New halo compounds of Si, P, As, and Sb bearing a bulky substituted fluorenyl group

Article abstract of DOI:10.1080/10426500390228639

New halo compounds of Si, P, As, and Sb, potential precursors of doubly-bonded derivatives of these elements, have been synthesized: dichloro-and difluorosilanes 2-6 bearing a methylfluorenyl group and a second substituent of various size (Me, Ph, Mes, R<

Full text of DOI:10.1080/10426500390228639

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Phosphorus, Sulfur, and Silicon and the Related
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New Halo Compounds of Si, P, As, AND Sb Bearing a
Bulky Substituted Fluorenyl Group
L. Baiget a , M. Bouslikhane a , J. Escudie a , G. Cretiu Nemes b , I. Silaghi-Dumitrescu b & L.
Silaghi-Dumitrescu b
a Université Paul Sabatier , Toulouse Cedex, France
b Babes-Bolyai University , Cluj-Napoca, Romania
Published online: 23 Aug 2006.
To cite this article: L. Baiget , M. Bouslikhane , J. Escudie , G. Cretiu Nemes , I. Silaghi-Dumitrescu & L. Silaghi-Dumitrescu
(2003) New Halo Compounds of Si, P, As, AND Sb Bearing a Bulky Substituted Fluorenyl Group, Phosphorus, Sulfur, and Silicon
and the Related Elements, 178:9, 1949-1961, DOI: 10.1080/10426500390228639
To link to this article: http://dx.doi.org/10.1080/10426500390228639
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Phosphorus, Sulfur, and Silicon, 178:1949–1961, 2003
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500390228639
NEW HALO COMPOUNDS OF Si, P, As, AND Sb
BEARING A BULKY SUBSTITUTED
FLUORENYL GROUP
L. Baiget,a M. Bouslikhane,a J. Escudie,a G. Cretiu Nemes,b
I. Silaghi-Dumitrescu,b and L. Silaghi-Dumitrescub
Universite´ Paul Sabatier, Toulouse Cedex, Francea and
Babes-Bolyai University, Cluj-Napoca, Romaniab
(Received March 25, 2003; accepted April 3, 2003)
New halo compounds of Si, P, As, and Sb, potential precursors of doubly-
bonded derivatives of these elements, have been synthesized: dichloro-
and difluorosilanes 2–6 bearing a methylfluorenyl group and a second
substituent of various size (Me, Ph, Mes, R2CMe); dichlorophosphines
13 and 14, fluoro- and difluoroarsines 15 and 16 and fluorostibine 17,
substituted by the diphenyl (or dimesityl) phosphinofluorenyl group.
Phosphine oxide and sulfide 9 and 10 also have been prepared.
Keywords: Dichlorophosphines; dihalosilanes; fluorenyl compounds;
fluoroarsines; fluorostibines; phosphine oxides; sulfides
The study of doubly-bonded systems of main group elements is cur-
rently under active investigation. Many groups in the world are work-
ing in derivatives containing one (I) or two double bonds (conjugated
(II) or cumulated (III)):1
These compounds generally are stabilized by a large steric hin-
drance which prevents the approach of two monomers to form dimers or
M.B. thanks the “Comite´ Mixte Interuniversitaire Franco Marocain” for the Action
Inte´gre´e no 216/SM/00.
Address correspondence to Jean Escudie, Universite´ Paul Sabatier, He´te´rochimie Fon-
damentale et Applique´e, UMR 5069, 118 route de Narbonne, 31062 Toulouse Cedex 04,
France.
1949

1950
L. Baiget et al.
oligomers. Thus, the design of synthetically available routes to bound
groups on M and Mꢁ that present a great steric hindrance is extremely
important. Moreover, as the dihalo compounds MX2 (X = F, Cl, Br) of
group 14 and 15 elements are generally involved in the process to
derivatives I–III, their preparation must be the first step in the syn-
thesis of the latter:
Thus, we report in this article the synthesis of dihalo derivatives
of the type MX2, with M being an element of group 14 (silicon) or 15
(phosphorus, arsenic, and antimony).
RESULTS AND DISCUSSION
The choice of the bulky group on M is very important. In order to pre-
pare large quantities of MX2 compounds at the lowest possible price, it
is necessary to use a group easily prepared from an inexpensive com-
mercially available starting material, such as fluorene. Moreover, the
fluorenyl group allows simple purification by easy crystallization and,
due to the presence of three fused cycles, presents a large steric hin-
drance. Thus, we used it on all MX2 compounds we have synthesized.
Dihalosilanes
We have prepared derivatives of type V from IV where, in order to
avoid side reactions that could occur (hydrogen easily substitutable by
lithium), we have replaced hydrogen by an alkyl group such a methyl,
which is the simplest one.
We have used groups Rꢁ of various size on silicon (Me, Ph, Mes,
R2CMe) to obtain dihalosilanes >SiX2, precursors of low-coordinated

Fluorenyl Compounds
1951
silicon species, presenting a large scale of steric hindrance. As RꢁSiCl3,
we generally have used MeSiCl3 or PhSiCl3, which are commercially
available.
2–5 are synthesized nearly quantitatively from 1, easily prepared
from fluorene.2
2–5 are characterized by 1H and 13C NMR and mass spectroscopy. In
compounds 2–4, the protons of the fluorenyl group appear in 1H NMR as
a complex multiplet. By contrast, in 5, a first order spectrum is observed
for the eight aromatic protons (two doublets and two triplets) with a
high field shift of about 0.50 ppm compared to 2–4. Such a phenomenon
is due to the presence of a second fluorenyl group which presents a high
magnetic anisotropy. The influence of a fluorenyl group on a second one
previously has been reported in Me2Si(CMeR2)2.3
As reduction, alkylation or monoelectronic transfers sometimes oc-
cur in the reaction of chlorosilanes with lithio compounds, we also
have prepared in one case a difluorosilane derivative. Fluorination of
chlorosilanes with hydrofluoric acid in water is generally a good route
to the corresponding fluorosilanes,4 but attempts to prepare 6 by such
a route from 3 failed: We only have observed the cleavage of the ben-
zylic Si CR2 bond with formation of 1 and of an unidentified silicon
compound:
Note that in similar conditions, the Ge-CHR2 bond is not cleaved
and fluorine derivatives can be synthesized from their chloro analogues
and HF/H2O.5 However, 6 was prepared in high yield by reaction of

1952
L. Baiget et al.
R2C(Me)Li with phenyltrifluorosilane obtained from its trichloro ana-
logue and antimony trifluoride.6
Dihalides of Group 15 Elements
Synthesis of Precursors
As there is only one substituent on M in −MX2 (M = P, As, Sb), it is
necessary to increase its size by comparison with the case of Si where
there are two bulky substituents. So, we decided to use the fluorenyl
group but, instead of a methyl on carbon 9, we have chosen a bulkier
group. As NMR of arsenic and antimony is not available, we used a
phosphorus group in order to have a NMR probe allowing easy identi-
fication of derivatives even in a complex mixture.
The phosphines 7 and 8 with phenyl or mesityl groups were pre-
pared in excellent yield by reaction of the fluorenyllithium with
chlorodiphenyl (or dimesityl) phosphine:
For the synthesis of 8, it is possible to use the crude reaction mixture
of Mes2PCl/Mes2PBr obtained from MesMgBr and PCl3.7
1
A proof of the great steric hindrance of 8 is given by the H NMR:
Two singlets are observed for the aromatic hydrogens of the mesityl
groups. Surprisingly, the six methyl groups (ortho and para) present
the same chemical shift.
Due to the presence of two aromatic groups on phosphorus, 7 and 8
are not very air-sensitive and can be handled easily and used. However,
7 is oxidized by gaseous oxygen and sulfurized to form air-stable 9 and
10:
As expected, larger JPC coupling constants are observed for PIV com-
pounds 9 and 10 than for PIII. Whereas C2−7 do not couple with P in 7

Fluorenyl Compounds
1953
4
5
and 8, JPC and JPC are observed between C2,3,6,7 and P in 9 and 10,
and even 4JPC between C4,5 and P in 10.
In order to see if this group R2C(PRꢁ2) is potentially available as sub-
stituent on M15, we determined the experimental conditions to get the
lithio compound R2C(Li)PRꢁ2 11. The use of n-butyllithium in THF ap-
peared to be suitable to give 11, and the formation was evidenced by
quenching with methyl iodide:
All the compounds 7–10 and 12 were characterized by NMR and
2
mass spectroscopy. Note that whereas the JHP coupling constant in 7
is close to zero, a large 3JHP coupling (13.0 Hz) is observed for 12.
Synthesis of Halophosphines, Arsines, and Stibines
Addition of 11 to phosphorus trichloride afforded the expected
diphosphines 13 and 14:
13 and 14 were characterized by 31P NMR, which displays two dou-
blets as expected. Note a shift of about 30 ppm at high field for the
phosphorus of PMes2 in comparison with the one of PPh2, but the most
striking feature is the extremely large difference between the two 2JPP
coupling constants: 167.8 Hz in 13 and 409.0 Hz in 14. The latter is very
high and generally corresponds to a 1JPP. This great coupling constant
in 14 probably is due to the large size of mesityl groups which induce
a nearly planar phosphorus atom and particularly to a special confor-
mation of the P C P moiety. A similar huge difference in the 2JPP cou-
pling constant previously has been observed in ArP = C(Cl) P(Cl)Tsi
(Tsi: (Me3Si)3C) (89 and 457 Hz) and was related to the difference in
the conformation.8
From 11 and AsF3,9 we also obtained, in addition to the expected
dihalo derivative 15, the monofluoroarsane 16:

1954
L. Baiget et al.
TABLE I 19F and 31P NMR Spectra of Fluoro- and Difluoroarsines
Difluorinated
compound
Chemical shift
in 19F (ppm)
Monofluorinated
Chemical shift
in 19F (ppm)
compound
R2C(PPh2)-AsF2 15
ArAsF2
−35.1
−21.8
[R2C(PPh2)]2AsF 16
−132.4
−114.4
ArP C(Br)-As(Dmt)F11
(Dmt: 2,6-Mes2-4-MeC6H2)
ArP C(Cl)-As(Tsi)F11
10
(Ar: 2,4,6-tBu3C6H2)
11
TsiAsF2
−32.4
−114.3
(Tsi: (Me3Si)3C)
15 and 16 were identified in 19F and 31P NMR: They present charac-
teristic chemical shifts in 19F NMR for a fluoro- (−110/−135 ppm) or a
difluoroarsine (−20/−30 ppm) as shown in Table I.
Moreover, the P F coupling constants (d in 19F and t in 31P NMR for
15 and t in 19F and d in 31P NMR for 16) unambiguously prove their
structure.
The formation of mono- and disubstituted derivatives 15 and 16 con-
trasts with the results observed in the case of phosphorus. Indeed, only
the smaller size of phosphorus allows monosubstitution on PCl3 to give
13 and 14 while the larger radius of arsenic allows the disubstitution.
As very few doubly-bonded derivatives of antimony are known, it
seemed interesting to synthesize dihalogeno compounds SbX2. How-
ever, in the reaction of 11 with SbF3, only the disubstituted antimony
compound 17 was formed:
The structure of 17 was evidenced by its high field shift in 19F
NMR (−125.0 ppm), characteristic of a monofluoroantimony derivative.
Such types of chemical shifts already have been found in other R2SbF
compounds.12 Although the target difluoroantimony compound 18 has
not been obtained, this reaction is interesting since it leads to 17 which,
due to its high steric hindrance and the presence of a flurine atom, could
be used as a bulky protecting group.
The formation of the disubstituted arsenic and antimony derivatives
16 and 17 deserves some comments. Obviously the size of the M el-
ement (M = As, Sb) increasing from P to Sb going down the periodic
table is important, but does not constitute the only determining factor.
Indeed, whatever the experimental conditions we used (excess of MF3,

Fluorenyl Compounds
1955
temperature, addition of RLi to MF3, or reverse addition), we always
obtained the same results and we have been unable to prevent the dis-
ubstitution. Thus, it seems that the disubstitution is faster than the
mono- one, contrary to what is expected on the basis of steric and elec-
tronic arguments. We currently are studying the mechanism of these
reactions.
CONCLUSION
Two series of R2C(Me) Si(Rꢁ)X2 (X = F, Cl; Rꢁ =Me, Ph, Mes, R2CMe)
and R2C(Rꢁꢁ)-MX2 (X = F, Cl; M=P, As; Rꢁꢁ = PPh2, PMes2) derivatives
which present various group 14 and 15 elements, halogens, and steric
hindrance have been synthesized. Going down the periodic table, we
observed exclusive monosubsitution on Si and P, both mono- and dis-
ubstitution on As and only disubstitution on Sb.
The use of the dihalo derivatives 2–5 and 13–15 for stabilizing low
coordinated compounds is now under intensive investigation.
EXPERIMENTAL SECTION
All experiments were carried out in flame-dried glassware under a ni-
trogen atmosphere using high-vacuum line techniques. Solvents were
dried and freshly distilled from sodium benzophenone ketyl and care-
fully deoxygenated on the vacuum line by several “freeze-pump-thaw”
cycles. NMR spectra were recorded in CDCl3 on the following spectrom-
eters: 1H, Bruker AC200 (200.13 MHz) and sometimes when mentioned
1
Bruker AC80 (80.13 MHz); 13C{ H}, Bruker AC200 (50.32 MHz) (ref-
erence TMS); 19F, Bruker AC80 (75.39 MHz) (reference CF3COOH);
1
31P{ H}, Bruker AC200 (80.15 MHz) (reference H3PO4). Melting points
were determined on a Wild Leitz-Biomed apparatus. Mass spectra were
obtained on a Hewlett-Packard 5989A spectrometer by EI at 70 eV.
MeSiCl3, PhSiCl3, Ph2PCl, and SbF3 were available commercially
Solutions of n-BuLi 1.6 M in hexane were used. Some starting products
were synthesized according to the literature: PhSiF3,6 Mes2PCl,7 AsF3,9
MesSiCl3.13
Synthesis of Dichloro(methyl)(methylfluorenyl)silane 2
To a solution of methylfluorene 1 (2.50 g, 13.9 mmol) in Et2O (30 mL)
cooled at −78◦C were added 8.8 mL of a solution of n-BuLi (13.9 mmol).
After .5 h of stirring at room temperature, the red solution of R2C(Me)Li
was canulated to a solution of methyltrichlorosilane (2.07 g, 13.9 mmol)

1956
L. Baiget et al.
in Et2O (10 mL) cooled at −78◦C. After stirring the mixture at 20◦C for
2 h, LiCl was eliminated by filtration, then the solvents were removed in
vacuo and the residue dissolved in 20 mL of pentane. Cooling at −20◦C
afforded white crystals of 2 (3.38 g, 83%, mp: 110◦C).
1
NMR: H (80 MHz): 0.01 (s, 3H, MeSi), 1.87 (s, 3H, CMeR2), 7.35–
7.90 (m, 8H, arom H).
13C: 0.54 (MeSi), 17.81 (CMeR2), 46.74 (C9), 120.21 (C4C5), 125.03,
127.07, and 127.34 (C1−3C6−8), 140.61 (C12C13), 145.84 (C10C11).
MS: 292 (M, 18), 257 (M Cl, 2), 179 (CMeR2, 100).
The dihalogenosilanes 3–6 were synthesized by the same procedure
as 2.
Synthesis of Dichloro(phenyl)(methylfluorenyl)silane 3
R2C(Me)H, 1.27 g (7.1 mmol); BuLi, 4.40 mL (7.1 mmol); PhSiCl3, 1.50 g
(7.1 mmol); 3 (2.04 g, 81%, m.p. 84–85◦C).
NMR: 1H (80 MHz): 1.99 (s, 3H, Me), 6.92–7.30 (m, 5H, arom H Ph),
7.32–7.83 (m, 8H, arom H CR2).
13C: 18.02 (Me), 47.23 (C9), 120.08 (C4C5), 125.14, 126.82, 127.10 and
127.37 (C1−3C6−8 and m-CH Ph), 128.66 (ipso-C Ph), 131.31 (p-CH Ph),
134.10 (o-CH Ph), 140.95 (C12C13), 145.42 (C10C11).
MS: 354 (M, 18), 276 (M-Ph-1, 1), 179 (CMeR2, 100).
Synthesis of Dichloro(mesityl)(methylfluorenyl)silane 4
R2C(Me)H, 1.00 g (5.5 mmol); BuLi, 3.5 mL (5.5 mmol); MesSiCl3, 1.40 g
(5.5 mmol); 4 (1.57 g, 72%, m.p.: 118◦C).
NMR: 1H (80 MHz): 1.92 (s, 3H, Me), 2.03 (s, 6H, o-Me), 2.20 (s, 3H,
p-Me), 6.67 (s, 2H, arom H Mes), 7.20–7.76 (m, 8H, arom H CR2).
13C: 19.44 and 20.15 (CMeR2 and p-Me Mes), 26.39 (o-Me Mes), 49.70
(C9), 120.38 (C4C5), 123.22 (ipso-C Mes), 125.16, 126.92 and 127.40
(C1−3C6−8), 130.34 (m-CH Mes), 141.07, 141.43, 146.09 and 145.78
(C10−13 and o- and p-C Mes).
MS: 396 (M, 15), 217 (MesSiCl2, 78), 179 (CMeR2, 91), 119 (Mes,
100).
Synthesis of Dichloro[bis(methylfluorenyl)]silane 5
R2C(Me)H, 2.58 g (14.3 mmol); BuLi, 9.0 mL (7.1 mmol); SiCl4, 1.21 g
(7.1 mmol); 5 (2.14 g, 66%, m.p.: 243◦C).
1
3
NMR: H: 1.52 (broad s, 6H, Me), 6.85 and 7.08 (2t, JHH: 7.1 Hz,
3
2 × 4H, H on C2,3,6,7), 7.23 and 7.33 (2d, JHH: 7.1 Hz, 2 × 4H, H on
C1,4,5,8).

Fluorenyl Compounds
1957
13C: 21.05 (broad, Me), 45.52 (C9), 120.03 (C4C5), 124.70 (C1C8),
126.13, 126.74 (C2C7 and C3C6), 140.04 (C12C13), 145.81 (C10C11).
MS: 456 (M, 8), 421 (M-Cl, 1), 277 (M-CMeR2, 10), 179 (CMeR2, 100).
Synthesis of Difluoro(phenyl)(methylfluorenyl)silane 6
R2C(Me)H, 1.10 g (6.1 mmol); BuLi, 3.8 mL (6.1 mmol); PhSiF3, 0.99 g
(6.1 mmol); 6 (1.12 g, 75%).
NMR: 1H (80 MHz): 1.92 (s, 3H, Me), 6.90–7.78 (m, 13H, arom H).
2
13C: 17.76 (Me), 43.21 (t, JCF: 14.4 Hz, C9), 120.13 (C4C5), 124.38
(C1C8), 125.18 (t, 2JCF: 18.1 Hz, ipso-C Ph), 127.14, 127.23 and 127.62
(C2C7, C3C6 and m-CH Ph), 131.69 (p-CH Ph), 134.07 (o-CH Ph), 140.65
(C12C13), 146.06 (C10C11).
19F: −72.3.
MS: 322 (M, 23), 244 (M-Ph-1, 5), 179 (CMeR2, 100).
Synthesis of Diphenyl(fluorenyl)phosphine 7
19.70 mL (31.52 mmol) of n-BuLi were added to a suspension of fluorene
(5 g, 30.12 mmol) in Et2O (60 mL) at room temperature. The solution
turned red and after .5 h of stirring was added dropwise to one equiv-
alent of chlorodiphenylphosphine (6.64 g, 30.12 mmol) in solution in
Et2O (65 mL). The reaction mixture turned from red to yellow. 100 mL
of water were added and an abundant yellow precipitate appeared. This
yellow residue was recrystallized from THF to afford a white powder of
pure 7 (8.92 g, 84%, m.p.: 192◦C).
NMR: 1H: 5.01 (broad s, 1H, HC9), 6.97–7.32 (m, 18H, arom H).
1
3
13C: 46.19 (d, JCP: 24.0 Hz, C9), 119.82 (C4C5), 125.10 (d, JCP: 4.6
Hz, C1C8), 126.43 and 126.93 (C2C7 and C3C6), 128.15 (d, 3JCP: 6.5 Hz,
m-CH Ph), 129.14 (p-CH Ph), 133.80 (d, 2JCP: 20.3 Hz, o-Hz, o-CH Ph),
1
3
135.78 (d, JCP: 17.6 Hz, ipso-C Ph), 141.06 (d, JCP: 1.8 Hz, C12C13),
143.72 (d, 2JCP: 5.6 Hz, C10C11).
31P: 3.6.
MS: 350 (M, 18), 185 (PPh2, 43), 165 (R2CH, 100).
Synthesis of Dimesityl(fluorenyl)phosphine 8
5.20 mL (8.30 mmol) of n-BuLi were added to a suspension of fluorene
(1.32 g, 7.90 mmol) in Et2O (30 mL) at room temperature and stirred
for .5 h at this temperature. This solution was then added dropwise
to a solution of Mes2PCl/Mes2PBr (30/70; 2.72 g, 7.90 mmol) in Et2O
(40 mL). The reaction mixture turned red and a white precipitate ap-
peared. Then the solution turned green. After removal of the lithium

1958
L. Baiget et al.
salts, recrystallization from pentane afforded a white powder of pure 8
(2.81 g, 82%, m.p.: 138–142◦C (dec)).
NMR: 1H (80 MHz): 2.27 (s, 18H, p and o-Me), 5.74 (d, 2JPH: 3.1 Hz,
1H, HC9), 6.80 and 6.83 (2s, 2 × 2H, arom H Mes), 6.97–7.83 (m, 8H,
arom H CR2).
13C: 21.04 (p-Me Mes), 23.36 (d, 3JCP: 15.7 Hz, o-Me Mes), 43.03 (d,
1JCP: 28.7 Hz, C9), 119.81 (C4C5), 125.68 (d, 3JCP: 4.6 Hz, C1C8), 126.82
and 126.96 (C2C7 and C3C6), 130.36 (m-CH Mes), 131.63 (d, 1JCP: 31.4
Hz, ipso-C Mes), 138.37 (s), 141.20 (s), 143.48 (d, JCP: 16.6 Hz) and
145.04 (d, JCP: 10.2 Hz) (C10C11, C12C13, o-C Mes and p-C Mes).
31P: −14.3.
MS: 434 (M, 22), 419 (M-Me, 2), 315 (M-Mes, 1), 269 (M-R2CH, 100),
165 (R2CH, 1).
Synthesis of Diphenyl(fluorenyl)phosphine Oxide 9
A yellow solution of R2CHPPh2 7 (0.40 g, 1.14 mmol) in THF (10 mL)
was oxidized by gaseous oxygen at room temperature. After 5 min under
stirring, the solvent was removed in vacuo to afford a yellow powder of
pure 9 (0.21 g, 50%, m.p.: 223–227◦C).
NMR: 1H: 5.12 (d, 2JPH: 23.4 Hz, 1H, HC9), 7.12–7.62 (m, 18H, arom
H).
1
13C: 50.68 (d, JCP: 62.1 Hz, C9), 119.95 (C4C5), 126.21, 126.90 and
127.79 (3d, JCP: 2.6 Hz, 2.6 Hz and 1.7 Hz, C1C8, C2C7 and C3C6), 128.22
(d, 2JCP: 12.2 Hz, o-CH Ph), 129.98 (d, 1JCP: 99.4 Hz, ipso-C Ph), 131.74
3
4
(d, JCP: 8.7 Hz, m-CH Ph), 132.08 (d, JCP: 2.6 Hz, p-CH Ph), 139.07
and 141.90 (2d, JCP: 4.3 Hz and 4.4 Hz, C10C11 and C12C13).
31P: 31.7.
MS: 366 (M, 12), 201 (M-R2CH, 100), 165 (R2CH, 16).
Synthesis of Diphenyl(fluorenyl)phosphine Sulfide 10
0.10 g (0.39 mmol) of sulfur S8 were added to a solution of R2CHPPh2
7 (1.00 g, 2.80 mmol) in THF (25 mL); after 1 h of reflux under stirring,
the solvent was removed in vacuo. Recrystallization from THF afforded
pale yellow crystals of pure 10 (0.73 g, 72%, m.p.: 192–195◦C).
2
NMR: 1H: 5.23 (d, JPH: 18.1 Hz, 1H, HC9), 7.02–7.78 (m, 18 H,
arom H).
13C: 52.23 (d, 1JCP: 45.3 Hz, C9), 119.91 (d, 4JCP: 1.7 Hz C4C5), 125.99,
126.69 and 128.17 (3d, JCP: 3.5 Hz, 2.6 Hz and 2.6 Hz, C1C8, C2C7 and
C3C6), 128.35 (d, 2JCP: 12.2 Hz, o-CH Ph), 130.51 (d, 1JCP: 80.2 Hz, ipso-
C Ph), 131.82 (d, 4JCP: 2.6 Hz, p-CH Ph), 132.19 (d, 3JCP: 9.6 Hz, m-CH
Ph), 139.26 and 142.17 (2d, JCP: 4.4 Hz and 4.3 Hz, C10C11 and C12C13).

Fluorenyl Compounds
1959
31P: 48.9.
MS: 382 (M, 14), 217 (M-R2CH, 100), 165 (R2CH, 29), 139 (PhP(S)-1,
38).
Synthesis of Diphenyl(methylfluorenyl)phosphine 12
0.56 mL (0.90 mmol) of n-BuLi were added dropwise at room temper-
ature to a suspension of 7 (0.30 g, 0.86 mmol) in THF (10 mL). The
reaction mixture turned orange and was stirred for .5 h. 1.1 equivalent
(0.94 mmol) of methyl iodide were added and after 1 h, 10 mL of water.
Upon separation, the aqueous layer was extracted with Et2O. The com-
bined organic layers were dried over Na2SO4 and concentrated under
reduced pressure to afford a yellow powder of 12 (0.12 g, 38%, m.p.:
250◦C (dec)).
1
3
NMR: H: 2.61 (d, JCP: 13.0 Hz, 3H, R2CMe), 6.77–8.18 (m, 18H,
arom H).
31P: 3.3.
MS: 364 (M, 100), 165 (R2CH, 18).
Synthesis of Dichloro(diphenylphosphinofluorenyl)-
phosphine 13
2.55 mL (4.1 mmol) of n-BuLi were added dropwise to a solution of
7 (1.36 g, 3.88 mmol) in THF (25 mL) cooled at −30◦C. The mixture
(turned yellow) was allowed to warm to room temperature, then stirred
for .5 h, and finally was added dropwise to a solution of phosphorus
trichloride (2 eq., 7.77 mmol) in THF (20 mL). The solution turned
colorless. After removal of solvent, 20 mL of pentane and 20 mL of Et2O
were added. The lithium salts were removed by filtration, the filtrate
evaporated and the residue recrystallized from pentane/Et2O to afford
a white powder of 13 (0.75 g, 43%).
NMR: 1H (80 MHz): 7.10–8.10 (m, 18H, arom H).
13C: 120.26 (C4C5), 125.45 (dd, 3JCP: 4.8 Hz and 7.0 Hz, C1C8), 127.15
and 128.19 (C2C7 and C3C6), 128.27 (d, 3JCP: 7.8 Hz, m-CH Ph), 129.96
1
3
(p-CH Ph), 132.88 (dd, JCP: 18.3 Hz, JCP: 5.2 Hz, ipso-C Ph), 134.84
(dd, 2JCP: 22.7 Hz, 4JCP: 2.6 Hz, o-CH Ph), 141.52 (dd, 2JCP: 4.4 Hz and
10.5 Hz, C10C11), 141.57 (t, 3JCP: 1.75 Hz, C12C13).
31P: 6.4 (d, 2JPP: 167.8 Hz, PPh2), 179.8 (d, 2JPP: 167.8 Hz, PCl2).
Synthesis of Dichloro(dimesitylphosphinofluorenyl)-
phosphine 14
1.55 mL (2.47 mmol) of n-BuLi were added to a solution of R2CHPMes2
8 (0.98 g, 2.25 mmol) in THF (25 mL) cooled at −20◦C. After 20 min of

1960
L. Baiget et al.
stirring, the red solution was added dropwise at the same temperature
to a solution of phosphorus trichloride (1.54 eq., 0.3 mL) in Et2O (10 mL).
The reaction mixture was allowed to warm to room temperature and
then stirred for 1 h. After removal of the lithium salts, the product
was unambiguously characterized by NMR spectroscopy but could not
be isolated in pure form by crystallization. However, it can be used
without further purification.
2
2
NMR: 31P (THF): −26.4 (d, JPP: 409.0 Hz, PMes2), 167.2 (d, JPP
:
409.0 Hz, PCl2).
Reaction of R2C(Li)PPh2 with AsF3: Synthesis of 15 and 16
R2C(Li)PPh2 11 was prepared as previously described from 0.50 g
(1.40 mmol) of 7. The reaction mixture was then added at room temper-
ature to a solution of AsF3 (0.28 g, 2.1 mmol) in THF (15 mL) and turned
yellow. After .5 h of stirring, the mixture was analyzed and 15 (66%)
and 16 (33%) were characterized by NMR spectroscopy. Fractional crys-
tallization did not allow the separation of these two compounds.
NMR: 15: 19F: −35.1 (d, 3JPF: 28.1 Hz).
31P: −6.1 (t, 3JPF: 28.1 Hz).
16: 19F: −132.4 (t, 3JPF: 38.4 Hz).
31P: 7.9 (d, 3JPF: 38.4 Hz).
Reaction of R2C(Li)PPh2 with SbF3: Synthesis of
Fluoro[bis(diphenylphosphinofluorenyl)]antimony 17
R2C(Li)PPh2 11 was prepared as previously described from 1.81 g
(5.17 mmol) of 7, and added dropwise to a solution of SbF3 (1.8 g,
1.9 eq., 9.90 mmol) in THF (30 mL) cooled at −50◦C. The reaction mix-
ture turned orange and was allowed to warm to room temperature.
The solution turned brown, and after removal of the lithium salts, a
pale brown compound was obtained. 17 was not completely purified by
crystallization but crude solution can be used for further reactions.
NMR: 19F: −125.0 (t, 3JPF: 27.8 Hz).
31P: 2.6 (d, 3JPF: 27.8 Hz).
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1961
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