081. Rest electron density between
[12] (a) A. Marinetti, F. Mathey, Angew. Chem. 100 (1988) 1435;
Angew. Chem. Int. Ed. Engl. 27 (1988) 1382. (b) A. Marinetti, L.
Ricard, F. Mathey, Organometallics
9 (1990) 788. (c) A.
Marinetti, S. Bauer, L. Ricard, F. Mathey, Organometallics 9
(1990) 793. (d) A. Marinetti, P. Le Floch, F. Mathey,
Organometallics 10 (1991) 1190. (e) S. Shah, J.D. Protasiewicz,
Chem. Commun. (1998) 1585.
[13] (a) S.K. Hadjikakou, P.D. Akrivos, P. Karagiannidis, E. Rapto-
poulou, A. Terzis, Inorg. Chim. Acta 210 (1993) 27. (b) S.
Ramapabhu, N. Amstutz, E.A.C. Lucken, G. Bernardinelli, J.
Chem. Soc., Dalton Trans. (1993) 871. (c) M.R. Churchill, F.J.
Rotella, Inorg. Chem. 18 (1979) 166.
−1.29 and 1.51 e A−3. Molecular illustration, struc-
,
ture checking and calculations were performed with
the PLATON package [26].

M.J.M. Vlaar et al. / Journal of Organometallic Chemistry 617–618 (2001) 311–317
[14] K.B. Dillon, F. Mathey, J.F. Nixon, Phosphorus: The Carbon [21] A. Marinetti, F. Mathey, Organometallics 3 (1984) 456.
317
Copy, Wiley, Chichester, 1998, pp. 164–180.
[15] S. Attar, G.A. Bowmaker, N.W. Alcock, J.S. Frye, W.H. Bear-
den, J.H. Nelson, Inorg. Chem. 30 (1991) 4743–4753.
[16] (a) G.L. Soloveichik, O. Eisenstein, J.T. Poulton, W.E. Streib,
J.C. Huffman, K.G. Caulton, Inorg. Chem. 31 (1992) 3306. (b)
M. Shiotsuka, Y. Matsuda, Chem. Lett. (1994) 351. (c) H.
Werner, H. Otto, T. Ngo-Khac, Ch. Burschka, J. Organomet.
Chem. 262 (1984) 123.
[17] (a) E.C. Alyea, G. Ferguson, J. Malito, B.L. Ruhl, Inorg. Chem.
24 (1985) 3720. (b) G.A. Bowmaker, J.D. Cotton, P.C. Healy,
J.D. Kildea, S.B. Silong, B.W. Skelton, A.H. White, Inorg.
Chem. 28 (1989) 1462. (c) L.-J. Baker, G.A. Bowmaker, R.D.
Hart, P.J. Harvey, P.C. Healy, A.H. White, Inorg. Chem. 33
(1994) 3925.
[22] C.C. Santini, J. Fischer, F. Mathey, A. Mitschler, J. Am. Chem.
Soc. 102 (1980) 5809.
[23] A. Marinetti, F. Mathey, J. Fischer, A. Mitschler, J. Chem. Soc.
Chem. Commun. (1982) 667.
[24] R.C. Cookson, G.W.A. Fowles, D.K. Jenkins, J. Chem. Soc. 5
(1965) 6406.
[25] (a) S.O. Grim, D.A. Wheatland, W. McFarlane, J. Am. Chem.
Soc. 89 (1967) 5573. (b) G.T. Andrews, I.J. Colquhoun, W.
McFarlane, J. Chem. Soc., Dalton Trans. (1982) 2353.
[26] A.L. Spek, PLATON. A Multipurpose Crystallographic Tool,
Utrecht University, The Netherlands, 2000.
[27] P.T. Beurskens, G. Admiraal, G. Beurskens, W.P. Bosman, S.
Garcia-Granda, R.O. Gould, J.M.M. Smits, C. Smykalla, The
DIRDIF-97 Program System, Technical Report of the Crystallog-
raphy Laboratory, University of Nijmegen, The Netherlands,
1997.
[18] H. Fritzsche, U. Hasserodt, F. Korte, Chem. Ber. 97 (1964)
1988.
[19] A. Breque, F. Mathey, Ph. Sarignac, Synthesis (1981) 983.
[20] B. Lukas, R.M.G. Roberts, J. Silver, A.S. Wells, J. Organomet.
Chem. 256 (1983) 103.
[28] G.M. Sheldrick, SHELXL-97. Program for Crystal Structure
Refinement, University of Go¨ttingen, Germany, 1997.
.