Novel functionalised P-ligands: Advances and application

Article abstract of DOI:10.1016/j.jorganchem.2004.09.030

Novel endo- and exocyclic phosphine ligands possessing different functionalities obtained by reduction of the PO precursors with desired stereochemistry are discussed. The diastereoselective deoxygenation including the catalytic reduction processes, the factors defining the reactivity and the role of the substituents on the stability of phosphorus atom configuration in a series of 3-aryl-3-phosphabicyclo[3.1.0]hexanes are reported. The complexation features of the ligands with Rh(III) and Pd(II) were examined and Rh(III) complexes were tested in styrene hydroformylation showing the structure-activity dependence.

Full text of DOI:10.1016/j.jorganchem.2004.09.030

Journal of Organometallic Chemistry 690 (2005) 2559–2570
www.elsevier.com/locate/jorganchem
Novel functionalised P-ligands: advances and application
a,
a
a
Irina L. Odinets *, Natalya M. Vinogradova , Ekaterina V. Matveeva ,
a
a
b
Denis D. Golovanov , Konstantin A. Lyssenko , Gyo¨rgy Keglevich , Laszlo Kollar ,
c
´
´
´
d
Gerd-Volker Roe¨schenthaler , Tatyana A. Mastryukova
a
a
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
Vavilova Street 28, 11991 GSP1 Moscow, Russia
Budapest University of Technology and Economics, 1521 Budapest, Hungary
´ ´
University of Pecs and Research Group for Chemical Sensors of the Hungarian Academy of Sciences, Pecs, Hungary
b
c
d
Institut fu¨r Anorganische & Physikalische Chemie, Universita¨t Bremen, Germany
Received 2 July 2004; accepted 14 September 2004
Available online 14 October 2004
Abstract
Novel endo- and exocyclic phosphine ligands possessing different functionalities obtained by reduction of the P@O precursors
with desired stereochemistry are discussed. The diastereoselective deoxygenation including the catalytic reduction processes, the fac-
tors defining the reactivity and the role of the substituents on the stability of phosphorus atom configuration in a series of 3-aryl-3-
phosphabicyclo[3.1.0]hexanes are reported. The complexation features of the ligands with Rh(III) and Pd(II) were examined and
Rh(III) complexes were tested in styrene hydroformylation showing the structure–activity dependence.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Cyclic and acyclic phosphine oxides; Deoxygenation; Cyclic phosphines; 3-Cyano-1,2-thiaphosphacyclanes, 1-(Phosphino)cyclopropane
carbonitriles, Rhodium and palladium complexes; Stereostructure; Hydroformylation; Homogeneous catalysis
1. Introduction
compounds of the tetracoordinated phosphorus atom
and such approach is widely used.
Transition metal complexes incorporating r-donor
phosphines as the ligands are frequently used as catalyst
precursors in hydroformylation and hydrogenation
reactions [1]. Taking into account that search of novel
effective catalysts for a variety of applied processes is a
never-ending story we would like to demonstrate our re-
sults in this field.
In this paper, our findings on the deoxygenation of
the phosphine precursors bearing both endo- and exocy-
clic phosphorus atom and on the stereostructure of the
P-ligands, as well as the transition metal (Rh(III) and
Pd(II)) complexes based on the phosphines obtained
along with their catalytic activity are discussed.
In principle phosphine oxides are the most important
precursors of a variety of phosphine ligand-blocks as it
is much easier to carry out the modification of chemical
and stereochemical structure using stable in any sense
2. Results and discussion
For the preparation of phosphines, the reduction of
the corresponding phosphine oxides by silane hydrides
[2] is the best choice due to the selectivity and efficiency.
To the best of our knowledge the general limitations of
the method and comparison of the reactivity with the
*
Corresponding author. Tel.: +7095 1359356; fax: +7095 1355085.
E-mail address: odinets@ineos.ac.ru (I.L. Odinets).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.09.030

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compound structures are not discussed in literature. To
elucidate this problem three types of P@O precursors
were involved in trichlorosilane reduction, namely satu-
rated and non-saturated phosphacyclanes (1a–c, 4),
2-oxo-1,2k5-thiaphosphacyclanes (8c, 9f) which present
phosphacyclanes having the heteroatom in the a-posi-
tion to the phosphorus atom, and compounds (14–16)
with the exocyclic phosphorus atom bearing carbocycle
in a-position.
constants of ca. 480–500 Hz) could be observed
apparently due to the rupture of the endocyclic P–C
bonds.
At the same time, a similar reduction procedure used
for 1c possessing o-tolyl substituent at the phosphorus
atom led to two closely related forms of product (2c),
having dP signals in the phosphine region and the same
pattern of signals in the 13C NMR spectra. The ratio of
the components depended on the reaction time and was
95:5 after the standard procedure (2 h at 0 ꢁC followed
by 2 h at 20 ꢁC) and changed to 38:62 after a 6 daysꢀ
standing. These two products were assigned to syn-
and anti-diastereomers of 2c (Scheme 1).
2.1. Synthesis of the 3-phosphabicyclo[3.1.0]hexane and
dihydrophosphinine ligands and their RhIII and PdII
complexes
The interaction of phosphines 2a,b with dimeric pen-
tamethylcyclopentadienyl rhodium dichloride resulted
in the typical formation of complexes of type
CP*RhCl2L (3a,b) in high yield. The single crystal
X-ray analysis performed for 3b-syn confirmed the cis
disposition of the P-p-tolyl substituent and the cyclopro-
pane ring and similarity in spectral features of phos-
phines 2a,b and their complexes 3a and 3b allowed us
to conclude that complex 3a also has the syn-geometry
[6]. On addition of the Rh(III) precursor to the mixture
of phosphine isomers (2c-syn and 2c-anti) in different
times, the two different Rh(III) complexes (3c-syn and
3c-anti) were formed in the same ratio observed for
the phosphines 2c-syn and 2c-anti used in the complexa-
tion reaction. The stereostructure of both isomers of
complex 3c was confirmed by X-ray analysis (Figs. 1
and 2) justifying the tentative assignment, the syn or
the anti disposition of the P-aryl substituent and the
cyclopropane ring [6].
The facile synthesis of 6,6-dichloro-1-methyl-3-aryl-
3-phosphabicyclo[3.1.0]hexane 3-oxides (1a–c) used as
starting substrates of the first type by dichlorocyclo-
propanation of the corresponding 2,5-dihydrophosphole
oxide under phase transfer catalytic conditions was re-
ported by one of us earlier [3–5]. Such synthesis resulted
in single isomers with syn disposition of the cyclopro-
pane ring and the P-aryl substituent when the latter pre-
sents phenyl or p-tolyl. The corresponding o-tolyl
derivative (1c) was formed as a 6:4 mixture of syn-
and anti-isomers, which were separated by chromatogra-
phy [5]. For further reduction procedure the pure
syn-isomers 1a–c were utilized.
The deoxygenation of phosphine oxides 1a,b with
trichlorosilane proceeded very easily even at 0 ꢁC to
afford the desired phosphines 2a,b as the only reaction
product, Scheme 1 [6]. At a higher temperature (even
at ambient conditions), the formation of side-products
presenting according to the NMR data a series of pri-
mary and secondary phosphines (up to 45–50% in to-
It should be noted that according to the X-ray and
elemental analysis data rhodium (III) complexes 3a–c
were found to form strong solvates with dichlorometh-
1
tal, dP of ca. ꢀ40 ‚ ꢀ68 ppm and the JPH coupling
Scheme 1.

I.L. Odinets et al. / Journal of Organometallic Chemistry 690 (2005) 2559–2570
2561
Fig. 1. (a) The general view of 3c-syn-2CH2Cl2 in representation of atoms by thermal motion ellipsoids at 50% probability level. Hydrogen atoms
˚
and the solvent molecules are omitted for clarity. Selected bond lengths (A): P(3)–Rh(I) 2.3207(8), P(3)–C(2) 1.848(3), P(3)–C(4) 1.854(3), P(3)–C(8)
1.828(3). Selected bond angles and torsion angles (ꢁ): P(1)Rh(1)–centre(Cp*) 124.1, C(2)P(3)C(4) = 95.9(1), P(3)Rh(1)C(15)C(20) = 8.3(4),
C(2)P(3)C(8)C(9) = 61.3(3). (b) The scheme illustrating the crystal packing pattern of the CH2Cl2 solvate.
Fig. 2. (a) The general view of one of independent molecules of 3c-anti-2CHCl3 in representation of atoms by thermal motion ellipsoids at 50%
˚
probability level. Hydrogen atoms and solvent molecules are omitted for clarity. Selected bond lengths (A): P(3)–Rh(I) 2.300(1), P(3)–C(2) 1.834(4),
P(3)–C(4) 1.838(4), P(3)–C(8) 1.826(4). Selected bond and torsion angles (ꢁ): P(1)Rh(1)–centre(Cp*) 131.7, C(2)P(3)C(4) 91.6(1), P(3)Rh(1)C(15)
C(20) 7.4(3)/ꢀ9.9(3), C(2)P(3)C(8)C(9) 71.1(4). (b) The scheme illustrating the crystal parking pattern of the CHCl3 solvate.
ane used as a solvent for complexation and in some
cases we failed to remove the solvent even at prolonged
drying in vacuo at an elevated temperature. Moreover,
recrystallization of 3c-syn from chloroform gave the
corresponding pseudopolymorph modification as a
chloroform solvate, which structure was also confirmed
by X-ray diffraction investigation. Apparently, the sol-
vates are stabilized by numerous Hꢁ ꢁ ꢁCl interactions
formed between the RhCl2 moiety and the dichloro-
methane or the chloroform molecules. Figs. 1(b) and
2(b) show the crystal packing pattern of solvates ob-
tained for both isomers of 3c.

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The phosphines 2a,b-syn demonstrate chemical shifts
ory with the 6-31G* basis set for both the syn- and the
anti-isomers of phosphines 2a and 2c. According to
these calculations the corresponding anti-isomers are
thermodynamically more stable in both cases. The dif-
ference in energy between the two isomers is higher for
the unsubstituted phosphine 2a in comparison with 2c
(1.79 kcal/mol (2a) and 0.83 kcal/mol (2c)). At the same
time, going in the syn- to anti-direction the inversion
barrier estimated as the difference in energy between
syn-isomer and the transition planar state is somewhat
smaller for 2c than that for 2a (Esyn ꢀ ETS 33.256 and
33.943 kcal/mol correspondingly). Although the differ-
ence between these values is not significant (0.687 kcal/
mol), the tendency read from the energy values fits the
observation. Nevertheless, the rather high value of the
inversion barrier calculated suggests that one should
not exclude that reduction in the case of 1c proceeds
via the different mechanism (with partially inversion of
configuration) in comparison with its phenyl or p-tolyl
analogues 2a,b or is accompanied by the formation of
an intermediate with the pentacoordinated phosphorus
atom which may undergo the bipyramidal inversion.
This question is currently under detail investigation.
The analogous series of reactions (reduction by tri-
chlorosilane followed by complexation) was applied to
4-dichloromethylene-1,4-dihydrophosphinine 1-oxide 4
[8]. In this case, the reduction at 0 ꢁC and the subsequent
complexation with dimeric pentamethylcyclopentadie-
nyl rhodium dichloride or with trans-dichloro(dibenzo-
nitrile)palladium furnished phosphine 5 and complexes
6, 7, respectively (Scheme 2).
dP of ca. 25 ppm in CDCl3, signals of both isomers of 2c
are situated in the same region and at that 2c-syn has
upfield shift (22.6 ppm) as compared with the one for
2c-anti (27.9 ppm). The Rh(III) complexes are charac-
terized by dP shifts close to those for P@O precursors
1a–c and characteristic disposition of signals for syn-
and anti-isomers of 3c is the same as that observed for
the corresponding isomers of phosphine 2c (3c-syn has
upfield chemical shift at 67.8 ppm in comparison with
3c-anti (91.6 ppm)). In the 13C NMR spectra of 2a–c
and 3a–c the signals of the skeletal carbon atoms are sit-
uated in about the same regions that were observed for
their P@O precursors 1a–c with normal decrease in JPC
coupling constants passing from phosphine oxides 1a–c
to Rh(III) complexes 3a–c and further to phosphines
2a–c. The large value Dd between 2 and 3 suggested a
rather strong coordination between the phosphorus
and Rh(III) atoms in this series.
It is known that trichlorosilane alone or more con-
veniently its pyridine complex reduces phosphine oxides
with retention of configuration. Only in the presence of
amines of base strength greater than about pKb 5, such
as triethylamine, the inversion was observed to take
place predominantly [7]. Detailed mechanisms of both
processes with different stereochemistry outcome are still
unclear, but it was suggested [7] that in the absence of
amine the first step is the complexation of phosphoryl
oxygen by the silicon atom of the silane. Such complex
transfers oxygen to silicon leaving protonated phos-
phine. At using the mixture trichlorosilane/Et3N the first
step include the transfer of proton to the oxygen atom of
P@O moiety and subsequent attack by SiClꢀ3 anion
resulting in inversion.
2.2. Synthesis of 3-cyano-1,2k3-thiaphosphacyclanes
First of all one may assume that reduction of 3-
phosphabicyclohexane 3-oxides 1a–c by trichlorosilane
alone resulted in the formation of the corresponding
phosphine with preserved P-configuration that unex-
pectedly was followed by the inversion only in the case
of compound 2c bearing an o-tolyl substituent. As com-
monly phosphines do not undergo P-inversion at ambi-
ent conditions, in order to estimate the possibility of
easy inversion in the case of 2c we carried out quantum
chemical calculations at the B3PW91 DFT level of the-
Recently we have shown that the intramolecular
cyclization in a series of x-haloalkyl substituted thio-
phosphoryl compounds which mechanism involves the
S-alkylation of the P@S group followed by the dealky-
lation of the P-alkoxy group in the quasiphosphonium
salt formed, represents a convenient general route to 2-
oxo-1,2k5-thiaphosphacyclanes both functionalized or
not [9]. In the case of x-haloalkyl substituted
thiophosphorylacetonitriles, such methodology gave
rise to either mono or bicyclic cyanosubstituted thia-
Scheme 2.

I.L. Odinets et al. / Journal of Organometallic Chemistry 690 (2005) 2559–2570
2563
Scheme 3.
phosphacyclanes (Scheme 3) [10]. Compounds 8a–c,
9a–g and 10 were formed as mixtures of
RꢂP; RꢂC-cis and RPꢂ ; SꢂC-trans isomers differing in the mu-
tual disposition of the phosphoryl oxygen atom and the
cyano group in relation to the ring plane and separated
by chromatography. The cis- and trans-arrangements of
the substituents was unambiguously confirmed by the
X-ray data [9] and corresponded well to typical 1H
NMR spectroscopic analysis based on the deschielding
effect of the P@O bond on all the kinds of protons sit-
uated in the cis-position to the P@O group according to
[11]. Moreover, it was shown that a cis-isomer is char-
acterized by a downfield chemical shift for 8 while for
six-membered compounds 9 a downfield chemical shift
in the 31P NMR spectrum correspond to the trans dis-
position of the mentioned substituents [10]. The similar
characteristic disposition of the signals in the 31P NMR
spectra was observed for cyano substituted cyclic com-
pounds with tricoordinated phosphorus atom [12].
Thus, 31P NMR spectroscopy allows one to assign
unambiguously the type of geometric isomer and there-
fore the configuration of the asymmetric centers in the
case of 3-cyano-1,2-thaiphosphacyclanes bearing both
P(III) and P(IV) atoms.
Scheme 4.
1
tative yields as a single isomer. Surprisingly, the
reduction either in presence of triethylamine, or in the
absence of the latter one resulted in the products with
the same stereochemical configuration which was ascer-
tained by 31P NMR spectroscopic analysis. As the for-
mal seniority of the substituents changes passing from
tetracoordinated phosphorus compounds to the three
coordinated ones, in all the cases, RꢂP; RCꢂ -cis isomers
of 2-oxo-derivatives yielded the RꢂP; SCꢂ -trans isomers of
1,2k3-thiaphosphacyclanes and vice versa. That is to
say, the ring structure remained intact in the reaction
course.
It should be mentioned that the linear analogue of 2-
oxo-1,2-thiaphosphacyclanes, e.g. diphenyl(thiopropyl)
phosphine oxide – remains invariable either under the
same reduction conditions or more severe ones (refluxing
in xylene). This fact clearly indicates that cyclic phosphine
oxides are much more reactive than the linear ones.
As in the previous case, for further reduction we used
merely individual isomers. In contrast to the above men-
tioned phosphacyclanes 1a–c, 4, more severe conditions
are required for the reduction of 3-cyano-2-oxo-1,2-thi-
aphosphacyclanes 8c, 9f by trichlorosilane, namely
refluxing in benzene solution over 1–2 h (Scheme 4).
Nevertheless, side products were not observed in the
reaction mixtures and the target 3-cyano-1,2k3-thia-
phosphacyclanes 11, 12 are formed in practically quanti-
The complexation features of the 1,2k3-thiaphosphacyclanes will
be published elsewhere.
1

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2.3. Synthesis of the 1-(phosphino)cyclopropane carbo-
nitriles
diastereomersdiffering in phosphorusatom configuration
ðPSꢂCRꢂ CꢂR and PRꢂ CꢂRCRꢂ Þ [20].
As for the reduction of the cycloalkanecarbonitriles
14–16, the reduction rate is significantly lower in com-
parison with the above discussed phosphacyclanes
being in direct correlation with the ring size (Scheme
6). For comparison, the reduction of diphenylphospho-
ryl acetonitrile proceeds with about the same rate as in
the case of 2-oxo-1,2-thiaphosphacyclanes (1 h, C6H6,
80 ꢁC) yielding the corresponding phosphine in a
nearly quantitative yield. Passing from the correspond-
ing cyclopropane to cyclopentane derivatives not only
elongation of the reaction time, but also higher reac-
tion temperatures are necessary. Nevertheless, the reac-
tion was not completed even under rather severe
conditions (140 ꢁC, 37 h) in the case of cyclopentane
derivatives. Such result cannot be explained due to
the difference in electronic factors in a series of 1-
(phosphoryl)cycloalkane carbonitriles 14–16, as they
are practically the same in the all compounds. There-
fore the main reason of such behavior is likely con-
nected with increase of the steric hindrances growing
up with the increase of the cyclic size and preventing
the formation of the intermediate with the hypervalent
silicon atom. The influence of steric hindrances on the
reduction of phosphine oxides by HSiCl3 was con-
firmed by the model reaction, namely we failed to
reduce even at 140 ꢁC (40 h) 1-diphenylphosphoryl-1-
methylpropane nitrile which is the direct linear struc-
tural analogue of the above mentioned phosphorylated
cycloalkanecarbonitriles.
Among functionalized phosphine ligands, those con-
taining phosphorus and nitrogen complexing centers in
a molecule are of special interest showing high catalitic
activity in many reactions [1a]. Nevertheless, only a lim-
ited number of such ligands including sp-hybridized
nitrogen atom as a coordination site are reported in lit-
erature, e.g. cyanomethylphosphines [13–15] and cyano-
ethylphosphines [16–18]. Cyanosubstituted phosphines
with rather rigid stereochemical structure advantageous
for metal complex catalysis were of undoubted interest.
1-(Phosphino)cycloalkane carbonitriles potentially
containing a few stereogenic centers in the molecule meet
these conditions. Therefore the third group of compounds
involved in reduction presented 1-(phosphoryl)cycloalk-
ane carbonitriles. The precursors were obtained by cyclo-
alkylation of phosphorylacetonitriles 13a,b with a,x- and
a,w-dihaloalkanes under phase transfer catalysis condi-
tions (Scheme 5). The reaction with a,x-dihaloalkanes
was carried out according to procedure elaborated by us
earlier [19]. Despite in the case of a,w-dihaloalkanes one
could expect the formation of reaction products as statis-
tic mixture of cis- and trans-isomers, unexpectedly such
reaction of phosphoryl and thiophosphorylacetonitriles
turned out to proceed in a diastereoselective way, yielding
only trans-isomer with the identical configuration of
asymmetric carbon atoms ðCꢂRCRꢂ Þ. In the case of addi-
tional asymmetric phosphorus atom in the starting sub-
strate, trans-isomers are formed as a mixture of
Scheme 5.
Scheme 6.

I.L. Odinets et al. / Journal of Organometallic Chemistry 690 (2005) 2559–2570
2565
The attempt to carry out the catalytic reduction of 1-
(phosphoryl)cycloalkane carbonitriles using (EtO)3SiH
and catalytic amount of Ti(OiPr)4 according to [21] re-
sulted in about 40% formation of secondary phosphines
(either Ph2PH or PhiPrPH depending on the substitu-
ents at the phosphorus atom of the precursor) as side
products due to the rupture of P–C bond between the
phosphorus atom and carbocycle.
Thus, in comparison with phosphacyclanes the reac-
tivity of linear phosphine oxides in the reaction with
HSiCl3 is decreased and steric hindrances in the nearest
vicinity at the P@O group inhibit the reduction.
1-(Phosphino)cyclopropane carbonitriles 17a–c ob-
tained in practically quantitative yields after the reduc-
tion were further used in the subsequent complexation
with dimeric pentamethylcyclopentadienyl rhodium
dichloride resulting in the complexes 18a–c which struc-
tures were confirmed by a single crystal X-ray analysis
(Figs. 3 and 4).
As regards the spectroscopic analysis, the phosphines
17a–c show signals in 12–14 ppm region in their 31P
NMR spectra. Complexation with Rh(III) results in
coordination shift Dd = 21–25 ppm and the signals of
18a–b represent the typical doublets with the coupling
constants JPRh in the range of 146–150 Hz. In the H
and 13C NMR spectra of 17a–c and 18a–c the patterns
of the corresponding signals are similar in principle to
Fig. 4. The general view of molecule of {[[(1-diphenylphosphino)-2-
methyl]cyclopropane carbonitrile]pentamethylcyclopentadienyl} rho-
dium dichloride 18c in representation of atoms by thermal motion
ellipsoids at 50% probability level. Hydrogen atoms are omitted for
1
1
˚
clarity. Selected bond lengths (A): Rh(1)–P(1) 2.333(2), P(1)–C(1)
1.846(6), Rh(1)–centre(Cp*) 1.813. Selected torsion angles (ꢁ):
Rh(1)P(1)C(1)C(4) 151.3(4), Rh(1)P(1)C(1)C(2) 66.1(4).
those of the P@O precursors with typical changes in
JPC coupling constants. It should be noted also that
methyl groups of the P-isopropyl radical in 17b, 18b
1
are observed as separated signals both in the H and
13C NMR spectra indicating on the hindered rotation
relative to the P–C bond. An insignificant shift of the
CN absorbtion band in the IR spectra of 18a–c in com-
parison with the corresponding ligands means that
nitrogen atom is not involved in the coordination with
rhodium.
Finally, the catalytic reduction using (EtO)3SiH/
Ti(OiPr)4 turned out to be highly effective in the case of
phosphorylmethyl arenes bearing either one or two phos-
phoryl groups and known to be reduced with difficulties
by trichlorosilane [22] (Scheme 7). These phosphines
21, 22 were also involved in the complexation with rho-
dium(III) yielding complexes 23 and 24 correspondingly.
A representation of mononuclear complex 23 is shown in
Fig.5. The complex 24 has a composition M2L but the
phosphorus atoms are completely equivalent and appear
in the 31P NMR spectrum as a single doublet with the JPRh
coupling constant equal to ca. 142 Hz. In the IR spectrum
of 24 two absorption bands of the cyano group are ob-
served. One of them at 2220 cmꢀ1 corresponds to the
non-coordinated cyano group whereas the second one
shifted up to 2250 cmꢀ1 indicates apparently on the
Fig. 3. The general view of molecules of {[(1-diphenylphosph-
ino)cyclopropane carbonitrile]pentamethylcyclopentadienyl} rhodium
dichloride 18a in representation of atoms by thermal motion ellipsoids
at 50% probability level. Hydrogen atoms are omitted for clarity.
˚
Selected bond lengths (A): Rh(1)–P(1) 2.3461(8), P(1)–C(1) 1.838(3),
Rh(1)–centre(Cp*) 1.815. Selected torsion angles (ꢁ): Rh(1)P(1)C(1)
C(4) 171.3(4), Rh(1)P(1)C(1)C(2) 51.7(4).

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I.L. Odinets et al. / Journal of Organometallic Chemistry 690 (2005) 2559–2570
Scheme 7.
the model substrate that was reacted with CO/H2 (1/1) in
toluene at 40–100 ꢁC and at a pressure of 100 bar in the
presence of one of the catalyst precursors (Rh/sty-
rene = 1:4000). The reaction solutions were analyzed
immediately after the reaction by GC–MS analysis.
In such reaction in addition to the formyl linear and
branched regioisomers, some hydrogenation product is
also expected. Surprisingly, in all the cases the formation
of PhCH2CH3 was negligible (less than 0.5% and, in
most cases, less than the detection limit). Therefore the
chemoselectivity of the styrene hydroformylation was
excellent in all cases where the catalyst was active at all.
It was demonstrated that activity of 3a-syn and 6 in
this reaction is moderate and the conversions are very
similar to each other and do not exceed 28%. At that
the regioselectivity towards the branched regioisomer
Rbr was rather high at 100 ꢁC (83–85%) and in the case
of 6 increased up to 95% at lower temperature.The com-
plexes 3a-syn and 3c-syn formed by the syn-isomers of
6,6-dichloro-1-methyl-3-p-tolyl- or 3-o-tolyl-3-phosp-
habicyclo[3.1.0]hexanes 2b and 2c correspondingly, can
be considered as inactive at low temperatures (40 ꢁC),
but they provided excellent conversions (>99%) at
100 ꢁC in comparison with the catalyst precursor 3a-
syn containing ligand 2a with similar structure but bear-
ing phenyl group at the phosphorus atom. Thus, the
introduction of tolyl groups instead of the phenyl one
caused an unexpectedly high increase in activity in a ser-
ies of Rh(III)–Cp* complexes formed by 6,6-dichloro-1-
methyl-3-aryl-3-phosphabicyclo[3.1.0]hexanes. At the
same time the usage of 3b, 3c yielded in noticeable de-
crease in the regioselectivity Rbr (33–42%).
Fig. 5. The general view of molecule of Rh(III) complex 23 in
representation of atoms by thermal motion ellipsoids at 50% proba-
bility level. Hydrogen atoms and the second position of the disodered
˚
Cp* are omitted for clarity. Selected bond lengths (A): Rh(1)–P(1)
2.336(2), P(1)–C(1) 1.841(8), Rh(1)–centre(Cp*) 1.821. Selected torsion
angles (ꢁ): Rh(1)P(1)C(1)C(2) 177.0(4), P(1)C(1)C(2)C(7).
coordination of the cyano group nitrogen atom with rho-
dium in either intra- or intermolecular mode.
2.4. Hydroformylation reaction catalyzed by rhodium
(III) complexes containing the phosphine ligands under
investigation
In comparison with the complexes formed by phos-
phacyclanes, higher activities have been observed for
the complexes of 1-(phosphino)cyclopropane carbonit-
riles 18a and 18b bearing an exocyclic phosphorus atom.
For these compounds conversions was nearly quantita-
tive at temperatures in the range of 70–100 ꢁC. Moreover,
in longer reaction time, the complex 18b proved to be ac-
tive even at 40 ꢁC (the conversion was equal to 52.5%
over 70 h) but this complex formed by the more basic
phosphine 17b resulted in lower regioselectivities
(Rbr = 68% and 34% for 18a and 18b correspondingly
at 100 ꢁC) which changes in favor of the linear aldehyde.
Due to their high practical importance, hydroformy-
lation catalysts have received particular attention. Thus,
we estimated the catalytic activity of rhodium complexes
3a–c, 6, 18a–c of the RhCl2(Cp*)(L)-type, where L pre-
sents monodentate either P-heterocyclic or cyclopro-
pane-based P-ligand, as catalyst precursors in
hydroformylation reaction [23]. Styrene displaying a rel-
atively high reactivity among the alkenes was chosen as

I.L. Odinets et al. / Journal of Organometallic Chemistry 690 (2005) 2559–2570
2567
Furthermore, for 18a the lower the temperature was, the
lower Rbr value was observed, i.e. decrease of the temper-
ature increased the formation of the linear aldehyde. This
tendency is opposite to that observed with well-known
preformed (e.g. HRh(CO)(PPh3)3) or in situ prepared
rhodium–PPh3 systems [24]. The introduction of the
methyl substituent in the cyclopropane ring (complex
18c) in trans position to the phosphorus atom resulted
in a drastic decrease of the catalytic activity: even at ele-
vated temperature conversion is as small as 15%.
In those cases, when complexes of sterically demand-
ing phosphorus ligands (3b, 3c and 18b) were used, good
to excellent turnover frequences (TOFs) up to 1000 have
been obtained referring to the determining role of coor-
dinatively unsaturated HRh(CO)2(L) species of high
activity.
3.1.1. General procedure for the preparation of phosphines
2a–c and 5
To a cooled (0 ꢁC) stirred solution of precursor 1a–
c or 4 (0.3 mmol) in of a 1:1 mixture of CH2Cl2–C6H6
(10 ml) was added 0.15 ml (1.45 mmol) of HSiCl3un-
der argon atmosphere and on stirring. The mixture
was stirred at the same temperature for 2 h and at
ambient temperature for further 2 h. According to
31P NMR, the deoxygenation proceeded with high
selectivity. Then the volatile components were evapo-
rated in vacuo to yield the phosphines 2a–c and 5
quantitatively and in a pure form according to 31P
and 13C NMR (2c consisted of a 95:5% mixture of
the syn- and the anti-isomers). On standing at room
temperature for 6 days, the isomeric mixture of 2c
was converted to a 38:62% mixture of the syn- and
the anti-isomers. For the NMR parameters of 2a–c
and 5, see [6].
Considering the whole ligand series investigated it
turnedoutthatthehighactivitywasaccompaniedbyprac-
tically complete chemoselectivities towards aldehydes.
3.1.2. General procedure for the preparation of 3-cyano-2-
phenyl-1,2k3-thiaphosphacyclanes (11, 12)
2.5. Concluding remarks
To a solution of the corresponding 3-cyano-2-oxo-
1,2k5-thiaphosphocyclane 8c-cis, 8c-trans, 9f-cis or 9f-
trans (1.00 mmol) in benzene (60 ml) trichlorosilane
(5.00 mmol) was added at ambient temperature. The
reaction mixture was refluxed under argon atmosphere
for 2 h, cooled and evaporated to dryness. Acetonitrile
(30 ml) was added to the residue and the precipitate of
siloxane polymer was filtered off under argon. The fil-
trate was evaporated in vacuo yielding the yellowish sol-
ids of the phosphines 11, 12 with high purity according
the NMR analysis.
11-cis (obtained from 8c-trans): Yield: 98%; 31P
NMR (CDCl3): 42.78; 1H NMR (CDCl3): d 1.27 (t,
3JHH = 7.6 Hz, 3H, CH3), 1.66–1.79 (m, 1H, CH2CH3),
1.85–1.92 (m, 1H, CH2CH3), 2.27–2.34 (m, 1H,
CH2C(CN)), 1.98–2.07 (m, 1H, CH2C(CN)), 2.87–2.94
(m, 1H, SCH2), 3.34–3.39 (m, 1H, SCH2), 7.42–7.46,
7.65–7.69 (two m, 5H, C6H5P); 13C NMR (CDCl3):
In summary, the reduction of phosphine oxides by
HSiCl3 is a sterically sensitive reaction and reactivity
of P@O precursors used decreases when going from sat-
urated and non-saturated phosphacyclane oxides to
2-oxo-1,2-phosphacyclanes and further to compounds
with exocyclic phosphorus atom. The former ones are
reduced easily at 0 ꢁC, while for the reduction of the
linear phosphine oxides, the prolonged reflux in high-
boiling solvents is required. The new type of P-ligands
were utilized in the synthesis of Rh(III) complexes which
activity was tested in the hydroformylation of styrene.
3. Experimental
3.1. General
1
3
All reactions were conducted under an inert atmos-
phere of dry argon by using Schlenk glassware and vac-
uum line techniques. Solvents were freshly distilled from
standard drying agents. The NMR spectra were re-
corded on a ‘‘Bruker AMX-400’’ spectrometer in CDCl3
solutions using residual proton signals of deutero sol-
vent as an internal standard (1H, 13C) and 85% H3PO4
(31P) as an external standard. IR spectra were recorded
in KBr pellets on a Fourier spectrometer ‘‘Magna-
IR750’’ (Nicolet) with a resolution of 2 cmꢀ1 after 128
scans. The starting phosphine oxides 1a–c [3–5], 4 [8],
8c, 9f [10], 14a–c, 15a–d, 16a–d [20] used as precursors
for the ligands were obtained as described earlier. All
the phosphines obtained had the purity >97% according
NMR spectral analysis and were used in the subsequent
complex formation without further purification. All the
compounds have satisfactory elemental analysis data.
51.79 (d, JPC = 30.3 Hz, P–C), 10.67 (d, JPC = 13.4
Hz, CH3), 26.96 (d,2JPC = 13.4 Hz, CH2CH3), 32.68
2
(d, JPC = 1.6 Hz, C(CN)CH2), 36.41 (d, JPC = 3.7
2
2
Hz, SCH2), 119.51 (d, JPC = 8.3 Hz, CN), 128.00 (d,
2JPC = 6.5 Hz, o-C in C6H5–P), 129.88 (p-C in C6H5–
3
P), 131.77 (d, JPC = 20.6 Hz, m-C in C6H5–P); IR
(CH2Cl2): mCN 2220 cmꢀ1
.
12-trans (obtained from 9f-cis): Yield: 95%. 31P
NMR (CDCl3): d 15.82. IR (KBr): mCN 2230 cmꢀ1
12-cis (obtained from 9f-trans): Yield: 96%. 31P
NMR (CDCl3): d 13.00. IR (KBr): mCN 2232 cmꢀ1
.
.
3.1.3. General procedure for the preparation of (1-
phosphino)cyclopropanecarbonitriles 17a–c
The procedure was essentially the same as for 11, 12,
except for the reaction time was 12–13 h.
For the characterization of 17a, see [25].

2568
I.L. Odinets et al. / Journal of Organometallic Chemistry 690 (2005) 2559–2570
1-(Isopropylphenylphosphino)cyclopropane carbonit-
1
and 6-fold volume excess of pentane was added. The
dark orange crystals of the complexes formed were fil-
tered off and dried in vacuo.
rile 17b: Yield: 97%; 31P NMR (CDCl3): d 13.51; H
3
3
NMR (CDCl3): d 0.86 (dd, JHH = 6.8 Hz, JPH = 17.1
3
Hz, 3H, (CH3)CH), 0.95 (dd, JHH = 6.8 Hz,
For the physical–chemical data and spectral charac-
terization of 3a–c, 6, 7, see [6]. Complexes 18a–c have
satisfactory elemental analysis data.
3JPH = 17.1 Hz, 3H, (CH3)CH), overlapped with 0.92–
1.27 (m, 3H, CH2), 1.37–1.46 (m, 1H, CH2), 2.43–2.60
(m, 1H, CH), 7.31–7.69 (m, 5H, C6H5); 13C NMR
18a: Yield: 76%; m.p. 160 ꢁC (decomposition); 31P
1
1
1
(CDCl3): d 5.00 (d, JPC = 27.1 Hz, P–C(CN)), 12.61
(d, JPC = 11.3 Hz, CH2), 16.96 (d, JPC = 18.8 Hz,
NMR (CDCl3): 35.02 (d, JPRh = 148.3 Hz); H NMR
(C6D6): d 1.33 (15H, d, JHPh = 3.2 Hz, CH3(Cp*)),
1.45–1.51 (2H, m, CH2), 1.57–1.62 (2H, m, CH2),
7.47–7.55, 7.97–8.03 (10H, m, C6H5); 13C NMR
(CDCl3): d 8.52 (CH3(Cp*)), 18.40–19.10 (br, CH2).
99.82 (d, J = 6.8 Hz, Cp*), 122.25 (CN), 128.20 (d,
3JPH = 9.8 Hz, m-C in C6H5P), 131.40 (p-C in C6H5P),
2
2
2
CH2), 18.88 (d, JPC = 20.3 Hz, (CH3)CH–P), 19.21 (d,
2JPC = 17.3 Hz, (CH3)CH–P), 25.25 (d, JPC = 6.0 Hz,
1
2
PCH), 121.19 (d, JPC = 6.0 Hz, CN), 128.61 (d,
3JPC = 6.0 Hz, m-C in C6H5P), 130.11 (p-C in C6H5P),
2
132.97 (d, JPC = 20.6 Hz, o-C in C6H5P, tentative
1
assignment), 134.18 (d, JPC = 12.8 Hz, ipso-C in
2
133.87 (d, JPH = 8.0 Hz, o-C in C6H5P), signal of the
central carbon atom of the cyclopropane ring does not
appear because of the rather low solubility of the com-
C6H5P); IR (KBr): mCN 2224 cmꢀ1
1-(Diphenylphosphino)-2-methylcyclopropane carbo-
.
nitrile 17c: Yield: 95%; 31P NMR (CDCl3): d 12.72; H
plex; IR (KBr): mCN 2225 cmꢀ1
.
1
NMR (CDCl3): d 1.23–1.32 (m, 1H, CH), 1.44 (d, 3H,
3JPH = 5.9 Hz, CH3), 1.47–1.57, 1.61–1.73 (two m,
1H + 1H, CH2), 7.37–7.43, 7.47–7.59 (two m,
6H + 4H, C5H5P); 13C NMR (CDCl3): d 12.98 (d,
18b: Yield: 54%; m.p. 232 ꢁC; 31P NMR (CDCl3): d
1
37.83 (d, JPRh = 146.34 Hz). 1H NMR (CDCl3): d
1.28 (d, JRhH = 3.5 Hz, 15H, CH3(Cp*)), 1.35 (dd,
3
3JPH = 9.4 Hz, JHH = 7.5 Hz, 3H, CH(CH3)2), 1.57
2
3
3
1JPC = 24.9 Hz, P–C–CN), 21.77 (d, JPC = 16.6 Hz,
(dd, JPH = 15.7 Hz, JHH = 7.0 Hz, 3H, CH3(CH)),
1.57–1.63 (m, 1H, CH2), 1.68–1.76 (m, 1H, CH2),
1.82–1.91 (m, 1H, CH2), 2.61–2.70 (m, 1H, CH2),
3.36–3.50 (m, 1H, CH(CH3)2), 7.43–7.53, 7.90–7.95 (m,
2
CH), 22.21 (d, JPC = 12.8 Hz, CH2), 15.52 (CH3),
2
120.03 (d, JPC = 4.5 Hz, CN); 127.57 (d, JPC = 7.5
Hz), 128.62 (d, JPC = 6.0 Hz), 129.25, 129.63, 132.06,
1
132.41, 132.80, 133.19, 134.71 (d, JPC = 10.1 Hz, ipso-
1
5H, C6H5); 13C NMR (CDCl3): d 2.47 (d, JPC = 26.1
1
C in C6H5P), 135.01 (d, JPC = 9.6 Hz, ipso-C in
Hz, PC(CN)), 8.75 (CH3(Cp*)), 16.09 (CH2), 17.57 (d,
2JPC = 2.5 Hz, CH2), 19.41 (d, JPC = 2.5 Hz, CH3CH),
C6H5P); IR (KBr): mCN 2223 cmꢀ1
.
2
2
1
19.70 (d, JPC = 7.4 Hz, CH3CH), 29.06 (d, JPC = 23.6
Hz, PC(CH3)2), 99.38 (dd, J = 2.5 Hz, J = 7.4 Hz,
3.1.4. General procedure for the preparation of 2-(diph-
enylphosphino)methyl substituted benzenecarbonitriles
21, 22
2
Cp*),122.55 (d, JPC = 5.0 Hz, CN), 128.46 (d,
3JPC = 8.7 Hz, m-C in C6H5P), 130.63 (d, JPC = 2.5
4
1
Hz, p-C in C6H5P), 131.45 (d, JPC = 38.0 Hz, ipso-C
To a mixture of benzenecarbonitrile 19 or 20 (0.63
mmol) and triethoxysilane (0.70 ml; 3.79 mmol) in 10
ml of benzene 46.5 l of Ti(OiPr) (0.16 mmol) was added.
The resulting suspension was refluxed for either 1 h (19)
or 2 h (20) until the light green clear solution was
formed. The mixture was evaporated to dryness and
phosphines 21 and 22 correspondingly having the purity
over 95% was used in subsequent complexation reac-
tions without further purification.
2
in C6H5P),131.46 (d, JPC = 8.2 Hz, o-C in C6H5P); IR
(KBr): mCN 2225 cmꢀ1
.
18c: Yield: 68%; m.p. 234–235 ꢁC; 31P NMR
(CDCl3): d 34.68 (d, JPRh = 149.6 Hz); 1H NMR
1
3
(CDCl3): d 1.08–1.14 (1H, m, CH), 1.29 (d, JPH = 8.0
Hz, 3H, CH3), 1.33 (15H, d, JHRh = 3.9 Hz, CH3(Cp*)),
1.86–2.02, 2.12–2.32 (1H + 1H, two m, CH2), 7.48–7.51,
7.91–7.99 (10H, m, C6H5). 13C NMR (CDCl3): d 8.35
(CH3(Cp*)), 15.04 (s, CH3), 19.90 (CH2), 20.67
(CH(CH3)), 99.62 (d, J = 4.5 Hz, Cp*), 120.33 (d,
2JPC = 4.52 Hz, CN), 127.80 and 128.04 (both d,
21: 31P NMR (C6H6): d ꢀ7.26 ppm (100% purity). IR
(C6H6): mCN 2220 cmꢀ1 (br).
22: 31P NMR (C6H6): d ꢀ7.86 ppm (95% purity). IR
(C6H6): mCN 2225 cmꢀ1 (br).
2
3JPC = 9.9 Hz, m-C in C6H5P), 131.13 (d, JPC = 7.6
Hz, o-C in C6H5P), 133.37 (p-C in C6H5P), the signals
of the central carbon atom of the cyclopropane ring
and ipso-C in C6H5P do not appear because of the rather
low solubility of the complex; IR (KBr): mCN 2225 cmꢀ1
.
3.1.5. General procedure for the preparation of rho-
dium(III) complexes of phosphines
To a stirred solution of the corresponding phosphine
(0.30 mmol) in CH2Cl2 (25 ml)
a
solution of
23: Yield: 70%, m.p. 250 ꢁC (dec.). 31P NMR (CDCl3):
d 36.38 (d, 1JPRh = 143.95 Hz). 1H NMR (CDCl3): d 4.48
(d, 2JPH = 10.1 Hz, 2H, CH2–P), 6.71 (d, 3JHH = 7.2 Hz,
1H, C6H4P), 6.97–7.04 (m, 2H, C6H4P), 7.22 (d,
3JHH = 7.2 Hz, 1H,C6H4P), 7.33–7.36, 7.43–7.47, 7.72–
7.77 (m, 10H, C6H5P). 13C NMR (CDCl3): d 8.49
[Cp*RhCl2]2 (97.85 mg, 0.15 mmol (for P-monodentate
phosphines 2a–c, 5, 17a–c, 21 or 195.7 mg, 0.30 mmol in
the case of 22)) in CH2Cl2 (ca. 5 ml) was added under
argon. The stirring was continued for 0.5 h. The reaction
mixture was evaporated to the final volume of ca. 1 ml

I.L. Odinets et al. / Journal of Organometallic Chemistry 690 (2005) 2559–2570
2569
Table 1
Crystallographic data for complexes 18a, 18b and 23
18a
18b
23
Formula
T (K)
C26H29Cl2NPRh
298
C27H31Cl2NPRh
120
C30H31Cl2NPRh
163
Syntex P21
Diffractometer
Crystal system, space group
Siemens P3/PC
Monoclinic, P21/c
18.348(4)
8.479(2)
17.025(3)
108.86(3)
2506.6(9)
4(1)
Smart CCD
Monoclinic, P21/c
9.149(2)
36.287(8)
8.617(2)
115.757(8)
2576.5(9)
4(1)
Orthorhombic, P212121
8.069(2)
15.752(3)
˚
a (A)
˚
b (A)
˚
c (A)
21.891(4)
b (ꢁ)
3
˚
V (A )
2782.3(10)
4(1)
Z(Z0)
M
560.28
9.72
574.31
9.48
610.34
8.83
1248
l(Mo Ka) (cmꢀ1
F(000)
)
1144
1.485
1176
1.481
qcalc (g cmꢀ3
Scan type
2hmax (ꢁ)
)
1.457
x
50.00
x
55.00
x
55.00
No. of refl. measured (Rint
)
5947 (0.0252)
5748
3759
18079 (0.0483)
5883
4560
2778 (0.0)
2778
1978
No. of independent refl.
No. of refl. with I > 2r(I)
No. of parameters
R1
285
0.0310
295
0.0733
312
0.0441
0.0824
0.893
wR2
GOF
Max./min peak (e A
0.0730
0.932
0.1730
1.101
ꢀ3
˚
)
0.453/ꢀ0.352
1.134/ꢀ0.570
0.718/ꢀ0.519
1
(CH3), 34.49 (d, JPC = 21.3 Hz, CH2), 98.67 (dd,
C–C bond lengths and angles (AFIX 5). Hydrogen
atoms in all complexes were placed in geometrically cal-
culated positions and included in final the refinement
using the ‘‘riding’’ model with the Uiso(H) parameters
equal to 1.2 Ueq(Ci) or 1.5 Ueq(Cii), where U(Ci) and
U(Cii) are, respectively, the equivalent thermal parame-
ters of the aromatic and methylene carbon atoms to
which corresponding H atoms are bonded. Crystal data
and structure refinement parameters for 18a, 18b and 23
are given in Table 1. All calculations were performed
using the SHELXTL software [26].
1
1JCRh = 2.8 Hz, JPC = 6.8 Hz, Cp*), 113.54 (d,
3JPC = 4.0 Hz, C1 in C6H4), 116.96 (CN), 126.31 (d,
1
3JPC = 2.4 Hz, C3 in C6H4), 127.29 (d, JPC = 40.5 Hz,
3
ipso-C inC6H5P), 127.88 (d, JPC = 10.0 Hz, m-C in
4
C6H5P), 128.14 (C5 in C6H4), 131.08 (d, JPC = 2.4 Hz,
4
p-C in C6H5P), 131.46 (d, JPC = 4.9 Hz, C3 in C6H4),
4
132.16 (d, JPC = 1.2 Hz, C4 in C6H5P), 134.44 (d,
2
2JPC = 8.8 Hz, o-C in C6H5P), 139.35 (d, JPC = 12.8
Hz, C2–C6H4). IR (KBr): mCN 2230 cmꢀ1. Anal. Calc.
for C30H36Cl2NPRh Æ 0.25 CH2Cl2: C, 56.95; H, 5.15;
N, 2.19. Found: C, 56.97; H, 5.15; N, 2.13%.
24: Yield: 64%; m.p. >290 ꢁC (dec.); 31P NMR
1
(CDCl3): d 36.18 (d, JPRh = 142.34 Hz); 1H NMR
4. Supplementary material
2
(CDCl3): d 4.24 (d, JPH = 10.48 Hz, 4H, CH2P), 6.25–
6.27 (3H, m, C6H3P), 7.23–7.25, 7.34–7.35, 7.58–7.62
Crystallographic data for the structures reported in
this paper have been deposited to the Cambridge Crys-
tallographic Data Centre as Supplementary Nos.
CCDC-225065 for 3c-antiÆ2CHCl3, CCDC-225066 for
3c-synÆ2CH2Cl2, CCDC-225067 for 3c-synÆ2CHCl3;
CCDC-249192 for 18a; CCDC-249193 for 18b;
CCDC-249191 for 23. Copies of the data can be ob-
tained free of charge on application to CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (fax: (internat.) +44-
1223/336-033; e-mail: deposit@ccdc.cam.ac.uk).
(3m, 20H, C6H5P). IR (KBr): mCN 2222, 2250 cmꢀ1
.
Anal. Calc. for C53H59Cl4NP2Rh2 ÆCH2Cl2: C, 54.62;
H, 4.97; N, 1.16. Found: C, 53.79; H, 5.06; N, 1.16%.
The complexation features of the 1,2k3-thiaphospha-
cyclanes will be published elsewhere.
3.2. X-ray structure determination
The structures were solved by direct method and re-
fined by the full-matrix least-squares against F2 in aniso-
tropic approximation for non-hydrogen atoms. The
analysis of Fourier density synthesis revealed that Cp*
ligand in 23 is disordered by two positions with equal
occupancies. All atoms of the disordered ring were re-
fined in isotropic approximation with the restraints on
Acknowledgments
This work was partially supported by Russian Basic
Research Foundation (Grant No. 02-03-33073), the

2570
I.L. Odinets et al. / Journal of Organometallic Chemistry 690 (2005) 2559–2570
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Federal
Program
on
Support
of
Leading
Scientific Schools (Grant Nos. SS-1100.2003.3,
1060.2003.3) and German Science Foundation 436
RUS 113/766/1-1. Gy. K. is grateful for the OTKA-
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