Synthesis of New Cyclopentadienyl-, Indenyl- and Fluorenylphosphanes by the Reaction of Carbanions of the Cyclopentadienyl Type with Alkyl(aryl)chloro-N,N-dialkylaminophosphanes

Article abstract of DOI:10.1515/znb-2001-0815

A number of alkyl(aryl)chloro-N,N-dialkylaminophosphanes RP(Cl)NR¹R² (1a-o) were synthesized starting from alkyl(aryl)dichlorophosphanes RPCl₂ and amines by a convenient procedure with nearly quantitative yields. The reactivity of alkyl(aryl)-N,N-dialkylamino(halogeno)phosphanes RP(Hal)NR¹R² (Hal = Cl, I) with cyclopentadienyl, bis(cyclopentadienyl), indenyl, bis(indenyl) and fluorenyl carbanions has been investigated. The new aminocyclopentadienylphosphanes R_nCp(R)PNR¹R² 2a-f and 3a-c (R_nCp = Ind, Flu, Cp₂CMe₂, Ind₂CEt₂, Ind₂(CH₂)₂) were characterized by spectroscopic techniques and elemental analyses. Flu(t-Bu)PN(H)t-Bu (2f) was characterized by X-ray diffraction analysis.

Full text of DOI:10.1515/znb-2001-0815

Synthesis of New Cyclopentadienyl-, Indenyl- and Fluorenylphosphanes
by the Reaction of Carbanions of the Cyclopentadienyl Type with
Alkyl(aryl)chloro-A^A^-dialkylaminophosphanes
Vasily V. Kotova,#’, Evgeni V. Avtomonov*5, Nikolai A. Ustynyukb,
and Dmitry A. Lemenovskii
3
a Department of Chemistry, M. V. Lomonosov Moscow State University,
Leninskie Gory, 119899, Moscow, Russia
b A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
Vavilova str.28, 117813, Moscow, Russia
# Present address: Institute of Organic Chemistry, University of Münster, Corrensstrasse 40,
D-48149 Münster, Germany
Reprint requests to Dr. Vasily V. Kotov.
Fax: +49-(0)251-833-6503. E-mail: kww@uni-muenster.de
Z. Naturforsch. 56b, 812-822 (2001); received March 30, 2001
Cyclopentadienylphosphanes, Alkyl(aryl)chloro-./V,/V-dialkylaminophosphanes,
(Amino)cyclopentadienylphosphanes
A number of alkyl(aryl)chloro-iV,/V-dialkylaminophosphanes RP(C1)NR
synthesized starting from alkyl(aryl)dichlorophosphanes RPC1 and amines by a convenient
procedure with nearly quantitative yields. The reactivity of alkyl(aryl)-iV,iV-dialkylamino(halo-
geno)phosphanes RP(Hal)NR (Hal = Cl, I) with cyclopentadienyl, bis(cyclopentadienyl),
indenyl, bis(indenyl) and fluorenyl carbanions has been investigated. The new aminocyclo-
pentadienylphosphanes R„Cp(R)PNR 2a-f and 3a-c (R„Cp = Ind, Flu, Cp CMe2,
Ind CEt2, Ind (CH2)2) were characterized by spectroscopic techniques and elemental analy-
ses. Flu(r-Bu)PN(H)f-Bu (2f) was characterized by X-ray diffraction analysis.
1
R
2
(la-o) were
2
1
R
2
1
R
2
2
2
2
Introduction
scribed up to now, e.g. [Me
(I) [1,2], [Cp(CH NMe]MCl
CH )NR]MC1 [9], [Me Cp(BN/-Pr
[10] (R = Alk; M = Ti(IV), Zr(IV), Hf(IV)).
We have been exploring the synthesis of new li-
gands derived from the alkyl(amino)cyclopentadie-
4
Cp(SiMe
2
)Nf-Bu]MCl
], [Cp(C=
)NPh]MCl
2
2
)
2
2
[
8
2
2
4
2
2
So called CGC (Constrained Geometry Cata-
lysts) complexes (I) as a new class of homogeneous
olefin polymerization catalysts were reported ten
years ago by researchers of Dow and Exxon [1-3].
These group 4 mono-cyclopentadienyl-amido de-
rivatives are based on the ligand system first
described by Bercaw [4] for organoscandium com-
plexes, and are distinguished by a sterically accessi-
ble catalyst active site, which allows incorporation
of other olefins into polyethylene. There is a
number of reports in the literature dealing with the
copolymerization of ethylene and linear a-olefins
nylphoshanes RnCpP(R)NR
1
R
2
(R„, R, R1, R =
2
Aik, Ar or H) in an attempt to probe this class of
compounds as ligands in transition metal chemistry.
The choice of R„CpP(R)NR
1
R2 was stimulated by
the expectation that the presence of two strong o-
donors connected with the cyclopentadienyl frame
could have an impact on the catalytic properties of
the target complexes due to electron donating ef-
fects of the R
2
N(R)P-moiety.
such as propene,
1
-butene,
1
-hexene and -octene
1
[
1 ,2
] with cyclic monomers such as ethylidene-nor-
bornene [5,6]. Additionally, when compared to bis-
cyclopentadienyl metallocenes, the activated CGC
catalysts are thermally more stable up to reaction
temperatures of 160 °C and generally produce
polymers of higher molecular weight [7]. Several
types of complexes of such kind have been de-
R-PX
..N
R2"" I
R1
\
,.*C1
P-NV»2
M,
Cl
Hal
III
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V. V. Kotov et al. • Synthesis of New Cyclopentadienyl-, Idenyl- and Fluorenylphosphanes
813
at the cyclopentadienyl ring. To avoid an oligo-
merization of the target product we used bulky
substituents at the phosphorus atom (e.g. R =
r-Bu) and alkyl-substituted cyclopentadienes, as
well as their benzocondensed analogues such as
indene or fluorene, and bridged biscyclopenta-
There are two main synthetic approaches to the
type II of ligands (Scheme 1), containing a three-
coordinated phosphorus atom: a)
a stepwise
nucleophilic substitution of the halogen atoms at
the phosphorus center by cyclopentadienyl type
carbanions and amines and b) the reaction of
cyclopentadienyl anions with alkyl(aryl)chloro- dienes with a carbon bridge as educts.
Generally, alkyl(aryl)chloro-./V,./V-dialkylamino-
phosphanes RP(C1)NR are easily accessible
from the reaction between an alkyl(aryl)dichloro-
phosphane RPC1 and an amine/amide in diethyl
ether [16-18] or a trimethylsilyl-substituted amine
Me SiNR [19]. In both cases a fractional distil-
-/V,Af-dialkylaminophosphanes (III). Both routes
have been applied for the preparation of the
ligand precursors in our work.
1
R
2
2
/ 5^Rn
5
RPCl,
\ \ J
+ 2 HNR'R2
3
1
R
2
lation had to be applied for the isolation of the
product. In our work we modified the procedure
[16] (see experimental part) and prepared a series
of alkyl(aryl)chloro-./V,Af-dialkylaminophosphanes
R
+
RV-N --------------------------------------
1
RP(C1)NR
1
R
2
by a direct reaction of RPC1
2
with
Li
Hal'
R2
b
an amine HNR*R
(Scheme 2).
2
in hexane at low temperature
RnCp = Cp, Ind, Flu; R = Alk, Ar; R1= H or R2; R2 = Aik or Ar.
Scheme 1.
R
R
P-N
Cl
R
hexane
U
P-Cl + 2 HNR'R2
la-o
e
The route “a” is a common pathway to alkylam-
ino(cyclopentadienyl)phoshanes and has been de-
scribed previously in the literature [1 1 -1 3 ]. This
method is, however, confined to bulky cyclopenta-
dienyl and alkyl substituents at the phosphorus
atom.
The second route “b” for which alkyl(aryl)-
chloro-Af N-dialkylaminophosphanes might be
used as starting key-compounds has not been ex-
plored so far. It could advantageously be used for
the preparation of sterically less encumbered de-
rivatives. To the best of our knowledge, only one
example of such reactions, i.e. that of FluLi with
Cl
R2
d
1
a
b
c
R
R
R
f-Bu
r-Bu
H
t-Bu
Et
r-Bu
t-Bu
r-Bu
Ph
H
1
2
Et
(CH2 ) 5 (CH
2
2
2
CH2)20
CH2)0
CH2)20
h
i
1
f
g
j
R
R
R
Me
r-Bu
H
Me
Et
Et
Me
Me
Me
Ph
1
2
(CH2 ) 5 (CH
m
n
1
k
1
o
Cl(Ar)PNEt
Flu(Ar)PNEt
2
leading to the corresponding
(Ar = 2,6-dimethylphenyl) in good
2
R
R
R
Ph
f-Bu
H
Ph
Et
Et
Ph
Ph
Ph
Ph
H
yield, has been described in the literature [14].
Here we report the synthesis of new alkylamino-
(cyclopentadienyl)phosphanes (II), using route
“b” as a synthetic strategy, and the unexpected be-
havior of alkyl(aryl)chloro-7V,./V-dialkylamino-
phosphanes (III).
1
2
(CH2 ) 5 (CH
Scheme 2.
Two types of aminophosphanes RP(C1)NR2H
and RP(C1)NR (with primary and secondary
1
R
2
amine substituents), are selectively obtained from
this reaction in high yield. The use of hexane as a
solvent for these transformations is essential. On
one hand, a very low solubility of the ammonium
Results and Discussion
It is well known that cyclopentadienylphos-
phanes are a thermally labile class of compounds
[15]. They readily undergo Diels-Alder reactions salt in aliphatic solvents makes further purification
which are promoted by the phosphanyl substituent of the product by distillation unnecessary. Even
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814
V. V. Kotov et al. • Synthesis of New Cyclopentadienyl-, Idenyl- and Fluorenylphosphanes
traces of the ammonium salt in the resulting pro- were applied in the reaction with different precur-
duct are responsible for the degradation of sors la-p . The reactions of R„CpLi, R„CpNa,
RP(C1)NR
1
R
2
[20,21]. Thus, a very low impurity R„CpK and (R„Cp)2Mg with la -p lead to a mix-
of the ammonium salt in the product that is ture with similar ratios of products, according to
achieved in the aliphatic solvent admits a long 31P and XH NMR data (Scheme 4).
storage of the product (no decomposition after
3 months according to 31P NMR spectra).
From the formal point of view, Cp-salts react
with compounds la -p in two different ways, i.e.
via a formal nucleophilic substitution reaction at
P -C l and P -N bonds. The ratio of the products
does not depend on the nature of the metal cation,
the solvent, and the type of the halogen substitu-
ent (Cl or I). It is worth to note that CpTl and
/-Bu
Et
t-Bu.
Et
Et
benzene
+
Nal
P-N
P-N
lp
/
\
A; 5 h
-NaCl
Cl'
I
Et
Me
4
CpSnMe do not react with alkyl(aryl)chloro-
3
Scheme 3.
AfTV-dialkylaminophosphanes at all.
It appears that the formation of the target pro-
The chlorine substituent in the aminoalkylchlo- duct R„Cp(R)PNR
rophosphanes (la -o ) can be replaced by iodine
using Nal as iodinating agent [22] to form alkyl- sent in the reaction mixture. In this case
1
R
2
proceeds slowly, while an
excess of the starting RP(Hal)NRxR is still pre-
2
N,Af-dialkylamino(iodo)phosphanes (Scheme 3). RP(Hal)NR
/-Butyl-jty,./V-diethylamino(iodo)phoshane (lp) has R„Cp(R)PNR
1
R
1
2
may react with the product
leading to R„Cp(R)PHal and
R
2
been obtained by this method in quantitative RP(NRxR2)2, respectively.
yield. The highly air- and moisture sensitive pro-
ducts la -p were characterized by EI-MS, *H and RP(NRxR2 ) 2 with cleavage of the P -N bond in
31P NMR spectroscopy, and elemental analyses. the presence of R3MgBr has been described and
The second step of method „b“ is the alkylation used for the synthesis of alkylphosphanes
of the phosphorus(III) atom by organometallic de- RP(R )NR*R (R = Me) [23]. In order to exclude
The reactivity of alkyldiaminophosphanes
3
2
3
rivatives of alkyl-substituted cyclopentadienes, in- the possibility that mono-Cp-organometallics can
denes and fluorenes. These carbanions are dif- react with alkylaminochlorophosphanes in the
ferent in structure and nucleophilicity. The first same manner, an investigation of the reaction of
experiments have demonstrated that the reaction R„CpM or R„CpM xL (M = Li; L = TMEDA or
takes place only in THF as a solvent. In an attempt crown-4) with MeP(NEt2 ) 2 was performed under
to prepare f-butyl-(A^,A^-diethylamino)-(tetrameth- different conditions. The reaction was monitored
ylcyclopentadienyl)phosphane, tetramethylcyclo- by 31P NMR spectroscopy. It does not proceed
pentadienyllithium (Me
one equivalent of £-BuP(Cl)NEt
-78 °C. The reaction resulted in an unexpected
4
CpLi) was reacted with
over one week upon stirring of the reaction mix-
ture at room temperature or even over one week
at reflux in THF. In all cases the starting materials
2
(lb) in THF at
mixture of products (Scheme 4). For the sake of a could be recovered unchanged. This fact demon-
strates that the proposed interpretation is proba-
better understanding different cyclopentadienides
V\j
+
'A
+
RP(NR‘R2)2
PWR
2
1
/ P w R
Hal
r 2r ‘n
-50%
-35%
-15%
M = Li, LixTMEDA, Lixcrown-4, Na, K, Mg; RnCp = Cp, f-BuCp, Me4Cp, Cp*; Hal = Cl, I.
Scheme 4.
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V. V. Kotov et al. • Synthesis of New Cyclopentadienyl-, Idenyl- and Fluorenylphosphanes
815
bly correct, although a detailed study of the mech- and to further oligomerization of these very reac-
anism would be necessary. We speculate that the tive species.
All compounds synthesized are highly soluble in
aliphatic solvents and exist as a mixture of isomers.
mechanism of this kind of ligand redistribution is
similar to the well known exchange reaction for
the derivatives of tin [24], arsenic, antimony, and The structure of Flu(?-Bu)PN(H)r-Bu (2f) was de-
bismuth [25-28],
termined by an X-ray analysis (Fig. 1).
Surprisingly, the reactions of alkyl(aryl)amino-
The geometry at the phosphorus atom can be
chlorophosphanes with indenyl, fluorenyl, bis- best described as a distorted tetrahedron with the
cyclopentadienyl or bis-indenyl lithium/dilithium bond angles ranging from 101° to 106° [N(l)~
salts lead to the target compounds 2a-f and 3a-c P (l)-C (ll)], which indicates a certain sterical
in high yields (Scheme 5).
strain in the molecule. The P (l)-N (l) bond of
1.680(2) Ä and the bond P (l)-C (ll) of 1.923(2)
A are somewhat longer than the typical P(III)-N
and P (III)-C bond distances in most substituted
organophosphorus compounds [30], which again
confirms the steric hindrance in 2f. All other struc-
tural fragments do not reveal any peculiarities.
Compounds 3a-c have been characterized by
XH, 1 3 C, 31P NMR spectroscopy and elemental
analyses. The substances possess four stereogenic
centers and exist as a complex mixture of stereo-
isomers. Eight diastereomers are theoretically pos-
sible, some of them happen to have the same
chemical shifts, and only four (three enantiomeric
pairs and one meso-iorm) can be destinguished by
31P NMR. The proposed number of stereoisomers
R
+
RV_ NRl THF / -78°C
n ' p 2 - LiCl
[ ^
V
^
N
r ' r 2
Li
r
95-98%
2
a
b
c
d
e
f
R
r-Bu
Me
r-Bu
f-Bu
Me
f-Bu
Et
Et
R1
R2
Et
Et
Et
Et
r-Bu
H
Et
Et
r-Bu
H
RnCp
Ind
Ind
Ind
Flu
Flu
Flu
95-98%
3
a
b
/-Bu
Et
c
r-Bu
Et
R
r-Bu
Et
R1
R2
Et
Et
Et
(R„Cp)2Z
(Ind)2(CH2)2
Cp2CMe2
(Ind)2CEt2
Scheme 5.
Bis(aminocyclopentadienyl)phosphanes
3a-c
could not be prepared by method “a” as a syn-
thetic strategy [29], and this result may be attrib-
uted to the allylic structure of the bis(alkylchloro-
cyclopentadienyl)phosphanes and/or the high
sterical hindrance in these encumbered substrates.
Fig. 1. ORTEP diagram of the molecule of Flu(f-
Bu)PN(H)f-Bu (2f). Selected bond distances (Ä): P (l)-
N (l) = 1.680(2), P (l)-C (5 ) = 1.865(2), P (l) -C (ll)
=
=
=
1.923(2), C (ll)-C (1 2 )
1.509(3); Selected bond angles [°]: N (l)-P (l)-C (5 )
101.5(1), N ( l) - P ( l) - C ( ll)
C (ll) 101.13(9), C (1 2 )-C (ll)-C (2 3 )
=
1.504(3), C (ll)-C (2 3 )
=
105.94(9), C (5 )-P (l)-
102.5(2),
116.0(1), C (2 3 )-C (ll)-P (l) =
The addition of amines (e.g. Me
?-BuNH2, /-Pr NH) leads to the formation of phos-
phafulvene intermediates via /?-“HCl”-elimination
2
NH, Et NH,
2
=
=
2
C (1 2 )-C (ll)-P (l)
=
108.9(1).
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816
V. V. Kotov et al. • Synthesis of New Cyclopentadienyl-, Idenyl- and Fluorenylphosphanes
is seen for 2,2-bis[(r-butyl-N,Ar-dialkylaminophos-
phanyl)indenyl]pentane (3c) (Fig. 2).
been developed. This type of ligands are interest-
ing with respect to application in transition metal
The 31P NMR spectra confirm this assumption chemistry; this work is under way.
and show seven resonances. The meso-iorm has
Experimental
two phosphorus atoms that are equivalent and
give rise to only one resonance. Each molecule of
the rac-form has two nonequivalent phosphorus
atoms that give two signals in the 31P NMR
All manipulations involving air- and moisture
sensitive materials were carried out by standard
Schlenk techniques under an atmosphere of dry
spectrum. A total of seven resonances are ob- argon. Solvents were dried and distilled prior to
use and stored under an inert atmosphere. XH, 13C
and 31P NMR spectra were recorded at 25 °C on
Bruker AC250P, Bruker ARX300 and Varian
VXR-400 spectrometers. Mass spectra (EI-MS)
were recorded on a Varian CH-7a device using
electron impact with an ionization energy of
70 eV; all assignments were made with reference
to the most abundant isotopes. C, H and N ele-
mental analyses were carried out by the Microana-
lytical Division of the A. N. Nesmeyanov Institute
of Organoelement Compounds, Russian Academy
of Sciences. IR spectra were recorded on a Nicolet
510 FT-IR spectrometer. CpCMe2Cp [31], IndCEt2-
served, having different integral intensities. For
the reason of complexity of the isomeric mixtures
we were not able to make a detailed analysis of
the proton and carbon NMR spectra. In the case
of the bis(cyclopentadienyl) compound 3a the
and 13C spectra are even more complex and the
structure is proposed solely on the basis of C, H,
N analysis and 31P NMR spectra.
Conclusions
We have developed a new facile route to a class
of P-functionalized phosphano-substituted cyclo-
pentadienes, indenes and fluorenes and their
bis(cyclopentadienyl) analogues 2 a -f and 3a-c.
Ind [32], IndCH
prepared according to the literature methods.
?-BuPCl has been used as a 1.02 M solution in
hexane. Li, Na and K salts of the cyclopentadienyl
aminoalkyl(aryl)halogenophosphanes la - o has ligand precursors and of indene and fluorene were
2
CH2Ind [33], f-BuPCl
2
[34] were
2
A
straightforward procedure to iV-alkyl(aryl)-
meso-
rac-
(S,S/R,R)
(S,R/S,R)
r 2r ‘n
1 0
NR R
(R,S/R,R)
(R,R/R,R)
Fig. 2.
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V. V. Kotov et al. • Synthesis of New Cyclopentadienyl-, Idenyl- and Fluorenylphosphanes
817
obtained by deprotonation with a 1.6 M solution
of /i-BuLi (purchased from Merck), NaH (Merck)
or PhCH2K [35] by standard procedures.
XH NMR (400 MHz, C
6
D6): d = 2.7 (broad s,
1H , -N H ), 1.09 (d, 9 H, r-BuN-,4^ 31? - ^ )
0.8 Hz), 1.01 (d, 9 H, r-BuPCl-, V ^ P ^ H )
13.6 Hz). - 3 1 P{ H} NMR (162 MHz, C
137.5. - MS (El,70 eV): m/z (%) = 196 (56)
[M+], 1 9 C1NP (195.67): calcd. C 49.11,
=
=
1
6
D6): (5 =
General procedure for the preparation o f la,f,k
-
C8 H
H 9.79, N 7.16; found C 48.98, H 9.67, N 7.22.
The total amount of the amine H
= r-Bu, Ph) was added at once to a solution of
RPC1 (1 mol) in hexane at -100 °C (in the case
2
NR
2
(2 mol;
R
2
t-Butyl-chloro-N,N-diethylaminophosphane (lb)
2
of R = r-Bu, at room temperature), and the mix-
ture was stirred for 5 h, while warming to room
temperature (R = f-Bu for 24 h). Then the precipi-
tated ammonium salt was removed by filtration.
The filtrate was concentrated in vacuum (3 Torr)
at room temperature to yield the product as an
oily colorless liquid or as a white solid. The yields
were in all cases nearly quantitative.
Obtained from 6.15 ml of f-BuPCl
and 1.33 ml of Et2NH (12.5 mmol).
2
(6.28 mmol)
XH NMR (400 MHz, C
-N C // CH3), 1.09 (d, 9 H, t-BuPCl-,
XH) = 14.4 Hz), 0.87 (t, H, -N C H CH3,
lH) = 12.0 Hz). - 3 1 P{ H} NMR (162 MHz, C
<3 = 158.0. - MS (El 70, eV): m/z (%) = 167 (14)
[M+-CH CH2]. 1 9 C1NP (195.67): calcd.
6
D6): <3 = 2.9 (m, 4 H,
2
3
/( 3 1 P -
6
2
3
7(
1
H -
1
6
D6):
2
-
C8 H
C 49.11, H 9.79, N 7.16; found C 49.00, H 9.67,
N 7.03.
General procedure for the preparation of
lb,c,e,g,h,ij ,l,m,n,o
t-Butyl-chloro-N-piperidylphosphane (lc)
A
solution of HNRXR
(amine/hexane = 1/30) was slowly added to a solu-
tion of RPC1 (1 mol) in hexane at -100 °C (in the
2
(2 mol) in hexane
Obtained from 6.15 ml of f-BuPCl
and 1.22 ml of piperidine (12.5 mmol).
XH NMR (400 MHz, C D6): (3 = 2.93 (m,
4 H, -N (C 7/ (CH2)3), 1.25 (broad s, H,
-N (C H (C7/2)3), 1.08 (d, H, r-BuPCl-,
V P P ^ H ) = 14.4 Hz). - 3 1 P{ H} NMR (162 MHz,
D6): d = 155.1. - MS (El, 70 eV) m/z (%) =
150 (1) [M+-?-Bu], - C 1 9 C1NP (207.68): calcd.
2
(6.28 mmol)
2
6
case of R = f-Bu, at room temperature) and the
mixture was stirred for 5 h, while warming to room
temperature (R = t-Bu for 24 h). Then the precipi-
tated ammonium salts were removed by filtration.
The transparent colorless solutions were concen-
trated in vacuum (3 Torr) at room temperature to
yield the products as oily colorless liquids or white
solids. The yields were in all cases nearly quantita-
tive.
2
)
2
6
2
)
2
9
1
C
6
9
H
C 52.05, H 9.22, N 6.74; found C 52.18, H 9.13,
N 6.81.
t-Butyl-chloro-N-morpholinyl-phosphane (ld)
Obtained from 6.15 ml of r-BuPCl
and 1.1 ml of morpholine (12.5 mmol).
*H NMR (400 MHz, C D6): <5 = 3.32 (m, 4 H,
-N C H CH 0 ), 2.86 (m, 4 H, -N C // CH 0 ), 1.05
(d, 9 H, r-BuPCl-, V P P ^ H ) = 14.4 Hz). -
H} NMR (162 MHz, C D6): (3 = 154.2. - MS
(El, 70 eV): m/z (%) = 152 ( ) [M+-r-Bu]. -
H 17ClNOP (209.07): calcd. C 45.83, H 8.17,
; found C 45.70, H 8.03, N 6.77.
2
(6.28 mmol)
General procedure for the preparation of
2 a -f and 3 a-c
6
2
2
2
2
The total amount of an A/,./V-dialkylaminoalkyl(-
halogeno)phosphane ( 1 mol) was added at once to
a solution/suspension of the alkali metal cyclopen-
tadienide (1 mol) in THF at -78 °C, and the mix-
ture was stirred for 24 h, while warming to room
temperature The red or light-red solution was con-
centrated in vacuum. A product was extracted
3 1 P{
1
6
8
C
N
8
6
.
6 8
t-Butyl-chloro-phenylaminophosphane (le)
Obtained from 6.15 ml of J-BuPC1 (6.28 mmol)
and 1.14 ml of PhNH (12.5 mmol).
XH NMR (400 MHz, C D6): Ö = 7.14-6.70 (m,
5 H, Ar), 3.05 (broad s, 1 H, PhN//- ) , 0.97 (d,
9 H, r-BuPCl-, H) = 13.6 Hz). - 3 1 P{ H}
NMR (162 MHz, C D6): d = 131.2. - MS (El,
70 eV): m /z (% ) = 215 (58) [M+], - C1 0
with a mixture of Et 0/hexane (20/80), and the
2
precipitated LiCl was removed by filtration. The
solution obtained was concentrated in vacuum at
room temperature to yield the product as an oily
liquid or as a colored solid. Yield: 95-98% .
2
2
6
3
/ ( 1 3 P -
1
1
6
N-t-Butylamino-t-butyl-chlorophosphane (la)
H
1 5 C1NP
Obtained from 30.05 ml of r-BuPCl
2
(30.6
(215.06): calcd. C 55.69, H 7.01, N 6.49; found
C 55.60, H 6.93, N 6.55.
mmol) and 6.48 ml of f-BuNH (61.3 mmol).
2
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818
V. V. Kotov et al. • Synthesis of New Cyclopentadienyl-, Idenyl- and Fluorenylphosphanes
[M+]. - C
7
H 9 C1NP (173.01): calcd. C 48.44, H 5.23,
t-Butylamino-chloro-methylphosphane (If)
N 8.07; found C 48.55, H 5.13, N 7.96.
Obtained from 0.76 ml of MePCl
and 1.8 ml of r-BuNH (17.1 mmol).
XH NMR (400 MHz, C D6): d = 2.73 (broad s,
1 H, -NH), 1.37 (d, 3 H, CH PC1-, H) =
10.8 Hz), 1.08 (d, 9 H, t-B uN -, V ^ P -^ H ) =
1.2 Hz). - 3 1 P{ H} NMR (162 MHz, C D6): (3 =
124.3. - MS (El, 70 eV): m/z (%) = 154 (23)
[M++H]. - 1 3 C1NP (153.04): calcd. C 39.10, XH) = 13.6 Hz), 1.13 (d, 9 H, r-BuN-, V ^ P ^ H ) =
2
(8.55 mmol)
2
t-Butylamino-chloro-phenylphosphane (lk)
6
3
2
/( 3 1 P -
1
Obtained from 0.75 ml of PhPCl
and 1.18 ml of ?-BuNH (11.1 mmol).
*H NMR (400 MHz, C D 6): d = 7.71 (m, 2 H,
Ar), 7.15 (m, 3 H, Ar), 3.0 (d, 1 H, -NH,
2
(5.58 mmol)
2
1
6
6
2
/( 3 1 P -
C H
5
1.1 Hz). - 3 1 P{
117.1. - MS (El, 70 eV): m/z (%) = 216 (93)
[M++H], - C1 0 1 5 C1NP (215.06): calcd. C 55.69,
1
H} NMR (162 MHz, C D6): (3 =
6
H 8.53, N 9.12; found C 39.25, H 8.41, N 9.03.
Chloro-(diethylamino)-methylphosphane (1 g)
H
H 7.01, N 6.49; found C 55.78, H 6.90, N 6.38.
Obtained from 0.76 ml of MePCl
and 1.77 ml of Et2NH (17.1 mmol).
2
(8.55 mmol)
Chloro-(diethylamino)-phenylphosphane (11)
XH NMR (400 MHz, C
-N C // CH3), 1.44 (d, 3 H, M ePCl-, V ^ P ^ H ) =
12.3 Hz), 0.85 (t, H, -N C H CH3, 3J(lH - XH) =
7.1 Hz). - 3 1 P{ H} NMR (162 MHz, C
145.4. - MS (El, 70 eV): m/z (%) = 153 (
[M+]. 1 3 C1NP (153.04): calcd.
6
D6): (3 = 2.85 (m, 4 H,
Obtained from 0.75 ml of PhPCl
and 1.15 ml of Et2NH (11.1 mmol).
2
(5.58 mmol)
2
6
2
XH NMR (400 MHz, C
Ar), 7.14 (m, 2 H, Ar), 7.08 (m, 1 H, Ar), 2.87
(m, 4 H, -N C H CH3), 0.83 (t, H, -N C H CH3,
7( H - H) = 7.1 Hz). - 3 1 P{ H} NMR (162 MHz,
D6): (5 = 140.3. - MS (El, 70 eV): m/z (%) =
216 (13) [M++H], - C1 0 1 5 C1NP (215.06): calcd.
6
D6): (3 = 7.69 (m, 2 H,
1
6
D6):
6
=
)
8
2
6
2
-
C
5
H
C 39.10,
H 8.53, N 9.12; found C 39.22, H 8.41, N 9.25.
3
1
1
1
C
6
H
Chloro-methyl-piperidylphosphane (lh)
C 55.69, H 7.01, N 6.49; found C 55.76, H
N 6.34.
6
.
8
8
,
Obtained from 0.76 ml of MePCl
and 1.67 ml of piperidine (17.1 mmol).
lH NMR (400 MHz, C D6): (5 = 3.83 (broad s,
4 H, - N(C7f (CH2)3), 1.43 (d, 3 H, M ePCl-,
V P P ^ H ) 12.7 Hz), 1.24 (broad s, H,
-N (C H (C //2)3). - ^PpH} NMR (162 MHz,
D6): = 141.3. - MS (El, 70 eV): m /z (% ) =
165 [M+]. 1 3 C1NP (165.04): calcd.
2
(8.55 mmol)
6
Chloro-piperidyl-phenylphosphane (1 m)
2 2
)
=
6
Obtained from 0.75 ml of PhPCl
and 1.15 ml of piperidine (11.1 mmol).
XH NMR (400 MHz, C D 6): Ö = 7.68 (m, 2 H,
Ar), 7.3-7.0 (m, H, Ar), 2.85 (m, 4 H,
-N (CH (CH2)3), 1.2 (m, H, -N(CH (CH2)3). -
H} NMR (162 MHz, C D 6): (5 = 138.9. - MS
227 (20) [M+].
2
(5.58 mmol)
2
)
2
6
C
6
6
3
(
8
6
)
-
C6 H
2
)
2
6
2 )2
C 43.52, H 7.91, N 8.46; found C 43.41, H 7.83,
N 8.58.
3 1 P{
1
6
(El, 70 eV): m/z (%)
=
-
Cn H 15ClNP (227.06): calcd. C 58.03, H 6.64,
Chloro-methyl-(N-morpholinyl)phosphane (li)
N 6.15; found C 57.89, H 6.71, N 6.28.
Obtained from 0.76 ml of MePCl
and 1.49 ml of morpholine (17.1 mmol).
*H NMR (400 MHz, C D6): d = 3.3 (m, 4 H,
-N C H CHzO), 2.73 (m, 4 H, -N C // CH 0 ), 1.34
(d, 3 H, M ePCl-, V ^ P ^ H ) = 11.9 Hz). - ^PpH}
NMR (162 MHz, C D6): (3 = 142.0. - MS (El,
70 eV): m/z (%) = 167 (70) [M+]. - Q H u ClNOP
(167.02): calcd. C 35.84, H 6.62, N 8.36; found
C 35.71, H 6.54, N 8.23.
2
(8.55 mmol)
Chloro-(N-morpholinyl)-phenylphosphane (In)
6
Obtained from 0.75 ml of PhPCl
and 0.97 ml of morpholine (11.1 mmol).
XH NMR (400 MHz, C D6): d = 7.65 (m, 2 H, Ar),
7.14 (m, 2 H, Ar), 7.09 (m, 1 H, Ar), 3.27 (m, 4 H,
-N C H CH 0 ), 2.75 (m, 4 H, -N C tf CH 0). -
H} NMR (162 MHz, C D6): (3 = 136.9. - MS
229 (54) [M+].
2
(5.58 mmol)
2
2
2
6
6
2
2
2
2
3 1 P{
1
6
(El, 70 eV): m/z (%)
=
-
C1 0 H 1 3 C1NOP (229.04): calcd. C 52.30, H 5.71,
Chloro-methyl-(phenylamino)phosphane ( lj)
N 6.10; found C 52.21, H 5.82, N 5.97.
Obtained from 0.76 ml of MePCl
and 1.56 ml of PhNH (17.1 mmol).
*H NMR (400 MHz, C D 6): d = 7.05 (m, 2 H,
Ar), 6.9 (m, 2 H, Ar), . 8 (m, 1 H, Ar), 4.45 (broad
s, 1 H, PhNH -), 1.25 (d, 9 H, r-BuPCl-,
XH) = 11.3 Hz). - 3 1 P{ H} NMR (162 MHz, C
<5 = 118.5. - MS (El, 70 eV): m/z (%) = 173 (5)
2
(8.55 mmol)
2
Chloro-phenylamino-phenylphosphane (lo )
6
Obtained from 0.75 ml of PhPCl
and 0.5 ml of PhNH (11.1 mmol).
*H NMR (400 MHz, C D 6): Ö = 7.56 (m, 2 H,
Ar), 7.2-6.7 (m, H, Ar and PhN), 4.82 (d, 1 H,
2
(5.58 mmol)
6
2
2
/ ( 1 3 P -
6
1
6
D6):
8
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V. V. Kotov et al. • Synthesis of New Cyclopentadienyl-, Idenyl- and Fluorenylphosphanes
819
Diethylamino(lH-inden-3-yl)methylphosphane (2b)
PhNH -, V ^ P ^ H ) = 25.0 Hz). - 31P{1H} NMR
(162 MHz, C6D6): <3 = 109.1. - MS (El, 70 eV):
m/z (%) = 235 (2) [M+], 200 (33) [M+-C1]. -
C12H n ClNP (235.03): calcd. C 61.16, H 4.70,
N 5.94; found C 60.01, H 4.64, N 5.83.
Obtained from 2.0 g of IndLi (16.4 mmol) and
2.51 g of MeP(Cl)NEt2 (1 g) (16.4 mmol).
*H NMR (400 MHz, C6D 6): <3 = 7.81 (m, 1 H,
Av) 7.36 (m, 1 H, Ar), 7.28-7.24 (m, 2 H, Ar),
6.95-6.91 (m, 1 H, Ar), 3.25 (m, 2 H, All, Ind),
2.8 (m, 4 H, -N C //2CH3), 1.08 (d, 3 H, MeP-,
V p W H ) = 9.8 Hz), 0.83 (t, 6 H, -N C H 2CH3,
3/(H -H ) = 7.7 Hz). - 13C{1H} NMR (75 MHz,
C6D6): <3= 146.3 (d, Cq, Ar, Ind, 3/( 31P - 13C) = 4.3
Hz), 141.4 (d, Cq, Ar, Ind, /( 31P-13C) = 28.5 Hz),
137.5 (d, CH, Vin, Ind, 2/( 31P-13C) = 7.2 Hz), 137.5
(d, CH, Vin, Ind, 2/( 31P-13C) = 10.1 Hz), 126.8
(CH, Ar, Ind), 126.5 (CH, Ar, Ind), 125.4 (CH,
Ar, Ind), 123.9 (CH, Ar, Ind), 43.6 (d, N C //2CH3,
t-Butyl-diethylamino-iodophosphane (lp)
To
a solution of 2.2 g f-BuP(Cl)NEt2 (lb)
(10.22 mmol) was added 2 g of Nal (>10 mmol).
Then the reaction mixture was refluxed for 5 h.
The solids were removed by filtration. A transpar-
ent yellow solution was concentrated in vacuum (3
Torr) at room temperature to yield the product as
an oily yellow liquid in quantitative yield.
XH NMR (300 MHz, C6D6): Ö = 2.85 (m, 4 H,
-N C //2CH3), 1.13 (d, 9 H, t-B uPCl-, V p W H ) =
2 / ( 3 i p
_
i
3
Q
=
1
4
6
H
z
)
3
9
5
(
q
A
1 1 I n
d
)
1 5
3
( d>
-N C H 2CH3, 37(31P - 13C) = 7.9 Hz), 11.0 (d,
M eP-, V(31P - 13C) = 28.4 Hz). - 31P{1H} NMR
(162 MHz, C6D6): Ö = 53.8. - MS (El, 70 eV):
m/z (%) = 233 (5) [M+], 218 (80) [M+-M e]. -
C14H20PN (233.13): calcd. C 72.08, H 8.64, N 6.00;
found C 72.22, H 8.78, N 5.89.
14.4 Hz), 0.87 (t, 6 H, -N C H 2CH3, V ^H ^H )
=
7.2 Hz). - ^CpH} NMR (75 MHz, C6D6): 6 = 48.1
(d, -N C //2CH3, 2/( 31P - 13C) = 12.0 Hz), 35.8 (d,
Cq, r-Bu, V(31P - 13C) = 42.0 Hz), 27.1 (d, CMe,
t-Bu, 2/( 31P - 13C)
=
19.3 Hz), 12.6 (d,
-N C H 2CH3, 3/( 31P - 13C) = 5.1 Hz). - 31P{1H}
NMR (162 MHz, C6D6, 25 °C): (3 = 174.0. - MS
(El, 70 eV): m/z (%) = 271 (2) [M+-C H 3+H], 216
t-Butylamino-t-butyl(1H-inden-3-yl)phosphane (2c)
(5) [M+-E t2N], 162 (11) [f-BuP(H)NEt2].
-
Obtained from 0.79 g of IndLi (6.50 mmol) and
1.27 g of ?-BuP(Cl)NH(?-Bu) (la) (6.5 mmol).
IR (film): v = 3000, 2961, 2771, 2380, 1635, 1578,
1540, 1192, 1180, 953, 736 (P-N ), 656. - *H NMR
(300 MHz, C6D 6): Ö = 7.80 (d, 1 H, Ar), 7.24 (d,
1 H, Ar), 7.18-7.12 (dt, 2 H, Ar), 6.22 (m, 1 H,
Vin), 3.07 (m, 2 H, All), 1.68 (d, 1 H, -N H ,
V ^ P ^ H ) = 11.9 Hz), 1.15 (s, 9 H, r-BuN), 1.05
(d, 9 H, t-BuP, V ^ P ^ H ) = 12.8 Hz). - 13C{1H}
NMR (75 MHz, C6D6): <5 = 147.7 (d, Cq, Ind,
C8H 19INP (287.12): calcd. C 33.47, H 6.67, N 4.88;
found C 33.58, H 6.53, N 5.04.
t-Butyl-diethylamino (1H-inden-1 -yl)phosphane (2a)
Obtained from of 0.49 g IndLi (4.01 mmol) and
0.78 g of f-BuP(Cl)NEt2 (lb) (4.01 mmol).
IR (film): v = 3000, 2950, 2875, 2864, 2396,1558,
1457, 1180, 1093, 874, 773, 736 (P -N ), 415. - *H
NMR (300 MHz, C6D6): Ö = 7.80 (m, 1 H, Ar),
7.23-7.18 (m, 1 H, Ar), 7.12 (m, 2 H, Ar), 6.43
(m, 1 H, Vin), 3.1-3.0 (m, 2 H, All), 2.93 (m, 4 H,
-N C //2CH3), 1.19 (d, 9 H, r-Bu, V ^ P ^ H ) =
12.9 Hz), 0.83 (t, 6 H, -N C H 2CH3, 3/(H -H ) =
5.4 Hz). - 13C{1H} NMR (75 MHz, C6D 6): (3 =
148.0 (d, Cq, Ar, Ind, 2/( 31P - 13C) = 23.6 Hz), 143.4
(Cq, Ar, Ind), 142.3 (d, Cq, Vin, Ind, V(31P - 13C) =
25.5 Hz), 136.6 (CH, Vin, Ind), 126.4 (CH, Ar,
Ind), 124.9 (CH, Ar, Ind), 123.6 (CH, Ar, Ind),
121.0 (d, CH, Ar, Ind, 3/( 31P - 13C) = 7.4 Hz), 46.5
(d, N C //2CH3, 2/( 31P - 13C) = 15.7 Hz), 40.2 (C,
All, Ind), 33.6 (d, Cq, f-Bu, V(31P - 13C) = 17.6 Hz),
28.1 (d, t-Bu, 2/( 31P - 13C) = 16.1 Hz), 15.1 (d,
-N C H 2CH3, 3/( 31P - 13C) = 3.2 Hz). - 31P{1H}
NMR (162 MHz, C6D6): d = 63.9. - MS (El,
70 eV): m/z (%) = 275 (7) [M+], 218 (76) [M+-r-Bu],
160 (27) [*-BuPN(H)r-Bu]. - C17H28PN (277.38):
calcd. C 73.61, H 10.17, N 5.05; found C 73.52,
H 10.27, N 4.91.
/(3iP _i3C) =
2
3
. 6 Hz), 147.4 (d, Cq, Ind, /( 31P -
13C) = 32.4 Hz), 144.6 (Cq, Ar, Ind), 141.1 (CH,
Vin, Ind), 126.3 (CH, Ar, Ind), 125.0 (CH, Ar,
Ind), 123.8 (CH, Ar, Ind), 122.4 (d, CH, Ar, Ind,
37(3ip_i3Q = 6 2 Hz), 50.7 (d, Cq, r-BuN, 2/( 31P -
13C) = 17.2 Hz), 39.4 (d, C, All, Ind, 3/( 31P - 13C) =
2.8 Hz), 32.1 (d, r-BuN, 3/( 31P - 13C) = 8.3 Hz), 27.4
(d, Cq, ;-BuP, V(31P - 13C) = 16.4 Hz), 26.6 (d,
r-BuP, 2/( 31P - 13C) = 15.0 Hz). - 31P{1H} NMR
(162 MHz, C6D6): <5= 21.7. - MS (El, 70 eV): m /
z (%) = 275 (9) [M+], 218 (65) [M+-r-Bu], 162
(100) [M-2-f-Bu]. - C17H28PN (277.38): calcd.
C 73.61, H 10.17, N 5.05; found C 73.69, H 10.01,
N 4.87.
t-Butyl-diethylamino(9-fluorenyl)phosphane (2d)
Obtained from 2.0 g of FluLi (11.61 mmol) and
2.26 g of r-BuP(Cl)NEt2 (lb) (11.61 mmol).
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820
V. V. Kotov et al. • Synthesis of New Cyclopentadienyl-, Idenyl- and Fluorenylphosphanes
10.3 Hz), 0.89 (d, 9 H, t-BuP, V ^ P ^ H )
12.5 Hz), 0.58 (s, 9 H, r-BuN). - 1 3 C{XH} NMR
(50 MHz, C D 6): <5 = 147.0 (d, Cq, Flu, 7(3 1 P -
=
XH NMR (200 MHz, C D6): d = 7.8-7.7 (m,
1 H), 7.68-7.60 (m, 1 H), 7.57-7.52 (m, 2 H),
7.20-6.97 (m, 4 H), 4.2 (d, 1 H, V ^ P ^ H ) = 6.2
6
6
1 3 C) = 15.1 Hz), 142.3 (Cq, Flu), 140.8 (Cq, Flu),
139.1 (d, Cq, Flu, /( 3 1 P - 1 3 C) = 3.3 Hz), 125.7 (CH,
Flu), 125.1 (CH, Flu), 124.9 (CH, Flu), 124.3 (CH,
Flu), 124.1 (CH, Flu), 124.1 (CH, Flu), 119.1 (CH,
Hz), 2.68-2.34 (m, 4 H, 2 -N C //
H, r-Bu, V f 1? - ^ ) = 13.0 Hz), 0.43 (t,
-N C H CH3, /(H -H ) = 7.0 Hz). - “ CpHJ NMR
(50 MHz, C D6): (5 = 145.8 (d, Q,, Flu, 7(3 1 P -
1 3 C) = 10.3 Hz), 145.1 (d, Cq, Flu, 7(? P - 1 3 C) = 2.1
Hz), 140.7 (Cq, Flu), 140.2 (d, Cg, Flu, /( 3 1 P -
1 3 C) = 2.5 Hz), 125.6 (d, CH, Flu J(3 1 P - 1 3 C) = 4.5
Hz), 125.5 (CH, Flu), 125.3 (CH, Flu), 125.1 (CH,
Flu), 124.7 (CH, Flu), 123.9 (CH, Flu), 118.9 (CH,
Flu), 118.4 (CH, Flu), 49.5 (C, All, Flu, V(3 1 P -
2
CH3), 1.09 (d, 9
6
H, 2
2
3
6
Flu), 118.5 (CH, Flu), 48.6 (d, Cq, t-BuN,
1 3 C) = 18.2 Hz), 47.3 (d, Cq, All, Flu, V(3 1 P - 1 3 C) =
39.2 Hz), 30.4 (d, t-BuN, /( 3 1 P - 1 3 C) = 7.8 Hz),
30.0 (d, Cq, f-BuP, /( 3 1 P - 1 3 C) = 13.6 Hz), 25.8 (d,
t-BuP, /( lP - 1 3 C) = 16.5 Hz). - 3 1 P{ H} NMR
(162 MHz, C D6): (5 = 49.5; - MS (El, 70 eV):
2
/( 3 1 P -
1
3
1
2
5
1
6
1 3 C) = 45.3 Hz), 45.2 (d, -N C tf
1 3 C) = 16.1 Hz), 34.1 (d, Cq, t-Bu, V(3 1 P - 1 3 C) =
2
CH3,
2
/( 3 1 P -
m/z (%) = 325 (1) [M+], 268 (5) [M+-r-Bu],
212(12) [M-2-r-Bu], 165 (36) [Flu], 160 (100)
[f-BuPNH-f-Bu].
-
C2 1 H28PN (325.43): calcd.
26.8 Hz), 27.8 (d, r-Bu, 2J ^ F - 13C) = 18.2 Hz),
C 77.51, H 8.67, N 4.31; found C 77.40, H 8.57,
13.5 (d, -N C H
2
CH3, /( 3 1 P - 1 3 C) = 2.1 Hz). -
3
3 1 P{
1
H} NMR (162 MHz, C D6): <5 = 63.3. - MS N 4.25.
6
(El, 70 eV): m/z (%) = 277 (3) [M+], 253 (35)
[M+-N E t2], 165 (100) [Flu]. - C2 1 H28PN (325.43):
calcd. C 77.51, H 8.67, N 4.30; found C 77.39,
H 8.51, N 4.23.
2.2-Bis[(t-butyl-diethylaminophosphanyl)cyclo-
pentadienyljpropane (3a)
Obtained from 1.6 g of [Cp
2
CMe
2
]Li
2
(4.76
mmol) and 1.86 g of r-BuP(Cl)NEt
mmol).
2
(lb) (4.76
Diethylamino(9-fluorenyl)methylphosphane (2e)
Obtained from 8.1 g of FluLi (47.06 mmol) and
Mixture of isomers: - 3 1 P{
D 6): d = 74.6, 74.0, 73.9, 73.8, 73.8, 73.5, 73.5,
73.3, 73.2, 73.0, 73.0, 72.9, 70.4. -
1
H} NMR (162 MHz,
7.22 g of MeP(Cl)NEt
lU NMR (400 MHz, C
2
(1 g) (47.06 mmol).
D6): (5 = 7.68 (m, 1 H,
C
6
6
C
2 9
H
5 2
P
2
N
2
Vin, Flu), 7.58 (d, 1 H, Vin, Flu), 7.23 (d, 1 H, Vin,
Flu), 7.23 (m, 4 H, Vin, Flu), 4.02 (d, 1 H, All, Flu,
(490.69): calcd. C 70.99, H 10.68, N 5.91; found C
70.90, H 10.79, N 5.78.
V ^ P ^ H ) = 6.5 Hz), 2.6 (m, 4 H, -N C tf
I.22 (d, 3 H, MeP, V ^ P ^ H ) = 8.4 Hz), 0.68 (t,
H, -N C H CH3, /( H - H) = 7.1 Hz). - 1 3 C{ H}
NMR (75 MHz, C D6): d = 145.4 (d, Cq, Flu,
/(3iP _i3C) = . 8 Hz), 144.8 (d, Cq, Flu, 7(3 1 P -
1 3 C) = 7.9 Hz), 141.9 (d, Cq, Flu, /( V - 1 3 C) = 2.2
2
CH3),
1.2-Bis[(t-butyl-diethylaminophosphanyl)indenylJ-
ethane (3b)
6
2
3
1
1
1
6
3
Obtained from 4.1 g of [Ind
2
(CH
2
)
2
]Li
2
(9.81
3
mmol) and 3.84 g of f-BuP(Cl)NEt
mmol).
2
(lb) (19.62
Hz), 141.2 (Cq, Flu), 126.7 (CH, Flu), 126.5 (CH,
Flu), 126.3 (CH, Flu), 125.5 (CH, Flu, 7(3 1 P -
1 3 C) = 6.02 Hz), 125.3 (CH, Flu, /( 3 1 P - 1 3 C) = 3.7),
120.4(CH, Flu), 120.1 (CH, Flu), 53.6 (d, C, All,
Mixture of isomers: - XH NMR (400 MHz,
C
6
D6): d = 1.9-1.2 (several m, 4 H, Ar, Ind),
6.8-6.0 (several m, 1 H, Vin, Ind), 4.2-3.7 (sev-
eral m, 1 H, All, Ind), 3.2-2.7 (several m, H,
-N C H CH and - C // CH2-), 1.5-0.5 (several m,
r-BuP and -N C H CH3). H} NMR
(75 MHz, C D6): d = 144.0-141.0 (several d, Cq,
/( 3 1 P _ 1 3 C) = 3.8 Hz), 131.1-131.0 (d, Cq, Ind,
/( iP —i C) = 61 ) 5 126.4-124.0 (several d, CH,
Flu,
-N C H 2CH3,
-N C H CH3,
M eP-, V ^ P - ^ C ) = 21.0 Hz). - 3 1 P[
(162 MHz, C D6): (5 = 59.4. - MS (El, 70 eV): m/z
1
/( 3 1 P - 1 3 C)
=
34.5 Hz), 44.2 (d,
/( 3 1 P - 1 3 C) = 14.9 Hz), 15.2 (d,
/( 3 1 P - 1 3 C) = 3.1 Hz), 13.4 (d,
H} NMR
6
2
2
3
2
2
3
2
-
1 3 C{
1
1
6
6
(%) = 212 (28) [M+-N E t2]. - C1 8 H22PN (283.14):
calcd. C 76.30, H 7.83, N 4.94; found C 76.45,
H 7.71, N 4.84.
3
3
H z
Ind), 68.0 (C, All, Ind), 51.0-48.0 (two d, Cq, t-
B uP-), 38.0 (~C H 2CH2-), 34.6 (a number of res-
onance, -N C //
r-BuP-), 15.0 (-N C H
(162 MHz, C D 6): = 91.7, 91.6, 91.6, 91.5,
86.7, . - MS (El, 70 eV): m/z (%) = 448
(1) [M+- t-B u- NEt +H], 160 (95) [r-BuPNEt2],
128 ( ) [r-BuPNEt - 2CH4], 104 (100) [H PN Etj,
74 (43) [H NEt2], 57 (26) [f-Bu]. - C3 6
2
CH3), 28.9 (several d, CH3,
t-Butylamino-t-butyl(9-fluorenyl)phosphane (2f)
2
CH3). H} NMR
-
3 1 P{
1
6
6
8
6
.8 ,
Obtained from 1.79 g of FluLi (5.8 mmol) and
1.13 g of r-BuP(Cl)NH(r-Bu) (la)(5.8 mmol).
8
6
.6
,
8
6 .6
2
XH NMR (200 MHz, C
6
D6):
6
= 7.53-749 (m,
8
6
2
2 H), 7.27-7.23 (m, 1 H), 7.15-7.08 (m, 5 H), 3.84
(s, 1 H, All), 1.56 (d, 1 H, -N H , V ^ P ^ H ) =
2
H
5 8
P
2
N
2
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821
Table 1. Crystal data and experimental details of the
V. V. Kotov et al. • Synthesis of New Cyclopentadienyl-, Idenyl- and Fluorenylphosphanes
(580.81): calcd. C 74.45, H 10.07, N 4.82; found
C 74.39, H 10.13, N 4.71.
crystal structure determination of
2
f.
Crystal data:
2,2-Bis[(t-butyl-diethylaminophosphanyl)indenyl]-
pentane (3c)
C21H28NP
325.41 g/mol
1.132 g/cm3
prism, yellow
0.45 x 0.30 x 0.25 mm
monoclinic
Chemical formula
Formula weight
Density (calcd)
Habitus, color
Crystal dimensions
Crystal system
Space group
Obtained
from
4.72 g of [Ind
2
CEt
2
2
]Li
2
(10.24 mmol )and 4.01 g of r-BuP(Cl)NEt
(20.48 mmol).
(lb)
Mixture of isomers: -
D6): (5 = 8.0-6.8 (several m, 4 H, Ar, Ind),
6.41 (several m, 1 H, Vin, Ind), 4.36-4.30 (several
m, 1 H, All, Ind), 3.5-2.21 (several m, H, -
N C // CH and -C C H 2CH 3), 1.64-1.0 (several m,
12 H, t-B uP- and -N C H CH3). - 1 3 C{ H} NMR
(50 MHz, C D6): (5 = 151.0-129.0 (several m, Cq,
NMR (200 MHz,
P2\/n, Z = 4
C
6
6
.8 -
Unit cell dimensions:
9.990(2)
« [A]
6
15.298(3)/101.33(3)°
12.742(3)
1909.4(7)
704
b [AVß [°]
2
3
c [ A ]
Volume [Ä3]
F(000)
.
2
1
6
Ind), 124.7-117.6 (several m, Cq and CH, Ind),
58.5-45.4 (two d, Cq and C, All, Ind), 29.5-29.1
Abs. coeff. [mm-1]
1.248
Data collection:
Radiation
(two
-C H 2CH3), 15.4 (-N C H
- ^P^H } NMR (162 MHz, C
broad m 89.0, 56.1, 55.3, 54.8; - MS (El, 70 eV):
m/z (%)
286.2 (25) [C1 8 2 5 NP], 160 (10)
[?-BuPNEt2], 115 (35) [Ind], 72 (30) [-N E t2], 58
(100) [r-BuH], 29 (80) [Et].
d,
CH3),
26.5-25.0
(several
m,
C u -K a (1.54178 Ä),
graphite monochromator
223(2)
4.57 to 60.05°
0 > (3h <311, 0 > 6 k <517,
-1 4 > 6 1 ö 14
2
CH3), 8.4 (-C H
2
CH3).
6
D6): Ö = 90.8, 90.6,
Temp. [K]
0-range
Index ranges
=
H
Solution and refinement:
Refl. coll./unique
Refl. obs. [I > 2 o(l)]
Largest peak/hole
Solution
Refinement
Data/parameters
wR2, all data
R(F) [I >2 o(I)}
Goodness-of-fit on F2
-
C
3 9
H
6 0
P
2
N
2
3020/2838
2450
0.246/-0.287 e/ Ä 3
direct methods
full-matrix, F2
2838/321
0.1336
0.0449
1.107
(618.86); calcd. C 75.69, H 9.77, N 4.53; found
C 75.54, H 9.90, N 4.40.
X-Ray structure determination o f 2f
Diffraction-quality crystals of 2f were obtained
by cooling an n-hexane solution. A crystal data
summary is given in Table 1. A yellow specimen
with dimensions of 0.45 x 0.30 x 0.25 mm was
3
mounted on the top of a glass fiber and studied on
an Enraf-Nonius CAD4 four-circle diffractometer
with C u -K a (1.54178 A) radiation at -50 °C. The
structure was solved in the space group P2i/n by di-
rect methods and refined by full-matrix least-
squares on F2 by using the SHELX-96 program
package [36]. All non-hydrogen atoms were refined
anisotropically. The hydrogen atoms were located
from the difference-Fourier maps and refined in an
isotropic approximation. Further details can be ob-
tained from the Cambridge Crystallographic Data-
base on quoting the depository number CCDC
160960. E-mail: deposit@ccdc.cam.ac.uk.
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822
V. V. Kotov et al. ■Synthesis of New Cyclopentadienyl-, Idenyl- and Fluorenylphosphanes
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