Ylidyl-substituted phosphonio-benzophospholides as chelating ligands

Article abstract of DOI:10.1002/zaac.200400217

Phosphonio-benzo[c]phospholides with an additional phosphonium ylide substituent in 3-position were synthesized by deprotonation of appropriately substituted 1,3-bis-phosphonio benzophospholide cations and characterized by spectroscopic and analytical data. The ability of these molecules to act as bidentate P,C-chelating ligands to transition metal atoms was demonstrated in the reactions with [W(CO)₄(norbornadiene)] and [MCl ₂(cyclooctadiene)] (M = Pd, Pt). The Pd^II and Pt ^II complexes are distinguished by a strong inclination towards addition of H₂O to the 10π-electron system of the ligand. The molecular structures of a W⁰ complex with a P,C-chelating ylidyl-phosphonio-benzophospholide ligand and of the product resulting from H₂O-addition to a corresponding Pt^II complex were determined. The structural parameters of the W⁰ complex provide evidence for the presence of substantial steric strain around the metal atom.

Full text of DOI:10.1002/zaac.200400217

Ylidyl-substituted Phosphonio-benzophospholides as Chelating Ligands
Zoltan Bajko, Dietrich Gudat*, Falk Lissner, Martin Nieger, and Thomas Schleid
Stuttgart, Institut für Anorganische Chemie der Universität
Received June 8th, 2004.
Dedicated to Professor Michael Veith on the Occasion of his 60th Birthday
Abstract. Phosphonio-benzo[c]phospholides with an additional
phosphonium ylide substituent in 3-position were synthesized by
deprotonation of appropriately substituted 1,3-bis-phosphonio
benzophospholide cations and characterized by spectroscopic and
analytical data. The ability of these molecules to act as bidentate
P, C -chelating ligands to transition metal atoms was demonstrated
in the reactions with [W(CO)4(norbornadiene)] and [MCl2(cyclooc-
tadiene)] (M ϭ Pd, Pt). The PdII and PtII complexes are dis-
tinguished by a strong inclination towards addition of H2O to the
10π-electron system of the ligand. The molecular structures of a W0
complex with a P,C-chelating ylidyl-phosphonio-benzophospholide
ligand and of the product resulting from H2O-addition to a corre-
sponding PtII complex were determined. The structural parameters
of the W0 complex provide evidence for the presence of substantial
steric strain around the metal atom.
Keywords: Phosphorus heterocycles; Benzophospholides; Ylides; P
ligands
Ylidyl-substituierte Phosphonio-benzophospholide als Chelatliganden
Inhaltsübersicht. Phosphonio-benzo[c]phospholide mit einem zu-
sätzlichen Phosphoniumylid-Substituenten in 3-Position wurden
durch Deprotonierung geeignet substituierter 1,3-Bis-phosphonio-
benzophospholid-Kationen dargestellt und durch spektroskopische
und analytische Daten charakterisiert. Die Fähigkeit dieser Mole-
küle als zweizähnige P, C -Chelatliganden zu agieren wurde in Reak-
tionen mit [W(CO)4(norbornadien)] und [MCl2(cyclooctadien)]
(M ϭ Pd, Pt) demonstriert. Die PdII und PtII Komplexe zeichnen
sich durch eine starke Neigung zur Addition von H2O an das 10π-
Elektronensystem des Liganden aus. Die Molekülstrukturen eines
W0-Komplexes mit einem P, C -chelatisierenden Ylidyl-Phosphonio-
benzophospholid-Liganden und eines aus der H2O-Addition an
den entsprechenden PtII-Komplex resultierenden Produktes wur-
den bestimmt. Die strukturellen Parameter des W0-Komplexes ge-
ben Hinweise auf das Vorhandensein einer beträchtlichen steri-
schen Spannung um das Metallatom.
Introduction
lated us to perform a study of the synthesis and coordi-
nation chemistry of 2a whose results will be reported here.
In the course of our investigations of the chemistry of zwit-
terionic phosphonio- benzophospholides we have shown
that the derivatives 1 and 4 (Scheme 1) can act as bidentate
chelating ligands via the ring phosphorus atom and the sul-
fur atom or a BH-σ-bond of the pendant thioxophosphor-
anyl or phosphine-borane substituents, respectively [1]. Re-
garding that thioxophosphoranes and phosphine-boranes
form a row of valence-isoelectronic compounds together
with monophosphazenes and phosphonium ylides and that
the ligand properties of the latter are well documented [2],
one can expect that the ylide- and phosphazene-substituted
phosphonio-benzophospholides 2a, 3 (Scheme 1) display a
similar ligand behavior as 1, 4. Some recent reports on the
coordination properties and catalytic application of bifunc-
tional phosphino-phosphonium ylide ligands [3, 4] stimu-
Results and Discussion
Preparation and characterization of ylidyl-substituted
phosphonio-benzophospholides
The target compounds were readily prepared from the pho-
sphinyl-substituted zwitterion 5 [5] by a standard two-step
procedure (Scheme 2). Reaction of 5 with appropriate alkyl
halides afforded first the 1,3-bis-phosphonio-benzophos-
pholide salts 6a-d which were isolated in good yield as air
and moisture stable solids. These salts were then reacted
with BuLi or metal amides such as LiN(SiMe3)2,
NaN(SiMe3)2, or NaNH2, respectively. 31P NMR studies
showed that the deprotonation of 6b proceeded unselec-
tively to give an inseparable mixture, but that the ylides
2a,c,d were formed in near quantitative yield. The choice of
the base had practically no influence on the outcome of the
deprotonation, but the use of NaN(SiMe3)2 facilitated the
separation of the ylides from the salts formed as by-prod-
ucts.
* Prof. Dr. Dietrich Gudat
Institut für Anorganische Chemie der Universität Stuttgart
Pfaffenwaldring 55
D-70550 Stuttgart
Fax: ϩ49 (0)711 685 4241
The stabilized ylides 2c,d were readily isolated as light
yellow solids. Isolation of 2a in pure form was prevented by
E-mail: gudat@iac.uni-stuttgart.de
Z. Anorg. Allg. Chem. 2004, 630, 1969Ϫ1976
DOI: 10.1002/zaac.200400217
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1969

Z. Bajko, D. Gudat, F. Lissner, M. Nieger, Th. Schleid
Scheme 1 (nbd ϭ norbornadiene)
Scheme 2 (6a: R ϭ RЈ ϭ H; X ϭ I; 6b: R ϭ H, RЈ ϭ Ph, X ϭ Br;
6c: R ϭ H, RЈ ϭ CN, X ϭ Cl; 6d: RRЈ ϭ 9-fluorenylidene, X ϭ Br)
Scheme 3
partial decomposition (mainly re-protonation and reductive
cleavage of a carbene fragment to produce 5) during work-
up, but the product was unambiguously identified by means
of NMR spectroscopy. Treatment of a freshly prepared
solution of crude 2a with ClPPh2 gave a mixture of two
compounds which were identified as the cations 6a and 6e
(cf. Scheme 3) by their characteristic patterns in 31P{1H}
and 1H,31P HMQC NMR spectra. Subsequent depro-
tonation by NaN(SiMe3)2 afforded the ylides 2a and 2e.
The latter precipitated together with the NaCl formed and
was characterized by NMR and mass spectrometry. At-
tempts to purify 2e by fractional crystallization failed, and
the product could thus not be obtained in pure form. The
reaction pattern leading to 2e is well established for phos-
phonium ylides [6] and can be considered as independent
validation of the identity of 2a.
2a decomposes rapidly in almost any solvent other than
toluene, whereas 2c can be handled in anhydrous THF or
DME, and 2d is soluble in most polar organic solvents, in-
cluding alcohols, and tolerates even the presence of water
without detectable decomposition. Interestingly, 2c un-
dergoes a quantitative reaction to give the phosphine 5 be-
sides unidentified by-products upon the attempted dissol-
ution in anhydrous CH2Cl2.
The identity of the ylides 2a,c,d was unambiguously es-
tablished by analytical and spectroscopic data. The most
characteristic NMR spectral changes as compared to the
conjugated acids, 6a,c,d, involve an increase by some 70 Hz
1
of the JPC coupling to the ylide carbon atom and a larger
The ylides 2a (as a mixture of the crude product and
NaI) and 2c,d are yellow solids which are stable in dry air.
The stabilization of the formal carbanion by an electron
withdrawing CN substituent or the incorporation into an
aromatic π-electron system in 2c,d induce a marked de-
crease in basicity and an increased chemical stability. Thus,
shielding of the directly attached protons (∆δ ϭ Ϫ1.9 (2a),
Ϫ3.6 (2c)). The variation of δ13C and δ31P of the atoms in
the ylide moiety upon deprotonation displays no common
trend, but the chemical shifts of the P-2 atoms in 2a,c,d
show a small, although hardly significant, additional shield-
ing by some 5 ppm.
1970
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Ylidyl-substituted Phosphonio-benzophospholides as Chelating Ligands
Scheme 4 (nbd ϭ norbornadiene; cod ϭ 1,5-cyclooctadiene)
Complex formation reactions of ylidyl-substituted
phosphonio-benzophospholides
In consideration of the recent report on a phosphino-phos-
phonium ylide complex of PdII [4], we attempted the syn-
thesis of Pd and Pt complexes of the potential P, C -bidentate
ylide 2c. Treatment of the ligand with one equivalent of
[PtCl2(COD)]
(COD
ϭ
1,5-cyclooctadiene)
or
[PdCl2(MeCN)2] resulted according to the results of 31P
NMR studies in clean formation of products which were,
in regard of the similarity of their spectral data with those
of previously reported Pt and Pd complexes with bis-phos-
phonio-benzophospholide cations [7], assigned as the ex-
pected complexes 7, 8 (Scheme 4). Attempted isolation of
the products was under all conditions prevented by the on-
set of hydrolytic decomposition1) to give a mixture of two
species assigned (see below) as the diastereomers 9a,b and
10a,b. The quantitative hydrolysis of 7 occurred upon pro-
longed exposition of the reaction mixture to moist air, and
a mixture containing nearly equal amounts of 9a and 9b
was isolated after precipitation with hexanes. The hydrolysis
of the Pt complex 8 proceeded less selectively; here, the ad-
dition products 10a,b were merely detectable as intermedi-
ates which decayed further under complete cleavage of the
five membered heterocyclic ring.
Fig. 1 Molecular structure of 10a. Thermal ellipsoids are drawn at
50 % probability level, and H atoms have been omitted for clarity.
˚
Selected bond lengths/A: Pt(1)-C(40) 2.071(7), Pt(1)-P(1) 2.1970(19), Pt(1)-
Cl(1) 2.3510(18), Pt(1)-Cl(2) 2.3922(19), P(1)-O(1) 1.493(5), P(1)-C(2)
1.850(8), P(1)-C(9) 1.907(7), C(2)-C(3) 1.532(10), C(2)-P(2) 1.836(7), C(3)-
C(8) 1.409(10), C(8)-C(9) 1.506(11), C(9)-P(3) 1.811(7).
square-planar coordination with bond angles (from 87.2(2)°
to 93.4(2)°) deviating only slightly from the ideal value. The
intra-ligand bond distances and angles display no peculiari-
ties and match closely the corresponding data in 11 [8] (cf.
The constitution of 9a,b and 10a,b was established by
one and two-dimensional NMR studies (see Experimental
section for data) and an X-ray diffraction study of a sample
of 10a which was serendipitously isolated during attempts
directed at the crystallization of 8. The structure of 10a
˚
Scheme 4). The Pt(1)-C(40) distance of 2.071(7) A fits well
into the range of known bond distances in Pt-complexes of
2)
˚
phosphonium ylides (2.04 Ϫ 2.16 A ).
The envelope conformation of the dihydrophosphole ring
in the ligand of 10a is similar as in 11, but the phosphonio-
substituents reside in trans- rather than cis-positions, and
the metal rather than the oxygen atom occupies the “flag-
pole” position at the P1 atom. This arrangement causes a
¯
(space group R 3) is composed of isolated molecular com-
plexes (Figure 1) and contains three solvent molecules
(THF) in the asymmetric unit. The metal atom adopts a
1) As 9a,b and 10a,b formed also slowly when the whole reaction
was conducted in carefully dried solvents and under complete ex-
clusion of oxygen and moisture in a glove box, it cannot be ex-
cluded that the source of H2O is provided by a wall reaction with
the material of the reaction flask.
2) Result of a query in the CSD database for complexes with the
structural fragment X3PtϪCX2ϪPR3 (X ϭ any group; R ϭ alkyl
or aryl)
Z. Anorg. Allg. Chem. 2004, 630, 1969Ϫ1976
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1971

Z. Bajko, D. Gudat, F. Lissner, M. Nieger, Th. Schleid
strong folding between the dihydrophosphole and the adjac-
ent PtPCPC-chelate rings and is presumably a consequence
of the geometrical constraints imposed by the confor-
mational rigidity of the heterocyclic rings and steric conges-
tion by peripheral substituents. The nitrile moiety at C(40)
resides in an endo-position with respect to the dihydrophos-
phole ring, leading to a cis-arrangement the two CH-bonds
in the chelate ring. Keeping in mind that the same confor-
mational constraints as in 10a (which fix the relative con-
figurations at three of the four stereo-centres present)
should also apply for the second diastereomer, both isomers
are most likely distinguished by an inverted configuration
at the ylide carbon atom. This suggests for 10b an arrange-
ment where the nitrile occupies the exo-position with re-
spect to the dihydrophosphole ring, and the CH-bonds in
the chelate ring are trans to each other. An attempt to verify
the relative stereochemistry of the diastereomeric Pd-com-
plexes 9a,b from 1H NOESY NMR spectra failed, owing to
the absence of any correlations interconnecting the three
ring hydrogen atoms.
The formation of the complexes 9, 10 resembles the
known activation of bis- phosphonio-benzophospholide
cations to undergo hydrolysis upon protonation [9] or tran-
sition metal coordination [8Ϫ10], and the spectroscopic and
structural data of 9a,b and 10a,b display indeed close simi-
larity to those of the products formed by hydrolysis of
HgII or AuI complexes with cationic bis-phosphonio-
benzophospholide ligands [8Ϫ10].
Fig. 2 Molecular structure of 12. Thermal ellipsoids are drawn at
50 % probability level, and H atoms have been omitted for clarity.
˚
Selected bond lengths/A: W1 C61 1.957(6), W1 C62 2.039(5), W1 C63
1.983(5), W1 C64 2.038(5), W1 C40 2.454(6), W1 P1 2.4130(11), P1 C9
1.710(4), P1 C2 1.722(4), P3 C9 1.754(4), P2 C2 1.752(4), C8 C9 1.431(5),
C8 C3 1.436(6), C2 C3 1.457(5).
Considering that complexes of zerovalent metal frag-
ments with bis-phosphonio-benzophospholides are more
stable towards hydrolysis than those with divalent metals
[7], we explored the reactions of 2c with [W(CO)4(COD)]
and [Pt(PPh3)2(C2H4)]. Whereas the Pt0 complex did not
react at all, the reaction of 2c with the W0 complex gave,
according to 31P NMR studies, a mixture of three phos-
phorus containing species. Whereas IR spectra showed νCO
bands indicating the presence of a cis-W(CO)4-fragment in
the major product, the absence of 183W satellites on any of
the signals attributable to the ring phosphorus atoms ex-
cluded that a chelate complex with a κ2-P, C -coordinated
ligand had formed3). As all attempts towards isolation of
pure products, or unequivocal spectroscopic identification
of the species in the reaction mixture remained unsuccess-
ful, the reaction was not pursued further. Similar results
were also obtained for the reaction of 2c with
[Cr(CO)4(nbd)].
and characterized by analytical and spectroscopic data and
a single-crystal X-ray diffraction study. Exclusive formation
of 12 was also observed during the reaction of 2d with a
slight excess of [W(CO)3(toluene)]. The absence of any spec-
ies with η5-coordinated cyclopentadienyl rings [11] in this
reaction owes presumably to the high degree of benzannel-
ation, as coordination of a metal atom to the five-mem-
bered ring would result in a very unfavorable loss of local
aromaticity in the adjacent six-membered rings.
The 31P NMR data of 12 reveal as most characteristic
features a deshielding of the resonance of the ylide phos-
phorus atom by some 15 ppm, and the presence of 183W
satellites with substantially different couplings between the
metal and the ring phosphorus (1JWP ϭ 240 Hz) and the
ylide phosphorus atoms (2JWP ϭ 3 Hz), respectively. The
13C NMR spectrum displays a characteristic set of three
signals with relative intensities of 1:2:1 for the cis-W(CO)4
unit, and the signal of the ylide carbon atom displays a
moderate negative coordination shift (∆δ ϭ Ϫ16) and a re-
The successful synthesis of a complex with a P, C -chelat-
ing phosphonio-benzophospholide-ylide ligand was finally
achieved by reacting [W(CO)4(COD)] with 2d to give 12
(Scheme 4) as the only detectable product. The complex was
isolated after layering the reaction mixture with hexanes,
1
duction of the magnitude of JPC from 127 to 42 Hz as
compared to 2d.
The molecular structure of 12 (Figure 2) bears close simi-
larities to that of the complex 13 [1] (cf. Scheme 1) with a
P, S -chelating phosphonio-benzophospholide ligand.
Common features in the structures of both complexes in-
clude the bidentate coordination of a cis-W(CO)4 unit by a
P, E -chelating ligand whose small bite angle (12: E ϭ C; P1-
W1-C40 77.6(1)°; 13: E ϭ S; P1-W1-S1 79.9(1)° [1]) induces
a “bent” coordination of the phosphorus atom (as illus-
3) As one of the products was also formed as the major product of
the reaction of 2c with [W(CO)5(cyclooctene)] and the IR data gave
evidence for the formation of a pentacarbonyl complex as side
product, the constitution of this species was tentatively assigned as
the ylide complex [W(CO)5(κ1-C-2c)].
1972
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Ylidyl-substituted Phosphonio-benzophospholides as Chelating Ligands
trated by the large difference in C9-P1-W1 (120.0(2)°) and
C2-P1-W1 (145.7(2)°) angles) and a marked deviation from
a regular octahedral coordination polyhedron at the metal
atom. The five-membered chelate rings adopt flat twist-con-
formations whose planarization (which might help to re-
duce the distortion in the metal coordination sphere) is pre-
sumably prevented by steric interference between the ancil-
lary CO ligands and the bulky Ph3P-group. The “intra-li-
The compounds may coordinate as bidentate chelating li-
gands to a transition metal atom, even though the struc-
tural features of a W0 complex suggest that the bonding is
hampered by a geometrical mismatch between the ligand
and the metal, and substantial steric crowding.Complexes
of PtII and PdII formed display further a high liability to
undergo reactions under addition to the benzophospholide
π-electron system which could limit their use in catalytic ap-
plications.
˚
˚
gand” bonds P1-C9 (12: 1.710(4) A; 13 [1]: 1.722(6) A) and
˚
˚
C9-P3 (12: 1.754(4) A; 13: 1.760(6) A) in the chelate rings
are similar in both complexes whereas the W1-P bond in 12
˚
(2.4130(11) A) is measurably shorter than in 13
(2.4605(15) A). The W1-E (12: 2.454(6) A; 13: 2.602(3) A)
Experimental Section
˚
˚
˚
˚
˚
General Remarks: All manipulations were carried out under dry
argon. Solvents were dried by standard procedures. NMR spectra:
Bruker DPX 400 (1H: 400.13 MHz, 31P 161.9 MHz, 13C:
100.3 MHz) or AC 250 (1H: 250 MHz, 31P 101.2 MHz) in thf-D8
at 30 °C; chemical shifts referenced to ext. TMS (1H, 13C), 85 %
H3PO4 (Ξ ϭ 40.480747 MHz, 31P); positive signs of chemical shifts
denote shifts to lower frequencies, coupling constants are given as
absolute values; prefixes i-, o-, m-, p- denote atoms of phenyl sub-
stituents, and atoms in the benzophospholide ring are denoted as
and P3-E bond distances (12: 1.824(5) A; 13: 2.015(2) A)
reflect the larger covalent radius of a sulfur as compared to
a carbon atom and are thus longer in 13. Further unique
structural features of 12 include a marked non-linearity in
the trans-W(CO)2-unit (C62-W1-C64 168.0(2)°) and the
presence of close non-bonding contacts involving these car-
bonyls and the fluorenylidene moiety (C64-C42 3.08 A,
C62-C52 3.31 A). These interactions are considerably
shorter than the sum of van-der-Waals radii (3.50 A) and
˚
˚
˚
1
C-4, 5-H, etc. The assignment of H, 13C and 31P resonances was
verified from two-dimensional 1H,1H COSY, 1H,31P and 1H,13C
HMQC, and 1H,13C HMBC NMR spectra where necessary. MS:
Kratos Concept 1H, Xe-FAB, m-NBA matrix. IR spectra: Perkin-
Elmer Paragon FT-IR spectrometer. Elemental analysis: Perkin-
Elmer 2400 CHSN/O Analyser. Melting points were determined in
sealed capillaries.
suggest that the non-linear distortion of the trans-W(CO)2-
unit is a consequence of a significant repulsive interference
between the carbonyls and the fluorenylidene moiety. Com-
parison of the structural data of 12 with further literature
data reveals that the W1-C40 and P3-C40 distances in 12
are much longer than average bond lengths in known tung-
sten complexes with phosphonium ylide ligands (W-C 2.30
4)
˚
˚
0.06 A; C-P 1.78 0.02 A ).
General procedure for the preparation of the
phosphonium salts 6a-d.
On the whole, the observed structural features of 12 sug-
gest rather weak bonding between the tungsten atom and
both donor atoms of the chelate ligand whose origin may
be related to two major sources, viz. (i) the mismatch of the
bite angle and the alignment of the coordinating lone-pairs
in the chelate ligand with respect to the steric requirements
of the metal atom, and (ii) additional steric strain resulting
from interference between the ancillary carbonyl ligands
with the bulky triphenylphosphonio- and fluorenylidene-
moieties in the chelate ligand. Comparison of the structural
parameters of the closely related complexes 12 and 13 indi-
cates that the importance of steric strain may be somewhat
more pronounced for the former.
One equivalent of the appropriate alkyl halide was added to a
stirred solution of 5 (0.20 to 2.00 g) in toluene (15 to 50 ml). The
solution was gently warmed (6a) or refluxed (6b-d), and stirring
was continued until a pale yellow to white precipitate separated.
The product was collected by filtration, washed with hexane (20 ml)
and ether (20 ml), and dried in vacuum.
The spectroscopic data of 6a,b were described previously [1].
[3-(Cyanomethyl-diphenyl-phosphonio)-1-triphenylphosphonio-
benzo[c]phospholide] chloride (6c). Colorless solid, yield 87 %, mp
234 °C. Ϫ
Anal. for C40H30ClNP3 (653.7): calcd. C 73.46 H 4.67 N 2.62 %;
found: C 67.37 H 4.78 N 2.14 %.
2
2
31P NMR: δ ϭ 237.9 (dd, JPP ϭ 90.2, 92.9 Hz, P-2), 11.9 (dd, JPP
ϭ
Conclusions
4
2
4
92.2 Hz, JPP ϭ 8.3 Hz, PPh2), 10.0 (dd, JPP ϭ 90.9 Hz, JPP ϭ 8.3 Hz,
PPh3). Ϫ 1H NMR (CD2Cl2): δ ϭ 8.07 (m, 4 H, o-H(PPh2)), 7.76Ϫ7.52
(m, 15 H, H(PPh3)), 7.25 (m, 2 H, p-H(PPh2)), 7.15 (m, 4 H, m-H(PPh2)),
7.12Ϫ6.88 (m, 4 H, 4-H Ϫ 7-H), 5.41 (d, 2 H, JPH ϭ 14.2 Hz, PCH2CN). Ϫ
13C{1H} NMR (CD2Cl2): δ ϭ 144.2 (ddd, JPC ϭ 16.9, 8.8, 2.2 Hz, C-7a/3a),
The synthesis and coordination abilities of phosphonio-
benzophospholide zwitterions with an additional ylide sub-
stituent in 3-position have been demonstrated. The stability
of these species depends crucially on the electronic stabiliz-
ation of the ylide moiety by electron withdrawing substitu-
ents or incorporation into a delocalized π-electron system.
4
144.0 (ddd, JPC ϭ 16.2, 9.3, 1.5 Hz, C-7a/3a), 134.5 (d, JPC ϭ 3.2 Hz, p-
4
2
C(PPh2)), 134.2 (d, JPC ϭ 3.2 Hz, p-C(PPh3)), 133.9 (dd, JPC ϭ 10.5 Hz,
4JPC ϭ 1.1 Hz, o-C(PPh3)), 133.6 (d, 2JPC ϭ 11.0 Hz, o-C(PPh2)), 129.8 (d,
3JPC ϭ 12.8 Hz, m-C(PPh3)), 129.7 (d, JPC ϭ 13.1 Hz, m-C(PPh2)), 122.7
3
(dd, 1JPC ϭ 90.8 Hz, 3JPC ϭ 2.9 Hz, I-C(PPh3)), 121.7 (s, C-4 -C-7), 121.6 (s,
1
C-4ϪC-7), 121.2 (d,JPC ϭ 2.6 Hz, C-4ϪC-7), 121.0 (dd, JPC ϭ 90.0 Hz,
3JPC ϭ 2.6 Hz, i-C(PPh2)), 120.5 (m, C-4ϪC-7), 112.8 (d, JPC ϭ 8.9 Hz,
2
1
3
CN), 110.9 (ddd, JPC ϭ 55.5 Hz, 96.0 Hz, JPC ϭ 15.0 Hz, C-1/3), 106.7
(ddd, 1JPC ϭ 57.2, 94.3 Hz, 3JPC ϭ 14.8 Hz, C-1/3), 19.1 (dd, 1JPC ϭ 56.8 Hz,
3JPC ϭ 7.4 Hz, PCH2). Ϫ MS ((ϩ)-Xe-FAB, mNBA): m/z ϭ 618 (100 %,
C40H30P3Nϩ). Ϫ
4) Average and standard deviation as result of a query in the CSD
database for complexes with the structural fragment R3PϪCX2ϪW
(X ϭ any group; R ϭ alkyl or aryl)
Z. Anorg. Allg. Chem. 2004, 630, 1969Ϫ1976
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1973

Z. Bajko, D. Gudat, F. Lissner, M. Nieger, Th. Schleid
[3-{(9-Fluorenyl)-diphenylphosphonio}-1-triphenylphosphonio-
benzo[c]phospholide] bromide (6d). Light yellow solid, yield 83 %,
mp 234 °C. Ϫ
Anal. for C51H38BrP3 (823.1): calcd. C 72.84 H 4.65 %, found: C
74.37 H 5.18 %.
3-(9-Fluorenylidene)-diphenylphosphonio-1-triphenylphosphonio-
benzo[c]phospholide (2d). A solution of sodium trimethylsilyl amide
(0.14 g, 0.77 mmol) in 20 ml of toluene was added via syringe to a
stirred suspension of 6d (0.60 g, 0.73 mmol) in 20 ml of toluene.
The mixture was gently warmed to 80 °C, and stirring was con-
tinued until a white-brown precipitate separated and the solution
become yellow. The precipitate was filtered off and washed with
toluene. The combined yellow filtrates were refluxed for 12 h, al-
lowed to cool to room temperature, and filtered again. The filtrate
was concentrated in vacuum and crystallised at Ϫ22 °C. The pre-
cipitated yellow crystals were collected by filtration, washed with
20ml of cold n-hexane, and dried in vacuum to give 0.34 g (63 %)
of 4d of mp 217 °C (dec). Ϫ
31P{1H} NMR: δ ϭ 237.2 (dd, 2JPP ϭ 92.5, 75.3 Hz, P-2), 22.3 (dd, 2JPP ϭ
4
2
4
75.3 Hz, JPP ϭ 8.0 Hz, PPh2P), 16.4 (dd, JPP ϭ 92.5 Hz, JPP ϭ 8.0 Hz,
PPh3). Ϫ 1H NMR (CD2Cl2): δ ϭ 7.70 (m, 3 H, p-H(PPh3)), 7.57 (m, 6 H,
o-H(PPh3)), 7.58 (m, 6 H, m-H(PPh3)), 7.54 (m, 4 H, o-H(PPh2)), 7.53 (m,
2 H, p-H(PPh2)), 7.50 (m, 2 H, Fl-H), 7.38 (m, 4 H, m-H(PPh2)), 7.22 (m,
2 H, Fl-H), 6.94 (m, 2 H, 4-HϪ7-H), 6.90 (m, 4 H, Fl-H), 6.65 (m, 2 H, 4-
H Ϫ7-H), 6.16 (dd, 1 H, JPH ϭ 16.7, 1.2 Hz, Fl-H). Ϫ 13C{1H} NMR
(CD2Cl2): δ ϭ 144.9 (ddd, JPC ϭ 16.3, 7.9, 2.1 Hz, C-7a/3a), 144.1 (ddd,
J
PC ϭ 16.5, 8.5, 1.8 Hz, C-7a/3a), 142.8 (dd, JPC ϭ 4.9, 1.1 Hz, Fl-C), 137.2
4
(d, JPC ϭ 4.6 Hz, Fl-C), 134.5 (d, JPC ϭ 3.1 Hz, p-C(PPh3)), 134.3 (dd,
Anal. for C51H37P3 (743.0): calcd. C 82.47 H 5.02 %, found C
80.18 H 5.56 %.
2JPC ϭ 10.5 Hz, JPC ϭ 1.1 Hz, o-C(PPh3)), 134.2 (d, JPC ϭ 3.1 Hz, p-
C(PPh2)), 133.8 (d, 2JPC ϭ 9.6 Hz, o-C(PPh2)), 130.0 (d, 3JPC ϭ 12.6 Hz, m-
C(PPh3)), 129.6 (d, 3JPC ϭ 12.4 Hz, m-C(PPh2)), 129.3 (d, JPC ϭ 2.5 Hz, Fl-
C), 127.4 (d, JPC ϭ 2.7 Hz, Fl-C), 127.0 (dd, JPC ϭ 3.9 Hz, Fl-C), 122.7 (dd,
1JPC ϭ 90.6 Hz, 3JPC ϭ 3.1 Hz, i-C(PPh3)), 121.4 (m, C-4ϪC-7), 121.3 (dd,
1JPC ϭ 85.2 Hz, 3JPC ϭ 2.6 Hz, i-C(PPh2)), 120.6 (d, 3JPC ϭ 1.3 Hz, Fl-C),
120.5 (s, C-4ϪC-7), 110.3 (ddd, 1JPC ϭ 95.8, 54.8 Hz, 3JPC ϭ 13.1 Hz, C-1/
3), 108.0 (ddd, 1JPC ϭ 87.9, 58.7 Hz, 3JPC ϭ 15.7 Hz, C-1/3), 45.8 (dd, 1JPC ϭ
4
4
2
2
31P{1H} NMR: δ ϭ 233.2 (dd, JPP ϭ 88.5, 87.7 Hz, P-2), 16.3 (dd, JPP
ϭ
4
2
4
88.5 Hz, JPP ϭ 8.0 Hz, PPh3), 0.8 (dd, JPP ϭ 88.5 Hz, JPP ϭ 8.0 Hz,
PPh2). Ϫ 1H NMR (CD2Cl2): δ ϭ 8.06 (m, 2 H, Fl-H), 7.77 (m, 4 H, o-
H(PPh2)), 7.61 (m, 3 H, p-H(PPh3)), 7.58 (m, 6 H, o-H(PPh3)), 7.46 (m, 6 H,
m-H(PPh3)), 7.42 (m, 2 H, p-H(PPh2)), 7.31 (m, 4 H, m-H(PPh2)), 7.22 (m,
1 H, 4/7-H), 6.94 (m, 1 H, 4/7-H), 6.85 (m, 2 H, Fl-H), 6.76 Ϫ 6.74 (m, 3 H,
5/6-H ϩ Fl-H), 6.70 (m, 1 H, 5/6-H), 6.47 (m, 2 H, Fl-H). Ϫ 13C{1H} NMR
(CD2Cl2): δ ϭ 146.0 (ddd, JPC ϭ 16.8, 8.7, 4.4 Hz, C-3a/7a), 144.8 (dd,
2JPC ϭ 14.8, 9.1 Hz, C-3a/7a), 141.9 (d, JPC ϭ 15.1 Hz, Fl-C), 134.7 (dd,
3
49.4 Hz, JPC ϭ 6.8 Hz, Fl-C). Ϫ MS ((ϩ)-Xe-FAB, mNBA): m/z ϭ 743
(100 %, C51H38P3ϩ). Ϫ
4
4
2JPC ϭ 10.3 Hz, JPC ϭ 2.1 Hz, o-C(PPh2)), 134.0 (d, JPC ϭ 2.9 Hz, p-
1-Methylenediphenylphosphonio-3-triphenylphosphonio-benzo[c]-
phospholide (2a). A solution of sodium trimethylsilyl amide (0.24 g,
1.31 mmol) in 15 ml of toluene was added via syringe to a cooled
(Ϫ78 °C) and stirred suspension of 6a (0.70 g, 1.18 mmol) in 40 ml
of toluene. The mixture was allowed to warm to room-temperature,
and stirring was continued for 24 hours. The precipitated solids
were filtered off, and the crude product identified by means of
NMR spectroscopy in the filtrate.
2
4
C(PPh3)), 133.4 (dd, JPC ϭ 10.3 Hz, JPC ϭ 1.3 Hz, o-C(PPh3)), 131.9 (d,
4JPC ϭ 2.9 Hz, p-C(PPh2)), 130.1 (d, JPC ϭ 13.8 Hz, Fl-C), 130.0 (dd, 1JPC ϭ
89.0 Hz, JPC ϭ 3.0 Hz, i-C(PPh2)), 129.8 (d, 3JPC ϭ 12.4 Hz, m-C(PPh3)),
3
3
1
3
128.8 (d, JPC ϭ 12.0 Hz, m-C(PPh2)), 124.1 (dd, JPC ϭ 90.1 Hz, JPC
ϭ
2.5 Hz, i-C(PPh3)), 123.3 (ddd, 1JPC ϭ 93.9, 52.6 Hz, 3JPC ϭ 13.8 Hz, C-3),
122.5 (s, Fl-C), 122.4 (m, C-4/7), 120.7 (d, JPC ϭ 1.9 Hz, C-5/6), 120.4 (s, C-
5/6), 119.5 (dd, JPC ϭ 5.2, 1.3 Hz, C-4/7), 119.3 (d, JPC ϭ 1.3 Hz, Fl-C),
1
3
117.3 (s, Fl-C), 115.1 (s, Fl-C), 102.9 (ddd, JPC ϭ 97.4, 56.6 Hz, JPC
13.6 Hz, C-1), 59.6 (dd, JPC ϭ 126.8 Hz, JPC ϭ 3.5 Hz, C-9(Fl)). Ϫ MS
((ϩ)-Xe-FAB, mNBA): m/z ϭ 743 (100 %, Mϩ). Ϫ
ϭ
1
3
2
2
31P NMR: δ ϭ 229.0 (dd, JPP ϭ 87.7, 82.0 Hz, P-2), 16.6 (dd, JPP
ϭ
4
2
4
82.0 Hz, JPP ϭ 6.7 Hz, PPh2), 13.7 (dd, JPP ϭ 87.7 Hz, JPP ϭ 6.7 Hz,
PPh3). Ϫ 1H NMR (C6D6): 7.94 (m, 4 H o-H(PPh2)), 7.79 (m, 2 H, p-
H(PPh2)), 7.47Ϫ7.41 (m, 12 H, m/o-H(PPh3)), 7.07 (m, 4 H, m-H(PPh2)),
6.87 (m, 3 H, p-H(PPh3)), 6.87Ϫ6.78 (m, 4 H, 4-H Ϫ 7-H), 0.81 (br d, 2 H,
2JPH ϭ 7 Hz, PCH2).
Reaction of 2a with Chlorodiphenylphosphine
Chlorodiphenylphosphine (0.22 g, 1.05 mmol) dissolved in 15 ml of
toluene was added to a solution of 2a (0.50 g, 0.85 mmol) in 20 ml
of toluene and the reaction mixture was stirredfor 24 h at room
temperature. The white precipitate formed was filtered off and
washed with 10 ml of cold toluene. A sample of the product was
dissolved in CH2Cl2 and shown by 31P{1H} and 1H,31P HMQC
NMR spectroscopy to consist of a mixture of the phosphonium
salts 6a and 6e, respectively. The product mixture was then again
suspended in 30 ml of toluene, 0.20 g (1.1 mmol) of NaN(SiMe3)2
dissolved in 10 ml of toluene were added, and the mixture was
stirred for 48 hours. The brown precipitate formed was filtered off,
washed with 10 ml of cold toluene, and dried in vacuum. The ylide
2e was identified in the crude product by 31P NMR and mass spec-
troscopy. Ϫ
3-{(1-Cyanomethylene)-diphenyl-phosphonio}-1-triphenylphos-
phonio-benzo[c]phospholide (2c). A solution of sodium trimethylsilyl
amide (0.14 g, 0.77 mmol) in 20 ml of toluene was added via syr-
inge to a cooled (Ϫ78 °C) and stirred suspension of 6c (0.50 g,
0.77 mmol) in 20 ml of toluene. The mixture was allowed to warm
to room-temperature, and stirring was continued for 24 hours. The
precipitated solids were filtered off and washed with 10 ml of THF.
The filtrate was evaporated to dryness to give 0.43 g (91 %) of a
brown solid of mp 156 °C (dec). Ϫ
Anal. for C40H30P3N1 (617.2): calcd. C 77.79 H 4.90 N 2.27 %;
found C 76.46 H 5.20 N 2.36 %.
31P{1H} NMR: δ ϭ 232.9 (dd, 2JPP ϭ178.9, 89.5 Hz, P-2), 16.1 (dd, 2JPP ϭ
4
2
4
6e: 31P{1H} NMR: δ ϭ 237.8 (ddd, 2JPP ϭ 92.5, 82.0 Hz, 4JPP ϭ 41.9 Hz, P-
178.9 Hz, JPP ϭ 7.6 Hz, PPh3), 14.6 (dd, JPP ϭ 89.5 Hz, JPP ϭ 7.6 Hz,
PPh2). Ϫ 1H NMR (THF-d8): δ ϭ 8.14Ϫ7.91 (m, 12 H, m/o-H(PPh3)),
7.91Ϫ7.77 (m, 7 H, o-H(PPh2)/p-H(PPh3)), 7.76Ϫ7.61 (m, 6 H, m/p-
H(PPh2)), 7.61 (m, 1 H, 4-H Ϫ 7-H), 7.25 Ϫ 7.05 (m, 2 H, 4-H Ϫ 7-H), 7.00
2
2), 17.2 (dd, 2JPP ϭ 92.5 Hz, 4JPP ϭ7.6 Hz, PPh3), 16.1 (ddd, JPP ϭ 82.0,
4
2
4
69.6 Hz, JPP ϭ 7.6 Hz, PPh2), -26.6 (dd, JPP ϭ 69.6 Hz, JPP ϭ 41.9 Hz,
P(Phosphanyl)). Ϫ
2
4
(m, 1 H, 4-H Ϫ 7-H), 1.77 (dd, 1 H, JPH ϭ 9.0 Hz, JPH ϭ 0.8 Hz,,
PCHCN). Ϫ 13C{1H} NMR (THFd8): δ ϭ 145.9 (ddd, JPC ϭ 13.2, 8.4,
4.7 Hz, C-3a/7a), 145.4 (dd, JPC ϭ 14.7, 8.9 Hz, C-3a/7a), 135.1 (dd, 2JPC ϭ
2e: 31P{1H}NMR: δ ϭ 237.8 (ddd, 2JPP ϭ 90.1, 81.5 Hz, 4JPP ϭ 10.0 Hz, P-
2), 21.0 (dd, 2JPP ϭ 90.1 Hz, 4JPP ϭ 8.6 Hz, PPh3), 20.9 (ddd, 2JPP ϭ 81.5,
151.6 Hz, 4JPP ϭ 8.6 Hz, PPh2), Ϫ11.5 (dd, 2JPP ϭ 151.6 Hz, 4JPP ϭ 10.0 Hz,
10.5 Hz, JPC ϭ 1.6 Hz, o-C(PPh3)), 134.4 (d, 4JPCϭ 3.6 Hz, p-C(PPh3)),
4
1
3
2
P(Phosphanyl)); MS: ((ϩ)-Xe-FAB, mNBA): m/z(%)
ϭ 777 (100 %,
133.9 (dd, JPC ϭ 89.4 Hz, JPC ϭ 2.6 Hz, i-C(PPh2)), 133.6 (dd, JPC
ϭ
(MϩH)ϩ).
4
4
10.0 Hz, JPC ϭ 1.6 Hz, o-C(PPh2)), 131.8 (d, JPC ϭ 2.6 Hz, p-C(PPh2)),
130.3 (d, 3JPC1 ϭ 12.1 Hz, m-C(PPh3)), 128.9 (d, 3JPC ϭ 12.1 Hz, m-C(PPh2)),
3
2
127.5 (ddd, JPC ϭ 98.7, 52.9 Hz, JPC ϭ 13.8 Hz, C-3); 127.0 (d, JPC
ϭ
1
3
8.0 Hz, CN), 125.3 (dd, JPC ϭ 89.9 Hz, JPC ϭ 2.6 Hz, i-C(PPh3)), 123.2
(dd, JPC ϭ 4.5, 4.5 Hz, C-4ϪC-7), 121.2 (d, JPC ϭ 4.2 Hz, C-4ϪC-7), 120.8
Reaction of 2c with [PdCl2(COD)]
1
(d, JPC ϭ 2.1 Hz, C-4ϪC-7), 120.4 (s, C-4ϪC-7), 102.3 (ddd, JPC ϭ 97.9,
57.5 Hz, JPC ϭ 14.2 Hz, C-1), 0.12(dd, JPC ϭ 136.5 Hz, 3JPCϭ 6.6 Hz,
3
1
To a toluene solution (20 ml) of 2c (0.50 g, 0.81 mmol) was added
[PdCl2(cod)] (0.23 g, 0.84 mmol). The resulting solution was stirred
PCH). Ϫ MS ((ϩ)-Xe-FAB, mNBA): m/z ϭ 618 (100 %, [MϩH]ϩ). Ϫ
1974
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2004, 630, 1969Ϫ1976

Ylidyl-substituted Phosphonio-benzophospholides as Chelating Ligands
for 3 d at room temperature. Reaction control by 31P NMR allowed
3JPC ϭ 5.2 Hz, i-C(PPh2)), 125.0 (dd, JPC ϭ 2.6 Hz, 1.4 Hz, Fl-C), 124.7 (d,
J
PC ϭ 2.3 Hz, Fl-C), 122.5 (dd, 1JPC ϭ 90.8 Hz, 3JPC ϭ 2.5 Hz, i-C(PPh3)),
121.7 (d, JPC ϭ 2.7 Hz, Fl-C), 120.9 (m, C-5/6), 120.5 (d, JPC ϭ 8.4 Hz, C-
5/6), 120.0 (d, JPC ϭ 1.1 Hz, C-4/7), 119.8 (s, Fl-C), 119.5 (ddd, JPC ϭ 6.40,
to monitor the formation of the complex 7 and the hydrolysis prod-
ucts 9a,b. The formation of the latter was complete after 3 d. The
mixture was then layered with 10 ml of hexane and stored until
a light yellow precipitate formed. This product was collected by
filtration, washed with 20 ml of hexane, and dried in vacuum to
give 0.58 g (yield 88 %) ofa mixture of the diastereomers 9a,b.
3.3, 0.7 Hz, C-4/7), 96.6 (ddd, JPC ϭ 103.7, 56.6 Hz, 3JPC ϭ 9.1 Hz, C-1),
1
43.6 (dd, 1JPC ϭ 42.3 Hz, 3JPC ϭ 2.6 Hz, Fl-C9), IR: (CH2Cl2, NaCl): ν(CO)
2003, 1901, 1882, 1839 cmϪ1. Ϫ MS ((ϩ)-Xe-FAB, mNBA): m/z ϭ 1038
(18 %, Mϩ), 1011 (22 %, Mϩ Ϫ CO), 982 (100 %, Mϩ Ϫ 2 CO).
2
2
7: 31P{1H} NMR: δ ϭ 191.9 (dd, JPP ϭ 110.6, 55.9 Hz), 23.3 (dd, JPP
ϭ
4
2
4
55.9 Hz, JPP ϭ 4.5 Hz, PPh3), 14.7 (dd, JPP ϭ 110.6 Hz, JPP ϭ 4.5 Hz,
PPh2). Ϫ 1H NMR (CD2Cl2): δ ϭ 8.11-7.60 (m, 25H, Ph), 7.7 (m, 1H, 4-H
Ϫ 7-H), 7.34-6.94 (m, 3H, 4-H Ϫ 7-H), 4.21 (m, 1H, CHCN). Ϫ
Crystal structure determinations:
10a: colorless crystals, C40H32Cl2NOP3Pt Ϫ 3 C4H8O, M ϭ 1117.9,
2
9a,b: isomer 1: 31P{1H} NMR: δ ϭ 91.8 (dd, JPP ϭ 16.5 Hz, 42.0 Hz, P-2),
¯
crystal size 0.15 x 0.10 x 0.05 mm, rhombohedral, space group R3
2
4
2
3
40.6 (dd, JPP ϭ 42.0 Hz, JPP ϭ 2.5 Hz, PPh2), 23.8 (dd, JPP ϭ 16.5 Hz,
4JPP ϭ 2.5 Hz, PPh3); Ϫ 1H NMR (CD2Cl2): δ ϭ 7.93-7.74 (m, 12H o,m-
H(PPh3)), 7.81-7.68 (m, 10H, H(PPh2)), 7.68-7.56 (m, 3H, p-H(PPh3)), 7.01-
7.15 (m, 3H, 4-H Ϫ 7-H), 6.91 (m, 1H, 4-H Ϫ 7-H), 6.29 (m, 1H, 1-H), 3.62
(m, 1H, CHCN), 3.04 (m, 1H, 3-H); isomer 2: 31P{1H} NMR: δ ϭ 86.2 (dd,
˚
˚
(No. 148): a ϭ 20.8201(3) A, Ͱ ϭ 107.773(1)°, V ϭ 7351.9(2) A ,
Z ϭ 6, ρ(calcd) ϭ 1.515 Mg mϪ3, F(000) ϭ 3384, µ ϭ 3.11 mmϪ1
,
70566 reflexes (2 θmax ϭ 50.0°) measured on a Nonius Kappa-CCD
˚
diffractometer at 123(2) K using MoKα radiation (λ ϭ 0.71073 A),
2JPP ϭ 18.4, 42.6 Hz, P-2), 36.2 (dd, JPP ϭ 42.6 Hz, JPP ϭ 2.5 Hz, PPh2),
2
4
8631 unique [Rint ϭ 0.105] used for structure solution (Direct
Methods, SHELXS-97 [12]) and refinement (full-matrix least-
squares on F2, SHELXL-97 [12]) with 524 parameters and 96 re-
straints, empirical absorption correction from multiple reflections,
H-atoms with a riding model, R1 (I > 2σ(I)) ϭ 0.046, wR2 ϭ 0.125,
23.0 (dd, JPP ϭ 18.4 Hz, JPP ϭ 2.5 Hz, PPh3); Ϫ 1H NMR (CD2Cl2): δ ϭ
8.04-7.92 (m, 4H, o-H(PPh2)), 7.93-7.68 (m, 18H, m,p-H(PPh3/PPh2)), 7.68-
7.56 (m, 3H, p-H(PPh3)), 7.15-7.01 (m, 3H, 4-H Ϫ 7-H), 6.91 (m, 1H, 4-H
Ϫ 7-H), 6.68 (m, 1H, 1-H), 3.40 (m, 1H, CHCN), 3.14 (m, 1H, 3-H); Ϫ MS:
((ϩ)-Xe-FAB, mNBA): m/z(%) ϭ 776 (64 %, MϩϪCl).
2
4
Ϫ3
˚
largest diff. peak and hole 1.316 and Ϫ0.788 e A
.
12: colorless crystals, C55H37O4P3W, M ϭ 1038.6, monoclinic,
space group Cc (No. 9): a ϭ 23.0640(3) A, b ϭ 10.5804(1) A, c ϭ
Reaction of 2c with [PtCl2(COD)]
˚
˚
3
˚
˚
The reaction of 2c (0.50 g, 0.81 mmol) and [PtCl2(cod)] (0.31 g,
0.83 mmol) was carried out as described above. Stirring the solu-
tion for 12 h produced a small amount of a crystalline light yellow
precipitate which was collected and identified as the hydrolysis
product 10a by single-crystal X-ray diffraction. Reaction control
by 31P NMR allowed to monitor the formation of the complex 8
and the hydrolysis products 10a,b. Prolonged stirring resulted in
the formation of a larger amount of a colorless precipitate that was
insoluble in polar and unpolar organic solvents and water and was
not further characterized.
20.5278(2) A, β ϭ 118.861(1)°, V ϭ 4387.13(8) A , Z ϭ 4,
ρ(calcd) ϭ 1.572 Mg mϪ3, F(000) ϭ 2072, µ ϭ 2.79 mmϪ1, Flack
x ϭ Ϫ0.0167(43), 55573 reflexes (2 θmax ϭ 54.9°) measured on a
Nonius Kappa-CCD diffractometer at 100(2) K using MoKα radi-
˚
ation (λ ϭ 0.71073 A), 9859 unique [Rint ϭ 0.095] used for structure
solution (Direct Methods, SHELXS-97 [12]) and refinement (full-
matrix least-squares on F2, SHELXL-97 [12]) with 569 parameters
and 2 restraints, numerical absorption correction [13], H-atoms
with a riding model, R1 (F0 > 4σ(F0)) ϭ 0.030, wR2 ϭ 0.071,
Ϫ3
˚
largest diff. peak and hole 1.348 and Ϫ1.191 e A
.
8: 31P{1H} NMR: δ ϭ 184.7 (dd, 2JPP ϭ 50.2, 101.1 Hz, 1JPtP ϭ 4658 Hz, P-
Crystallographic data (excluding structure factors) for the struc-
tures reported in this work have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication no.
CCDC-239656 (11a) and CCDC-240286 (13). Copies of the data
can be obtained free of charge on application to The Director,
CCDC, 12 Union Road, Cambridge DB2 1EZ, UK (Fax:
int.codeϩ(1223)336-033; e-mail:teched@chemcrys.cam.ac.uk).
2
4
2
2), 23.3 (dd, JPP ϭ 101.1 Hz, JPP ϭ 3.8 Hz, PPh2), 14.9 (dd, JPP
ϭ
4
50.2 Hz, JPP ϭ 3.8 Hz, PPh3). Ϫ
2
1
10a,b: isomer 1: 31P{1H} NMR: δ ϭ 60.7 (dd, JPP ϭ 34.9, 12.1 Hz, JPtP
ϭ
2
4
3616 Hz, P-2), 41.8 (dd, JPP ϭ 34.9 Hz, JPP ϭ 6.4 Hz, PPh2), 23.4 (dd,
2JPP ϭ 12.1 Hz, JPP ϭ 6.4 Hz, PPh3); isomer 2: 31P{1H} NMR: δ ϭ 55.2
4
2
1
2
(dd, JPP ϭ 36.2, 13.4 Hz, JPtP ϭ 2118 Hz, P-2), 39.5 (dd, JPP ϭ 36.2 Hz,
4JPP ϭ 6.7 Hz, PPh2), 22.6 (dd, JPP ϭ 13.4 Hz, JPP ϭ 6.7 Hz, PPh3).
2
4
[Tetracarbonyl-κ2-P,C-{1-Triphenylphosphonio-3-Fluorenylidenedi-
phenylphosphonio-benzo[c]phospholide}tungsten(0)] (12). A solution
of [W(CO)4(nbd)] (0.50 g, 1.35 mmol) and 2d (1.00 g, 1.35 mmol)
in 40 ml of THF was stirred for 72 h at room temperature and then
layered with 10 ml of hexane. The brown precipitate formed after
diffusion of the solvents was collected by filtration, washed with
20 ml of hexane, and dried in vacuum. Recrystallization from
CH2Cl2 gave 1.00 g (yield 72 %) of 12, m.p. 228 °C (dec.). Ϫ
References
[1] Z. Bajko, J. Daniels, D. Gudat, S. Häp, M. Nieger, Organo-
metallics 2002, 21, 5182Ϫ5189.
[2] See: A. W. Johnson, Ylides and Imines of Phosphorus, Wiley:
New York 1993, 447ff; 485ff.
[3] R. Zurawinski, B. Donnadieu, M. Mikolajczyk, R. Chauvin,
Organometallics 2003, 22, 4810Ϫ4817.
[4] R. Zurawinski, B. Donnadieu, M. Mikolajczyk, R. Chauvin,
J. Organomet. Chem. 2004, 689, 380Ϫ386.
31P{1H} NMR: δ ϭ 238.3 (dd, 2JPP ϭ 103.8, 63.7 Hz, 1JWP ϭ 243.6 Hz, P-
2), 21.7 (dd, 2JPP ϭ 63.7 Hz, 4JPP ϭ 6.1 Hz, PPh3), 15.1 (dd, 2JPP ϭ 103.8 Hz,
4JPP ϭ 6.1 Hz, 2JWP ϭ 5.7 Hz, PPh2). 183W NMR: δ ϭ 2541 (1JWP ϭ 240 Hz).
Ϫ
1H NMR (CD2Cl2): δ ϭ 7.92 (m, 6 H, o-H(PPh3)), 7.77 (m, 2 H, Fl-H),
[5] D. Gudat, V. Bajorat, S. Häp, M. Nieger, G. Schröder, Eur. J.
Inorg. Chem. 1999, 1169Ϫ1174; S. Häp, L. Szarvas, M. Nieger,
D. Gudat, Eur. J. Inorg. Chem. 2001, 2763Ϫ2772.
[6] O. I. Kolodiazhnyi, Phosphorus Ylides Ϫ Chemistry and Ap-
plication in Organic Synthesis, Wiley-VCH: Weinheim 1999,
226ff.
[7] D. Gudat, S. Häp, V. Bajorat, M. Nieger, Z. Anorg. Allg.
Chem. 2001, 627, 1119Ϫ1127.
[8] D. Gudat, M. Nieger, M. Schrott, Inorg. Chem. 1997, 36,
1476Ϫ1481.
7.54 (m, 6 H, m-H(PPh3)), 7.62 (m, 3 H, p-H(PPh3)), 7.29 (m, 2 H, p-
H(PPh2)), 7.16 (m, 4 H, o-H(PPh2)), 7.11 (m, 4 H, m-H(PPh2)), 6.92 (m,
2 H, 4-H Ϫ 7-H), 6.88 (m, 2 H, Fl-H), 6.80 (m, 1 H, 4-H Ϫ 7-H), 6.77 (m,
4 H, Fl-H), 6.75Ϫ6.64 (m, 2 H, 4-H Ϫ 7-H). Ϫ 13C{1H} NMR (CD2Cl2):
δ ϭ 210.2 (dd, 2JPC ϭ 43.1 Hz, 3JPC ϭ 0.7 Hz, CO), 207.2 (dd, 2JPC ϭ 5.5 Hz,
3JPC ϭ 0.9 Hz, CO), 204.7 (d, CO, 2JPC ϭ 10.1 Hz), 154.9 (dd, 2JPC ϭ 2.9 Hz,
4JPC ϭ 1.3 Hz, Fl-C), 145.8 (ddd, JPC ϭ 14.4, 8.6, 3.8 Hz, C-3a/7a), 143.1
(ddd, JPC ϭ 14.9, 6.8, 2.4 Hz, C-3a/7a), 135.0 (d, 3JPC ϭ 8.2 Hz, Fl-C), 134.6
(d, 2JPC ϭ 10.1 Hz, o-C(PPh3)), 134.1 (d, 4JPC ϭ 3.1 Hz, p-C(PPh3)), 133.8
2
4
(d, JPC ϭ 8.8 Hz, o-C(PPh2)), 132.2 (d, JPC ϭ 2.9 Hz, p-C(PPh2)), 130.1
(d, 3JPC ϭ 12.6 Hz, m-C(PPh3)), 128.6 (d, 3JPC ϭ 11.7 Hz, m-C(PPh2)), 127.5
(ddd, 1JPC ϭ 98.3, 59.3 Hz, 3JPC ϭ 11.2 Hz, C-3), 126.4 (dd, 1JPC ϭ 79.5 Hz,
Z. Anorg. Allg. Chem. 2004, 630, 1969Ϫ1976
zaac.wiley-vch.de
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
1975

Z. Bajko, D. Gudat, F. Lissner, M. Nieger, Th. Schleid
[9] A. W. Holderberg, G. Schröder, D. Gudat, H.-P. Schrödel, A.
Schmidpeter, Tetrahedron 2000, 56, 57Ϫ62.
McEwen, C. E. Sullivan, R. O. Day, Organometallics 1983,
2, 420Ϫ425.
[10] D. Gudat, M. Nieger, M. Schrott, Chem. Ber. 1995, 128,
259Ϫ266.
[12] (a) G. M. Sheldrick, Acta Crystallogr. 1990, A46, 467Ϫ473;
(b) G. M. Sheldrick, Univ. Göttingen 1997.
[11] Cf. e.g.: J. C. Kotz, D. G. Pedrotty, J. Organomet. Chem. 1970,
22, 425Ϫ438, G. Bombieri, G. Tresoldi, F. Faraone, G. Bruno,
P. Cavoli-Belluco, Inorg. Chim. Acta 1982, 57, 1Ϫ7; W.E.
[13] X-SHAPE software by STOE, based on the program HABI-
TUS by W. Herrendorf, Univ. Giessen, 1995.
1976
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2004, 630, 1969Ϫ1976