Synthesis of (indenylidene)phosphoranes - A novel class of ligand precursors for main-group and transition metal organometallics

Article abstract of DOI:10.1002/ejic.200400664

IndPPh₂ (1) reacts with RCH₂Br to form the phosphonium salts [RCH₂P(Ph)₂Ind]⁺Br ^- (2: R = Ph; 3: R = C₆F₅) in high yields. Oxidation of 1 with H₂O₂ in THF proceeds smoothly to give the phosphane oxide IndP(O)Ph₂ (4). Dehydrobromination of 2 and 3 with NaH in THF yields the corresponding indenylidenephosphoranes C ₉H₆=P(Ph)₂CH₂R (5: R = Ph; 6: R = C₆F₅). Further deprotonation of 6 with excess NaH results in formation of sodium 1-{[(pentafluorophenyl)methylidene]diphenylphosphoranyl} indenide (7), isolated as a solvate with three THF molecules. A detailed NMR study of new ligand precursors and X-ray structure studies of 5 and 7 have been accomplished. A short F→Na coordination contact in the molecular structure of 7 has been detected. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200400664

SHORT COMMUNICATION
Synthesis of (Indenylidene)phosphoranes ؊ A Novel Class of Ligand
Precursors for Main-Group and Transition Metal Organometallics[‡]
Konstantin A. Rufanov,*[a] Burkhard Ziemer,[a] Markus Hummert,[b] and Stefan Schutte[b]
Dedicated to Professor Manfred Meisel on the occasion of his 65th birthday
Keywords: Bridging ligands / Constrained geometry catalysts / Cyclopentadienyl ligands / Isoelectronic analogues / Isolobal
relationship / Phosphoranes / Phosphorus ylides / Indenyl / Sodium
IndPPh2 (1) reacts with RCH2Br to form the phosphonium
salts [RCH2P(Ph)2Ind]+Br− (2: R = Ph; 3: R = C6F5) in high
diphenylphosphoranyl}indenide (7), isolated as a solvate
with three THF molecules. A detailed NMR study of new li-
yields. Oxidation of 1 with H2O2 in THF proceeds smoothly gand precursors and X-ray structure studies of 5 and 7 have
to give the phosphane oxide IndP(O)Ph2 (4). Dehydrobromin- been accomplished. A short FǞNa coordination contact in
ation of 2 and 3 with NaH in THF yields the corresponding
indenylidenephosphoranes C9H6=P(Ph)2CH2R (5: R = Ph; 6:
R = C6F5). Further deprotonation of 6 with excess NaH results
in formation of sodium 1-{[(pentafluorophenyl)methylidene]-
the molecular structure of 7 has been detected.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
of the cyclopentadienylidenephosphoranes (B, right). Some
examples of similar compounds are known from the litera-
ture;[13] however, neither a general synthetic route towards
these ligand precursors for organometallic chemistry nor
their organometallic derivatives have been explored.
In this paper we describe a synthetic approach towards
and a detailed NMR study of type B ligand precursors on
the basis of stable Ph2PInd (1), as well as the first alkali
metal derivative of one such new ligand, along with their
crystal structures.
Linked (cyclopentadienylsilyl)amine systems A (Scheme
1) became one of the best established and developed classes
of specially designed ligand precursors[1Ϫ5] for bridged
cyclopentadienylϪamido early transition metal complexes,
the so-called ‘‘constrained geometry catalysts’’.[6] De-
pending on the nature of the ligand framework, these com-
plexes give high molecular weight PE with long-chain
branching. Furthermore, because of their more open coor-
dination spheres (relative to ansa-metallocenes), they have
the pronounced ability to incorporate higher olefins.[7Ϫ12]
Isoelectronic analogues of systems A are the linked cyclo-
pentadienylphosphoranylidene systems (B, left). These com-
pounds do exist in the thermodynamically more stable form
Results and Discussion
As the simple (cyclopentadienyl)phosphanes are eager to
dimerise by DielsϪAlder reaction, 1 was chosen for our
preliminary studies. Of the two isomers of this compound,
earlier described by Anderson and co-workers,[14] the
thermodynamically most stable is the vinylic isomer. It was
synthesised in 89% yield by a slightly modified procedure
starting from IndLi and Ph2PCl in toluene.[15] Quaternis-
ation of 1 with bulky tBuCH2Br or Me3SiCH2Br was un-
Scheme 1
[‡]
Organophosphorus(V) Ligands for Coordination and
Organometallic Chemistry, I
[a]
Institut für Chemie, Humboldt-Universität zu Berlin,
Brook-Taylor-Strasse 2, 12489 Berlin, Germany
[b]
Institut für Chemie, Technische Universität Berlin,
Strasse des 17. Juni 135, 10623 Berlin, Germany
Eur. J. Inorg. Chem. 2004, 4759Ϫ4763
DOI: 10.1002/ejic.200400664
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4759

K. A. Rufanov, B. Ziemer, M. Hummert, S. Schutte
SHORT COMMUNICATION
successful,[16] we therefore decided to use the more electro- with thermal ellipsoids of 50% probability as well as selec-
philic C6H5CH2Br and C6F5CH2Br. In both cases, using ted bond lengths and angles are shown in Figure 1.
20% molar excess of benzyl bromides, complete quaternis-
ation was achieved in THF at room temperature after 2 d
(Scheme 2). Corresponding phosphonium salts 2 and 3 are
only slightly soluble in THF and were isolated as white
powders in practically quantitative yields.[17]
Scheme 2
According to 31P NMR spectroscopic data, 2 and 3 exist
as mixtures of allylic (2a: δ ϭ 32.8 ppm; 3a: δ ϭ 15.6 ppm)
Scheme 4
and vinylic (2b: δ ϭ 31 ppm; 3b: δ ϭ 13 ppm) isomers de-
pending on the position of the double bond in the indenyl
ring. The ratio of isomers differs from one sample to an-
other in an irregular way, which precludes accurate assign-
ment of arylic and vinylic signals in 1H and 13C NMR spec-
tra that have been measured in [D6]DMSO. 1H NMR
benzylic signals are located between δ ϭ 5.0 and 5.5 ppm
and 13C signals at δ ϭ 30.0 ppm for 2 and δ ϭ 19.0 ppm
for 3. Allylic signals of isomers a are located at δ ഠ 6.3 ppm
(2JPH ϭ 21 Hz) and 44 ppm (1JP,C ϭ 42 Hz), while those
of isomers b are shifted downfield to δ ϭ 4 ppm and 42
1
ppm in the H and 13C NMR spectra, respectively.
Interestingly, a similar situation arises when phosphane
oxide 4 is synthesised by oxidation of 1 with H2O2 in THF
(Scheme 3).[18] Compound 4, obtained quantitatively, exists
as a 1:4 isomeric mixture of corresponding allylic and vi-
nylic phosphane oxides 4a and 4b, respectively.[19]
Figure 1. Molecular structure of 5 showing the atom numbering
scheme with 50% probability thermal ellipsoids; all hydrogen atoms
˚
are omitted for clarity; selected bond lengths [A] and angles [°]:
C(1)ϪP(1) 1.733(4), C(1)ϪC(2) 1.420(5), C(10)ϪP(1) 1.832(4),
C(1)ϪP(1)ϪC(10)
116.4(2);
C(1)ϪP(1)ϪC(Ph)
108.9(2),
C(Ph)ϪP(1)ϪC(PhЈ) 108.3(2)
Under the same reaction conditions, phosphonium salt 3
was converted directly into the Na salt 7. Obviously, CH
acidity of the benzylic CH2 group is much higher in the
case of the pentafluorobenzyl derivative, and further depro-
Scheme 3
The reaction of the phosphonium salt 2 with a five-fold tonation with NaH (applied in fivefold excess) proceeds
molar excess of NaH in THF was rather slow, took 3 d, quicker and results in the formation of sodium 1-
and resulted in a dark green solution (Scheme 4). Upon {[(pentafluorophenyl)methylidene]diphenylphosphoranyl}-
concentration of the solution to one quarter of its initial indenide (7).[23] The synthesis of 6 was achieved in another
volume, the desired indenylidenephosphorane 5 precipitated experiment using only 20% molar excess of NaH and a
at Ϫ78 °C after 1 d as a yellow-green, light-sensitive micro- shorter reaction time: after 6 h in THF, it was obtained in
crystalline powder.[20] Crystallisation from CH2Cl2 gave 78% yield as a yellow powder.[24] Both indenylidenephos-
block crystals. The X-ray structure of 5 was determined and phoranes 5 and 6 are rather stable and can be handled in
showed nearly ideal tetrahedral coordination of the central air without special care for several minutes. They are more
phosphorus atom with CϪPϪC angles between 104° and soluble in ethereal and aromatic solvents than in aliphatic
116°. The CϪP bond lengths are also not very different: ones. Gold-yellow Na salt 7 crystallises with three THF
˚
˚
1.828(4) A for PhCH2ϪP, 1.797(4) A for CPhϪP and molecules (coordinated by sodium) in the asymmetric
1.727(4) A for CIndϭP. [21,22] The molecular structure of 5 unit.[25,26] While their O atoms occupy fixed positions
˚
4760
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Eur. J. Inorg. Chem. 2004, 4759Ϫ4763

Synthesis of (Indenylidene)phosphoranes
SHORT COMMUNICATION
around the sodium atom, all carbon atoms are disordered.
The structure refinement of the latter had to be split on two
sides in each case. For this reason only the C atoms of the
major components could be refined anisotropically. The ra-
tios between major and minor components vary from 64:36,
66:34 to 83:17, respectively. The sodium atom shows pre-
dominantly η3-coordination with the allylic part of the in-
denyl fragment, with the shortest distance to the C2 atom
˚
(2.67 A). Similar delocalisation of the carbanionic charge
was found by Schmidbaur and co-workers in the crystal
structure of the solvent-free potassium salt of dimethylph-
osphonium bis(benzylide) K[Me2P(CHPh)2]. The lattice did
not contain discrete complex molecules, but was rather a
coordination polymer; the metal atoms interacted preferen-
tially with ylidic carbanions and the ortho and para posi-
tions of the benzylide rings.[27] In the molecular structure
of 7, a short FǞNa coordination contact was found. The
intramolecular distance between the sodium cation and one
Figure 2. Molecular structure of 7 showing the atom numbering
scheme with 50% probability thermal ellipsoids; all hydrogen atoms
except for H(10) of the bridging moiety are omitted; only oxygen
atoms of coordinated THF molecules are shown for clarity; selec-
˚
ted bond lengths [A] and angles [°]: PϪC(10) 1.714(2), PϪC(1)
1.747(1), PϪC(Ph) 1.827(2), PϪC(PhЈ) 1.828(2), C(1)ϪC(2)
1.431(2), C(2)ϪC(3) 1.383(2), NaϪC(1) 2.874(2), NaϪC(2)
2.679(2), NaϪC(3) 2.741(2), NaϪO(1) 2.373(2), NaϪO(2) 2.322(2),
NaϪO(3) 2.271(2), NaϪF(5) 2.669(1), F(5)ϪC(C6F5) 1.374(2),
˚
of the ortho-F atoms of the C6F5 group is only 2.67 A, i.e.
˚
more than 1 A shorter than the sum of the van der Waals
radii of these elements (3.74 A).[28] The molecular structure
˚
F(3)ϪC(C6F5)
C(10)ϪPϪC(Ph)
C(1)ϪPϪC(Ph)
PϪC(1)ϪNa
1.354(2);
103.51(8),
106.37(7),
125.21(8),
87.75(6),
C(10)ϪPϪC(1)
C(1)ϪPϪC(PhЈ)
C(Ph)ϪPϪC(PhЈ)
O(3)ϪNaϪO(2)
O(2)ϪNaϪO(1)
O(2)ϪNaϪF(5)
118.77(8),
109.02(8),
103.61(8),
116.93(6),
88.00(6),
78.87(5),
of 7 with thermal ellipsoids of 50% probability as well as
selected bond lengths and angles are shown in Figure 2.
Because of the importance of 5, 6 and 7 for further synth-
eses of organometallic derivatives, a detailed NMR study of
O(3)ϪNaϪO(1)
O(3)ϪNaϪF(5)
81.70(5),
O(1)ϪNaϪF(5) 157.07(5), C(C6F5)ϪF(5)ϪNa 140.0(1)
1
these compounds has been performed using H/13C COSY,
APT and DEPT methods and heteronuclear NMR spec-
troscopy. The complete set of data obtained is given in
Table 1. It is interesting to note that in the 13C NMR spec- also appear at a much lower field than in 6, while those of
trum of 7 signals for C1 appear considerably shifted down- meta-F substituents are almost unaffected. Also, no differ-
field, and the signals for C1Ј and PCH are shifted upfield, ence between the ortho-F atoms can be detected, which
relative to those in the spectrum of 6. In the 19F NMR indicates free rotation of the C6F5 substituent of 7 when it
spectrum the signals of ortho- and para-F substituents in 7 is in solution.
1
Table 1. Assignment of signals in H, 13C, 31P and 19F NMR spectra of 5, 6 and 7
1H: δ [ppm]
13C/31P/19F: δ [ppm]
6
5
6
7
5
7
1
2
3
Ϫ
6.65, t
6.44. t
Ϫ
6.57, t
6.43, t
7.62Ϫ7.39
6.77Ϫ6.55
Ϫ
Ϫ
6.66, t
6.16, t
7.32Ϫ7.26
6.57Ϫ6.46
Ϫ
59.9 (1JP,C ϭ 110 Hz) 62.2 (1JP,C ϭ 118 Hz) 24.5 (1JP,C ϭ 135 Hz)
126.9 (2JP,C ϭ 15 Hz) 126.1 (2JP,C ϭ 16 Hz) 127.4 (2JP,C ϭ 16 Hz)
117.3 (3JP,C ϭ 13 Hz) 106.9 (3JP,C ϭ 15 Hz) 101.0 (3JP,C ϭ 14 Hz)
4, 7 7.57Ϫ7.02
5, 6 6.76Ϫ6.57
8
120.1, 117.3
117.2, 116.7
137.6
119.6, 117.1
116.6, 116.3
137.8
119.6, 119.5
115.8, 115.2
136.7
Ϫ
9
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
135.1
135.4
135.2
1Ј
2Ј
3Ј
4Ј
1ЈЈ
124.6 (1JP,C ϭ 86 Hz) 123.1 (1JP,C ϭ 87 Hz) 137.5 (1JP,C ϭ 88 Hz)
133.3(2JP,C ϭ 10 Hz) 132.6 (2JP,C ϭ 10 Hz) 133.1 (2JP,C ϭ 9 Hz)
128.8 (3JP,C ϭ 12 Hz) 128.5 (3JP,C ϭ 12 Hz) 128.1 (3JP,C ϭ 11 Hz)
132.7 (4JP,C ϭ 3 Hz) 132.8(4JP,C ϭ 3 Hz) 130.2(4JP,C ϭ 2.5 Hz)
7.57Ϫ7.02
7.57Ϫ7.02
7.57Ϫ7.02
Ϫ
7.62Ϫ7.39
7.62Ϫ7.39
7.62Ϫ7.39
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
7.80Ϫ7.27
7.80Ϫ7.27
7.80Ϫ7.27
Ϫ
Ϫ
Ϫ
Ϫ
130.2 (2JP,C ϭ 8 Hz)
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
2ЈЈ 6.82Ϫ6.76
3ЈЈ 7.57Ϫ7.50
4ЈЈ 7.42Ϫ7.10
THF Ϫ
130.5
128.4
127.5
Ϫ
3.61, 1.76
68.3, 26.4
PCH 4.14 (2JPH ϭ 14 Hz) 4.16 (2JPH ϭ 13 Hz) 2.73 (2JPH ϭ 11Hz) 33.9 (1JP,C ϭ 53 Hz) 22.0 (1JP,C ϭ 55 Hz) 81.4 (1JP,C ϭ 124 Hz)
P
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
9.7
Ϫ
Ϫ
8.9
4.7
o-F
m-F
p-F
Ϫ139
Ϫ169
Ϫ155
Ϫ153
Ϫ170
Ϫ190
Ϫ
Eur. J. Inorg. Chem. 2004, 4759Ϫ4763
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 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4761

K. A. Rufanov, B. Ziemer, M. Hummert, S. Schutte
SHORT COMMUNICATION
Ph2PCl, C6H5CH2Br, C6F5CH2Br, nBuLi and NaH were used
as supplied (Merck, Aldrich). Starting Phosphane, Ph2PInd (1):
Indene (29 g, 250 mmol) was dissolved in pentane (900 mL).
While the solution was stirred vigorously and cooled with an
ice bath, nBuLi (110 mL 2.5  solution in hexanes, 275 mmol)
was added over a period of 2Ϫ3 h.. The mixture was stirred
overnight. The white precipitate of IndLi was filtered off,
washed with pentane (3 ϫ 100 mL) and dried in vacuo for
several hours. The thus obtained IndLi (12.2 g, 100 mmol) was
suspended in toluene (400 mL), and under continuous stirring
a solution of Ph2PCl (22 g, 100 mmol) in toluene (100 mL) was
added over a period of 4Ϫ5 h. The reaction mixture was stirred
overnight, LiCl was filtered off, toluene was removed in vacuo,
the crude product washed with hexane (4 ϫ 50 mL) and dried
in vacuo, to afford 1 in 89% yield and 95% purity as a light grey
powder. 1H NMR (200 MHz, C6D6, 25 °C): δ ϭ 7.52Ϫ6.98 (m,
14 H, HAryl), 6.12 (dd, 1 H, vinylic H), 3.07 (t, 2 H, allylic H)
ppm. 31P NMR (200 MHz, C6D6, 25 °C): δ ϭ Ϫ21 ppm.
No reaction was observed after stirring of 1 with 50% molar
excess of RCH2Br (R ϭ tBu or TMS) at room temperature in
THF for 30 h.
Conclusion
Series of phosphoranes B with different R substituents
can be synthesised easily using the developed synthetic
scheme or, alternatively, from chlorophosphonium ylides
with sterically encumbered {Cp}-type anions. A combi-
nation of these two methods allows a wide range of the type
B ligand precursors to be synthesised (Scheme 5).[29]
[16]
[17]
Scheme 5
Phosphonium Salts [C6H5CH2P(Ph)2Ind]ϩBrϪ (2) and
[C6F5CH2P(Ph)2Ind]ϩBrϪ (3): C6H5CH2Br (8.5 g, 50 mmol) or
C6F5CH2Br (13 g, 50 mmol) was added at once to a solution
of 1 (12 g, 40 mmol) in THF (300 mL). The reactions were
very slow and only after 3 d complete, resulting in a white
precipitate of 2 or 3, which was filtered off, washed with THF
and pentane, and dried in vacuo. Yields in both cases Ͼ 95%.
2: M.p. 253Ϫ255 °C. EIMS: m/z (%) ϭ 391.0 (100) [M]ϩ. 3:
M.p. 228Ϫ230 °C. EIMS: m/z (%) ϭ 481.0 (100) [M]ϩ.
Phosphane Oxide IndP(O)Ph2 (4): A 34% aqueous solution of
H2O2 (2 mL, 20 mmol) was slowly added with a syringe to a
stirred solution of 1 (3.0 g, 10 mmol) in THF (50 mL). After
30 min, the solution was quickly dried with Na2SO4, and THF
was removed in vacuo, yielding an off-white microcrystalline
powder of 4. Yield: 3.15 g (100%). M.p. 137Ϫ138 °C. EIMS:
m/z (%) ϭ 316.1 (32) [M]ϩ , 201.0 (100) [Mϩ Ϫ Ind]. C21H17OP
(316.34): calcd. C 79.73, H 5.42; found C 80.07, H 5.66.
NMR measured in CD2Cl2: 1H: 4a: δ ϭ 7.8Ϫ6.9 (m, aryl, Ph),
In this preliminary work we have formed the basis for the
further development and revival of organometallic chemis-
try in the so-called ‘‘post-metallocene’’ epoch. Systematic
study of thus developed linked cyclopentadienylphosphor-
anylidene ligands for the syntheses of alkali, rare-earth
and transition metal complexes is the subject of our cur-
rent efforts.
[18]
Acknowledgments
K. R. thanks Dr. Heinz-Jürgen Kroth for multinuclear NMR
experiments, Profs. Herbert Schumann (Berlin Technical Univer-
sity) and Igor Fedushkin (Razuvaev-Institute of Chemistry, Nizhnij
Novgorod, Russian Federation) for fruitful discussions and the
Graduate College Programme 352 of the DFG for a postdoctoral
fellowship.
[19]
[20]
3
6.83, 6.38 (AB system, JAB ϭ 3 Hz, vinylic protons), 4.72 (d,
2JPH ϭ 25 Hz, allylic H); 4b: δ ϭ 7.8Ϫ6.9 (m, aryl, Ph), 6.71
(dt, vinylic H), 3.5 (br. s, 2 allylic H ((AUTHOR: Change
ok?))) ppm. 31P: 4a: δ ϭ 32.3 ppm; 4b: δ ϭ 23.2 ppm.
Indenylidenephosphorane C9H6؍P(Ph)2CH2C6H5 (5): NaH (2.4
g, 100 mmol) was added under argon to a stirred suspension
of 2 (9.42 g, 20 mmol) in THF (100 mL). Slowly the solution
began to darken. The reaction was complete after 48 h, re-
sulting in a dark green solution and white precipitate, which
was filtered off. The filtrate was concentrated to one quarter
of its initial volume (ca. 20Ϫ25 mL). The desired ylide 5 pre-
cipitated from the solution at Ϫ78 °C after 1 d as a yellow-
green, light-sensitive microcrystalline powder. Yield: 6.16 g
(79%). M.p. 224Ϫ226 °C. EIMS: m/z (%) ϭ 390.1 (73) [M]ϩ,
299.0 (18) [Mϩ Ϫ C7H8], 276.1 (22) [Mϩ Ϫ Ind], 185.1 (100)
[Ph2P]ϩ. C28H23P (390.47): calcd. C 86.13, H 5.94; found C
86.19, H 5.70.
[1]
P. J. Shapiro, E. E. Bunel, W. P. Schaefer, J. E. Bercaw, Or-
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[2]
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[3]
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EP0420436A1, 1991.
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[10]
L. Jia, X. Yang, C. L. Stern, T. J. Marks, Organometallics 1997,
[21]
16, 842.
X-ray Crystallographic Study: Crystallisation of 5 was achieved
from CH2Cl2. A suitable light-yellow, nearly colourless crystal
with linear dimensions of 0.35 ϫ 0.20 ϫ 0.18 mm was mounted
on the end of a glass fibre and investigated with a Siemens
SMART CCD at 173(2) K, using graphite-monochromated
[11]
A. L McKnight, R. M. Waymouth, Chem. Rev. 1998, 98, 2587.
G. J. P. Britovsek, V. C. Gibson, D. F. Weiss, Angew. Chem.
[12]
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[13]
G. Becker, in Methoden Org. Chem. (Houben-Weyl), Georg
˚
Thieme Verlag, Stuttgart, 1985, Bd. V/2c, p. 494.
K. A. Fallis, G. K. Anderson, N. P. Rath, Organometallics
Mo-Kα radiation (λ ϭ 0.71073 A). Data were collected with an
[14]
area detector by use of ω scans. The structure was solved by
direct methods and expanded by difference Fourier syntheses
using the SHELX-97 software package; the intensities were
corrected for Lorentz, polarisation and absorption effects using
SADABS (Tmin. ϭ 0.9601, Tmax. ϭ 0.9777). G. M. Sheldrick,
SADABS, Programme for absorption correction, University of
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Göttingen, 1997.
1992, 11, 885.
[15]
General Remarks: All synthetic procedures were performed un-
der purified argon using standard Schlenk techniques. Solvents
were distilled from an appropriate drying agent and degassed
1
prior to use. The H, 13C, 19F and 31P NMR spectra were ob-
tained with Bruker ARX-200, -300 or -400 spectrometers. Mass
spectra were measured with a Varian CH-7a MAT device using
electron impact with an excitation energy of 70 eV. Indene,
4762
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Eur. J. Inorg. Chem. 2004, 4759Ϫ4763

Synthesis of (Indenylidene)phosphoranes
SHORT COMMUNICATION
[22]
Crystal Data and Structure Refinements Details: C28H23P, M ϭ
from THF. A suitable gold-yellow specimen with linear dimen-
sions of 0.48 ϫ 0.24 ϫ 0.22 mm was mounted on the end of a
glass fibre and investigated with a Siemens SMART CCD at
153(2) K, using graphite-monochromated Mo-Kα radiation
˚
˚
390.43, triclinic, a ϭ 9.5646(3) A, b ϭ 9.7692(3) A, c ϭ
˚
11.8500(4) A, α ϭ 98.242(2)°, β ϭ 94.528(2)°, γ ϭ 109.004(2)°,
3
Ϫ1
˚
V ϭ 1026.70(5) A , space group P1, Z ϭ 2, µ ϭ 0.145 mm
,
Dcalcd. ϭ 1.263 g·cmϪ3, θ range 1.75Ϫ26.00°, 6798 reflections
measured, 3971 unique (Rint ϭ 0.0990) which were used in all
calculations. GoF (on F2) ϭ 0.861. The final residuals RF and
(λ ϭ 0.71073 A). Data were collected with an area detector by
˚
use of ω scans. The structure was solved by direct methods and
expanded by difference Fourier syntheses using the SHELX-97
software package; the intensities were corrected for Lorentz,
2
wRF were 0.0723 [I Ͼ 2σ(I)] and 0.1638 (all). CCDC-233977
contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cam-
bridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; Fax: (internat.) ϩ 44-1223-336-033;
E-mail: deposit@ccdc. cam. ac. uk].
polarisation and absorption effects using SADABS (Tmin. ϭ
0.9324, Tmax. ϭ 0.9682). G. M. Sheldrick, SADABS, Pro-
gramme for absorption correction, University of Göttingen,
1996; G. M. Sheldrick, Programme for the refinement of crystal
structures, SHELX-97, University of Göttingen, 1997.
[26]
Crystal
Data
and
Structure
Refinements
Details:
[23]
˚
Sodium
1-{[(Pentafluorphenyl)methylidene]diphenylphosphor-
C40H41F5NaO3P, M ϭ 718.69, monoclinic, a ϭ 12.0079(2) A,
˚
˚
anyl}indenide (7): NaH (0.61 g, 25 mmol) was added under ar-
gon to a stirred suspension of 3 (2.72 g, 4.9 mmol) in THF (50
mL). The reaction proceeded exothermally with the evolution
of a large amount of gas (H2). The yellow solution was stirred
over a weekend. After concentration of the reaction mixture, it
was filtered and an equal amount of pentane was slowly poured
onto the solution. Crystallisation began immediately, yielding
gold-yellow crystals of Na salt 7 at 0 °C after 1 d. Yield: 1.5
g (59%).
b ϭ 15.8221(2) A, c ϭ 20.3386(3) A, α ϭ γ ϭ 90°, β ϭ
3
˚
106.918(1)°, V ϭ 3696.90(9) A , space group P21/c, Z ϭ 4, µ ϭ
0.148 mmϪ1, Dcalcd. ϭ 1.291 g·cmϪ3, θ range 1.77Ϫ25.50°, 22
887 reflections measured, 6866 unique (Rint ϭ 0.0993), which
were used in all calculations. GoF (on F2) ϭ 1.012. The final
residuals RF and wRF2 were 0.0637 [I Ͼ 2σ(I)] and 0.1488 (all).
CCDC-233976 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ 44-1223-336-033;
E-mail: deposit@ccdc.cam.ac.uk].
[24]
Indenylidenephosphorane C9H6؍P(Ph)2CH2C6F5 (6): Anal-
ogous to the preparation of 5 starting from 3 (5.6 g, 10 mmol)
and NaH (0.29 g, 12 mmol) but with a shorter reaction time
(6 h). Yield: 3.74 g (78%). M.p. 180Ϫ182 °C. EIMS: m/z (%) ϭ
[27]
H. Schmidbaur, U. Deschler, B. Milewski-Mahrla, B. Zimmer-
Gasser, Chem. Ber. 1981, 114, 608.
A. Bondi, J. Phys. Chem. 1964, 68, 441.
K. Rufanov, Chem. Eur. J., manuscript in preparation.
Received July 29, 2004
480.1 (9) [Mϩ], 366.1 (18) [Mϩ Ϫ Ind], 299.0 (10) [Mϩ
Ϫ
C6F5CH3], 185.1 (50) [Ph2Pϩ]. C28H18F5P (480.42): calcd. C
70.00, H 3.78; found C 68.15, H 4.20.
[28]
[29]
[25]
X-ray Crystallographic Study: Crystallisation of 7 was achieved
Eur. J. Inorg. Chem. 2004, 4759Ϫ4763
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4763