Syntheses and coordination behaviour of 2-(ortho-phosphinophenyl)-functionalised 1,3-dioxolanes and 1,3-dioxanes towards a [(COD)Rh]-complex fragment - Models for immobilised complexes

Article abstract of DOI:10.1016/j.jorganchem.2004.05.050

The syntheses are reported of the ether-phosphine ligands: 2-(ortho-diphenylphosphinophenyl)-1,3-dioxolane (1a), 2-(ortho-diisopropylphosphinophenyl)-1,3-dioxolane (1b), 2-(ortho-diphenylphosphinophenyl)-1,3-dioxane (1c), 2-(ortho-diisopropylphosphinophenyl)-1,3-dioxane (1d). Their reaction with [(COD)RhCl]₂ (COD: 1,5-cyclooctadiene) results in the formation of the mononuclear complexes: {chloro(COD)[2-(ortho-diphenylphosphinophenyl)-1,3-dioxolane]rhodium(I)} (2a), {chloro(COD)[2-(ortho-diisopropylphosphinophenyl) -1,3-dioxolane]rhodium(I)} (2b), {chloro(COD)[2- (ortho-diphenylphosphinophenyl)-1,3-dioxane]rhodium(I)} (2c), and {chloro(COD)[2-(ortho-diisopropylphosphinophenyl)-1,3-dioxane]rhodium(I)} (2d). The chloride ligands of compounds 2a and 2b were abstracted with TlPF₆, with accompanied insertion of an acetal oxygen atom of the ligands 1a and 1b into the coordination sphere of the metal centre, producing {(COD)[η²-P,O-2-(ortho-diphenylphosphinophenyl) -1,3- dioxolane]rhodium(I)}PF₆ (3a*PF₆) and {(COD)[η²-P,O-2-(ortho-diisopropylphosphinophenyl)-1,3- dioxolane]rhodium(I)}PF₆ (3b*PF₆). In contrast the dioxane analogues of 3, 3c*BF₄ and 3d*BF₄, were formed by reacting the ligands 1c, 1d with [Rh(COD)₂]BF₄. The ligands 1 and the complexes 2 serve as model compounds for their via acetalation to a polyvinylalcohol resin bound analogues. The complexes synthesised were employed as pre-catalysts in the hydroformylation reaction of 1-octene.

Full text of DOI:10.1016/j.jorganchem.2004.05.050

Journal of Organometallic Chemistry 689 (2004) 3117–3131
www.elsevier.com/locate/jorganchem
Syntheses and coordination behaviour of
2-(ortho-phosphinophenyl)-functionalised 1,3-dioxolanes and
1,3-dioxanes towards a [(COD)Rh]-complex fragment – models
for immobilised complexes
*
M. Ahlmann, O. Walter
ITC-CPV, Forschungszentrum Karlsruhe, P.O. Box 3640, 76021 Karlsruhe, Germany
Received 28 November 2003; accepted 26 May 2004
Available online 12 August 2004
Dedicated to Prof. Dr. Eckhard Dinjus to the occasion of his 60th birthday
Abstract
The syntheses are reported of the ether–phosphine ligands: 2-(ortho-diphenylphosphinophenyl)-1,3-dioxolane (1a), 2-(ortho-di-
isopropylphosphinophenyl)-1,3-dioxolane (1b), 2-(ortho-diphenylphosphinophenyl)-1,3-dioxane (1c), 2-(ortho-diisopropylphosphi-
nophenyl)-1,3-dioxane (1d). Their reaction with [(COD)RhCl]2 (COD: 1,5-cyclooctadiene) results in the formation of the
mononuclear complexes: {chloro(COD)[2-(ortho-diphenylphosphinophenyl)-1,3-dioxolane]rhodium(I)} (2a), {chloro(COD)[2-(or-
tho-diisopropylphosphinophenyl)-1,3-dioxolane]rhodium(I)} (2b), {chloro(COD)[2-(ortho-diphenylphosphinophenyl)-1,3-diox-
ane]rhodium(I)} (2c), and {chloro(COD)[2-(ortho-diisopropylphosphinophenyl)-1,3-dioxane]rhodium(I)} (2d). The chloride
ligands of compounds 2a and 2b were abstracted with TlPF6, with accompanied insertion of an acetal oxygen atom of the ligands
1a and 1b into the coordination sphere of the metal centre, producing {(COD)[g2-P,O-2-(ortho-diphenylphosphinophenyl)-1,3-di-
oxolane]rhodium(I)}PF6 (3a PF6) and {(COD)[g2-P,O-2-(ortho-diisopropylphosphinophenyl)-1,3-dioxolane]rhodium(I)}PF6
*
(3b PF6). In contrast the dioxane analogues of 3, 3c BF4 and 3d BF4, were formed by reacting the ligands 1c, 1d with
*
*
*
[Rh(COD)2]BF4. The ligands 1 and the complexes 2 serve as model compounds for their via acetalation to a polyvinylalcohol resin
bound analogues. The complexes synthesised were employed as pre-catalysts in the hydroformylation reaction of 1-octene.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Ether–phosphines; Hemilabile ligands; Rh-complexes; Catalysis; Immobilisation; Polyvinylalcohol
1. Introduction
ilar manner to solvent molecules without inhibiting the
reaction by formation of too stable complexes. If such
a development is successful the use of a solvent in such
a reaction would no longer be required. Accordingly the
use of cyano-phosphines in the Pd-catalysed co-oligome-
risation of butadiene and CO2 had lead to the possibility
of working under solvent free conditions [1]. Of the po-
tential ligand systems with donor groups of differing co-
ordinative potentials, transition metal complexes of
ether–phosphine ligands have attracted most attention
due to their interesting catalytic properties [2].
Ligands containing functional groups with varying
donor strengths show potential for application in catal-
ysis. During a catalytic reaction, functional groups with
a tendency for weaker coordination may enter the metal
coordination sphere and stabilise intermediates in a sim-
*
Corresponding author. Tel.: +49-7247-826509; fax: +49-7247-
822244.
E-mail address: olaf.walter@itc-cpv.fzk.de (O. Walter).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.05.050

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M. Ahlmann, O. Walter / Journal of Organometallic Chemistry 689 (2004) 3117–3131
[M]
PR2
1
R
OH
O
O
OH
O
O
OH OH
1
R
OH OH OH
OH OH OH
R2P
[M]
Fig. 1. Schematic view of polyvinylalcohol (left) and, via acetalation, phosphino-functionalised polyvinylalcohol (right, R1: spacer, [M]: transition
metal fragment).
Our interest, however, in these compounds did not lie
in the possible use of ether–phosphines as chelating lig-
ands, but the complexes described here serve as model
compounds for transition metal complexes which are
bound to polyvinylalcohol via transformation of its free
hydroxyl groups into 1,3-dioxanes or 1,3-dioxolanes
(Fig. 1). The 1,3-dioxolane ligands functionalised at
the 2-position and their complexes act correspondingly
as models for ‘‘head to head’’ linked vinylalcohol units;
the 1,3-dioxanes functionalised at the 2-position are the
corresponding models for the ‘‘head to tail’’ linkage.
The results on the syntheses and modifications per-
formed on the polymeric material are the subject of a
patent [3] and the details will be published elsewhere [4].
The ligands 1, and their complexes 2 and 3 described
here contribute to the description of phosphino-func-
tionalised polyvinylalcohol (PVA). The spectroscopic
data of the ligands 1 and their complexes 2 will allow
the characterisation of their PVA analogues. The use
of the complexes as pre-catalysts will form the starting
point for the development of the on PVA immobilised
systems towards a catalytic application.
the constitution of the ligands 1b–1d was determined by
X-ray crystallography (Fig. 2, Table 1 and Section 5).
Crystals of the ligands were obtained by direct recrystal-
lisation of the crude product or by allowing the oils to
crystallise slowly at low temperature.
As from the results of the single-crystal X-ray anal-
yses it is evident that the ligands do not show any un-
usual bond lengths and angles we refrain from a
detailed discussion and reporting of bond lengths and
angles. Of structural importance in this context is only
the rotational position of the planar phenyl ring in
comparison to the non-planar dioxolane or dioxane
ring. A quantitative analysis can be performed on the
basis of the torsion angle comprised of the proton on
the acetal C-atom, the acetal C-atom itself, the carbon
atom of the phenyl ring bound to the acetal C-atom
and one of its neighbouring C-atoms in the phenyl ring.
For 1b the angle [H(7)–C(7)–C(6)–C(5)] has been deter-
mined to be equal to 1.1ꢁ (Fig. 2) demonstrating that
the acetal proton lies essentially within the plane con-
taining the phenyl ring, with the two ring systems per-
pendicular to one another. For 1c and 1d the
corresponding torsion angles are 25ꢁ or 47ꢁ showing
that in the ligands 1 the different ring systems may
adopt a range of rotational positions.
2. Results and discussion
The reaction of 2-(ortho-phosphinophenyl)-function-
alised 1,3-dioxolanes or dioxanes (1) with [(COD) RhCl]2
Although the 2-(ortho-diphenylphosphinophenyl)-
1,3-dioxolane (1a) has been reported in the literature
[5], there are very few reported coordination compounds
of 2-(ortho-phosphino)-functionalised benzaldehyde
acetals [6]. We synthesised the ligands by first lithiation
of 2-(ortho-bromophenyl)-1,3-dioxolane, or its 1,3-diox-
ane derivative, with butyllithium at low temperature and
then by reacting the lithiated dioxolane or dioxane with
a disubstituted chlorophosphine. After purification by
condensation or crystallisation the ligands were ob-
tained in yields of 70–80% (Scheme 1).
Br
PR2
1) BuLi
2) R2PCl
O
O
O
O
(CH2)n
(CH2)n
1a, R: Ph, n: 0
1b, R: iPr, n: 0
1c, R: Ph, n: 1
1d, R: iPr, n: 1
The spectroscopic data of the ligands 1a–1d are in ac-
cordance with their structures. So e.g., the characteristic
signal of the acetal H-atom of the ligands is observed in
1
4
the H NMR spectra as a doublet (due to JPH cou-
plings) at 6.14–6.67 ppm. Besides the spectroscopic data,
Scheme 1. Formation of the ligands 1.

M. Ahlmann, O. Walter / Journal of Organometallic Chemistry 689 (2004) 3117–3131
3119
C4
C5
O1
C7
C8
C3
C9
C6
C1
C12
C2
C3
C4
C12
C11
C13
C5
O2
H7
C2
C4
C6
C3
C10
C6
C1
C10
C5
C7
O1
O2
O1
C2
C7
C22
C1
C9
C8
C10
C11
C9
C21
P1
P1
H7
P1
C12
C11
C17
O2
C13
C14
H7
C15
C20
C8
C15
C18
C16
C13
C16
C14
C15
C19
C14
Fig. 2. View of the molecular structures of 1b (left), 1c (centre, view of one of the molecules in the independent unit) and 1d (right). Torsion angles (ꢁ)
discussed 1b: H7–C7–C6–C5 1.1ꢁ, 1c: H7–C7–C6–C1 ꢀ48.6ꢁ (corresponding angle for the second molecule in the independent unit: 25.1ꢁ), 1d: H7–
C7–C6–C1 45.1ꢁ.
Table 1
Crystallographic data of the ligands 1
Compound
1b
1c
1d
Empirical formula
Formula weight
Crystal size (mm3)
Crystal system
Space group
Unit cell dimensions
a (pm)
C15H23O2P
266.30
C22H21O2P
348.36
C16H25O2P
280.33
0.45 · 0.45 · 0.1
Monoclinic
P21 (No. 4)
0.4 · 0.3 · 0.25
Triclinic
0.3 · 0.3 · 0.2
Tetragonal
P43 (No. 78)
ꢀ
P1 (No. 2)
840.68(6)
1008.98(7)
1036.2(2)
1370.0(2)
856.78(3)
856.78(3)
b (pm)
c (pm)
899.76(7)
90.0
1504.6(2)
66.242(2)
2136.5(1)
90.0
a (ꢁ)
b (ꢁ)
94.270(1)
90.0
761.1(1) · 106
2
1.162
85.205(2)
68.979(2)
1820.1(4) · 106
4
1.271
90.0
90.0
1568.3(1) · 106
4
1.187
c (ꢁ)
Volume (pm3)
Z
Dcalc (g/cm3)
Temperature (K)
h-Range (ꢁ)
Scan (ꢁ)
200
200
200
2.27 h 6 28.30
x-Scan, Dx = 0.3
ꢀ11 6 h 6 10, ꢀ13 6
k 6 13, ꢀ10 6 l 6 11
Flack x: ꢀ0.04(6)
8001
1.48 6 h 6 28.33
x-Scan, Dx = 0.45
ꢀ13 6 h 6 13, ꢀ18 6
k 6 18, ꢀ18 6 l 6 19
2.38 6 h 6 28.29
x-Scan, Dx = 0.45
ꢀ11 6 h 6 11, ꢀ11 6
k 6 11, ꢀ27 6 l 6 28
Flack x: 0.04(8)
16,647
Index ranges
Number of
Reflections measured
Unique reflections
Reflections observed
Parameters refined
Residual electron density (e/pm3)
Corrections
19,351
8671
3610
3368 (I > 2r)
174
0.23 · 10ꢀ6
Lorentz and polarisation,
experimental absorption
correction [20]
Direct methods
Full-matrix least-square on F2
SHELX-97 [21],
XPMA [22], WINRAY [23]
3849
3140 (I > 2r)
183
0.21 · 10ꢀ6
Lorentz and polarisation,
experimental absorption
correction [20]
Direct methods
Full-matrix least-square on F2
SHELX-97 [21],
XPMA [22],
6513 (I > 2r)
461
0.509 · 10ꢀ6
Lorentz and polarisation,
experimental absorption
correction [20]
Direct methods
Full-matrix least-square on F2
SHELX-97 [21],
XPMA [22], WINRAY [23]
Structure solution
Structure refinement
Programs used
WINRAY [23]
R1 = 0.0342 (I > 2r)
Rw = 0.0789 (all data on F2)
R indices
R1 = 0.0277 (I > 2r)
R1 = 0.0611 (I > 2r)
Rw = 0.0731 (all data on F2)
Rw = 0.1332 (all data on F2)
Standard deviations are given in parentheses.
results in the formation of the corresponding [(COD)
RhCl(Phosphine)] complexes (2) (Scheme 2) according
to a well known literature reaction [7].
Purification of complexes 2 was readily achieved by
extraction of the crude product with refluxing pentane.
During the extraction procedure yellow single crystals

3120
M. Ahlmann, O. Walter / Journal of Organometallic Chemistry 689 (2004) 3117–3131
The acetal O-atoms in the complexes 2 are not bound
to the Rh-centre and, as was observed in the crystal
structure for 1b, a twisting of the phenyl ring with re-
spect to the dioxolane or dioxane ring was observed.
For all of the complexes 2 the torsion angle, comprised
of the acetal proton, the acetal C-atom itself, the carbon
atom of the phenyl ring bound to the acetal C-atom, and
one of its neighbouring C-atoms in the phenyl ring, was
found to be less than 10ꢁ. This is close to the perpendic-
ular orientation of the two ring systems observed for 1b
and furthermore an indication that the overall steric hin-
drance in the complexes 2 has increased due to the coor-
dination of the ligands 1 to a transition metal fragment.
The coordination of the COD ligands in the complexes
2 is reflected in their 1H and 13C NMR spectra. In com-
parison to [Rh(COD)Cl]2, where the two coordinated
olefin units of the COD ligand show only one resonance
signal due to their chemical identity, for the complexes 2
a splitting of the corresponding resonances is observed.
This indicates that a rotational exchange between the
two different positions does not occur rapidly at room
PR2
PR2
Cl
Rh
O
O
O
O
0.5 [Rh(COD)Cl]2
(CH2)n
(CH2)n
1a, R: Ph, n: 0
1b, R: iPr, n: 0
1c, R: Ph, n: 1
1d, R: iPr, n: 1
2a, R: Ph, n: 0
2b, R: iPr, n: 0
2c, R: Ph, n: 1
2d, R: iPr, n: 1
Scheme 2. Formation of the complexes 2.
of the complexes 2b–2d were obtained which were suita-
ble for X-ray diffraction analyses. Only complex 2a crys-
tallised in the form of thin needles which diffracted
poorly. The coordination geometry at the Rh-centre in
2 can be described as distorted square planar (Fig. 3).
Accordingly the bond angles at the Rh-centre be-
tween two ligands in a cis-position to each other were
found to be in the range of 86.2ꢁ and 96.7ꢁ (taking the
centre of the double bonds of the COD as the reference
point for a coordination site). The bond angles for the
trans-positioned groups were determined to be larger
than 170ꢁ. The Rh–C distances vary depending on the
ligand which is in the trans-position to the correspond-
ing p-bond of the COD unit; the Rh–C bond distances
for the C-atoms in trans-positions to the chloride ligand
were determined to be 5–10 pm shorter than the Rh–C
distances for the double bond trans to the P-atom. This
is a consequence of the higher p-acceptor character of
the phosphine ligand compared to the chloride ligand,
and is in agreement with results obtained from similar
coordination complexes [8].
1
temperature. Correspondingly, in the H NMR spectra
of the complexes 2 the proton resonances of the olefin
unit coordinated trans to the chlorine ligand are ob-
served between 3.24 and 3.50 ppm, whereas the protons
of the coordinated olefinic unit in the trans-position to
the phosphine ligands are found between 5.38 and 5.59
ppm. A similar behaviour is observed in the 13C NMR
spectra of the complexes 2, proving the unsymmetrical
coordination of the COD-ligand in 2.
The existence of a Rh–Cl bond is evident from the
FIR spectra where the absorptions of the Rh–Cl-stretch-
ing vibrations are located around 283 cmꢀ1. Finally, the
31P NMR spectra of the coordinated phosphine ligands
in the complexes 2 show resonances which are well
C20
C21
C19
C9
C4
C22
C18
C8
O2
C10
O1
C17
C5
C3
C2
C25
O1
C8
C9
C7
C26
C27
C5
C6
C24
C23
C16
C15
C12
C4
O2
P1
H7
C7
H7
Rh1
C14
C13
C6
C11
C1
C2
C24
C3
C2
C12
C1
C12
C17
C3
Cl1
C1
P1
C11
C28
C30
C6
P1
Rh1
C29
C4
C22
C23
C17
H7
C7
C10
C13
C18
C19
C18
C13
C11
C16
Rh1
C5
Cl1
C14
C19
C23
O2
C10
O1
C8
C14
C21
C20
C20
C15
C9
C16
Cl1
C22
C15
C21
Fig. 3. View of the molecular structures of 2b (left), 2c (centre), 2d (right) determined by single crystal X-ray diffraction. Discussed bond distances
(pm) and torsion angles (ꢁ), 2b: O1–C7 141.6(3) pm, O(2)–C(7) 142.7(3) pm, H7–C7–C6–C5 7.2ꢁ; 2c: C7–O1 141.5(7) pm, C7–O2 142.6(6) pm, H7–
C7–C6–C1 ꢀ4.8ꢁ; 2d: C7–O1 141.0(3) pm, C7–O2 142.2(3) pm, H7–C7–C6–C1 ꢀ9.2ꢁ.

M. Ahlmann, O. Walter / Journal of Organometallic Chemistry 689 (2004) 3117–3131
3121
20
10
0
-10
-20
-30
-40
50
40
30
20
10
0
-10
-20
-30
-40
Fig. 4. 31P{1H} NMR spectra of the ligand 1a (left, bottom) and its via acetalation PVA immobilised derivative (left, top) and of the complex 2a
(right, bottom) and its on PVA immobilised corresponding complex (right, top).
shifted compared to the free ligands 1; the resonances in
corresponding derivatives on a PVA matrix show high
analogy. The main difference lies in the lower resolution
of the solution NMR spectra of the polymer bound de-
rivatives, according to their polymeric structure [3,4].
This can be seen e.g., from the 31P{1H} NMR spectra
of 1a compared with its PVA derivative (Fig. 4). The
corresponding spectrum of complex 2a compared with
its PVA derivative shows that the complexation on the
1
2 appear as doublets with JRh–P coupling constants in
the range of 145 Hz.
If the ligands 1 or complexes 2 are reasonable model
compounds their spectroscopic data must be very simi-
lar to the corresponding on the PVA matrix immobilised
ligands or complexes. A comparison of the spectroscop-
ic data of the ligands 1 and the complexes 2 with their
Table 2
Crystallographic data of the complexes 2
Compound
2b
2c
2d
Empirical formula
Formula weight
Crystal size (mm3)
Crystal system
Space group
Unit cell dimensions
a (pm)
C23H35ClO2PRh
512.84
C30H33ClO2PRh
594.89
C24H37ClO2PRh
526.87
0.35 · 0.20 · 0.20
Triclinic
0.2 · 0.1 · 0.05
Monoclinic
P21/c (No. 14)
0.30 · 0.40 · 0.15
Orthorhombic
Pna21 (No. 33)
ꢀ
P1 (No. 2)
846.98(4)
969.33(4)
1461.1(1)
878.03(8)
2494.1(3)
808.87(8)
b (pm)
c (pm)
1581.79(7)
94.287(1)
2023.1(2)
90.0
1167.2(1)
90.0
a (ꢁ)
b (ꢁ)
104.748(1)
112.6648(1)
1136.9(9) · 106
2
91.591(2)
90.0
90.0
90.0
2354.8(4) · 106
4
1.486
c (ꢁ)
Volume (pm3)
Z
2594.5(4) · 106
4
1.523
200
Dcalc (g/cm3)
Temperature (K)
h-Range (ꢁ)
Scan (ꢁ)
1.498
200
200
1.36 h 6 28.29
x-Scan, Dx = 0.3
ꢀ11 6 h 6 11, ꢀ12 6 k 6 12,
ꢀ21 6 l 6 21
1.39 6 h 6 28.30
x-Scan, Dx = 0.3
ꢀ19 6 h 6 19, ꢀ11 6 k 6 11,
ꢀ26 6 l 6 26
1.63 6 h 6 28.25
x-Scan, x = 0.45
ꢀ33 6 h 6 33, ꢀ10 6 k 6 10,
ꢀ15 6 l 6 15
Flack x: 0.12(3)
23,186
Index ranges
Number of
Reflections measured
Unique reflections
Reflections observed
Parameters refined
Residual electron density (e/pm3)
Corrections
11,971
5402
27,229
6348
5602
5549 (I > 2r)
322
0.314 · 10ꢀ6
Lorentz and polarisation,
experimental absorption
correction [20]
Direct methods
Full-matrix least-square on F2
SHELX-97 [21], XPMA [22],
WINRAY [23]
R1 = 0.0288 (I > 2r)
Rw = 0.0736 (all data on F2)
4774 (I > 2r)
268
0.573 · 10ꢀ6
Lorentz and polarisation,
experimental absorption
correction [20]
2827 (I > 2r)
389
0.591 · 10ꢀ6
Lorentz and polarisation,
experimental absorption
correction [20]
Structure solution
Structure refinement
Programs used
Direct methods
Full-matrix least-square on F2
SHELX-97 [21], XPMA [22],
WINRAY [23]
Direct methods
Full-matrix least-square on F2
SHELX-97 [21], XPMA [22],
WINRAY [23]
R indices
R1 = 0.0305 (I > 2r)
Rw = 0.852 (all data on F2)
R1 = 0.0457 (I > 2r)
Rw = 0.1278 (all data on F2)
Standard deviations are given in parentheses.

3122
M. Ahlmann, O. Walter / Journal of Organometallic Chemistry 689 (2004) 3117–3131
polymer proceeds quantitatively as no resonance for the
free ligand on the polymer at ꢀ16.3 ppm is observed any
more. The high congruence between the chemical shifts
of 1a and 2a, respectively, to those of their immobilised
analogues indicate that the ligands 1 as well as their
complexes 2 are suitable model compounds for via
acetalation on a PVA matrix immobilised systems.
The spectroscopic data of the complexes 2 as well as
the results from the single crystal X-ray analyses show
that the acetal groups do not form any interaction with
the Rh-centres (Fig. 3 and Table 2). To investigate the
effectiveness of the acetal O-atoms in the complexes 2
for coordination, a free coordination site at the metal
centre has to be created. Chloride abstraction from the
complexes 2 would liberate such a position which could
subsequently be occupied by coordination of one O-ac-
etal atom from the dioxolane or dioxane unit of the lig-
ands [9]. This is of direct relevance for e.g.,
hydroformylation reactions, as it has been hypothesised
that, during the course of catalysis, the chloride ligands
of the pre-catalysts leave the metal coordination sphere
[10].
+
PR2
PR2
Rh
BF4
O
O
O
[Rh(COD)2]BF4
O
1c: R = Ph
1d: R = iPr
3c: R = Ph
3d: R = iPr
Scheme 4. Reaction of the dioxane derivatives 1c,
[Rh(COD)2]BF4.
d with
ring protons can be assigned to different resonances
in the NMR spectra [12].
The coordination of the acetal O-atoms in complexes
3 is evident in the FIR and IR spectra of the complexes
3, moreover, the observed strong absorptions for the
mRh–Cl stretching vibrations at 283 cmꢀ1 in complexes
2 are no longer present in the complex cations 3.
Furthermore, significant changes in the energies of
the C–O stretching vibrations were observed in compar-
ing the IR spectra of the ligands 1 and the complexes 2
to those of the cationic complexes 3 (Fig. 5), indicating
that the dioxolane or dioxane ring systems are in differ-
ent environments, as for e.g., an acetal O-atom coordi-
nated to the Rh-centre. C–O stretching vibrations are
observed at 1130 and 1080 cmꢀ1 for ligand 1b and its
By reacting the complexes 2a, b in dichloromethane
with TlPF6 (as the dehalogenating agent) an insoluble
salt is formed and after filtration and removal of the sol-
vent the cationic complexes 3a, b PF could be isolated
*
6
in good yields (Scheme 3).
Chloride abstraction however is not suitable for cre-
ating the corresponding dioxane derivatives 3c, d, where
at least in one case a TlPF6 adduct was isolated and
characterised as the main product [11]. However, the
complexes 3c, d BF could be prepared in good yields
d
[Rh(COD)2]BF4 (Scheme 4).
*
by direct reaction of the ligands 1c,
4
1129
1130
with
The signal patterns in the NMR spectra of the neu-
tral complexes 2 and the complex cations 3 are very
similar. The coordination of one acetal O-atom in 3
does not cause a splitting of the resonances of the co-
ordinated dioxolane or dioxane rings, indicating that in
solution there is a fast exchange between the two pos-
sible coordinated O-atoms. For the corresponding
complexes of the type fac-{bromotricarbonyl[g2-P,O-
(1)]rhenium(I)} this exchange is slow such that all the
1137
1109
cm-1
1000
1200
Fig. 5. IR spectra of the ligand 1b (top) and its complexes 2b (middle)
and 3b (bottom) (from 1000 to 1240 cmꢀ1).
+
PR
2
PR
2
Rh
Rh
O
O
PF
6
O
TlPF
6
Cl
O
2a, R: Ph
2b, R: iPr
3a, R: Ph
3b, R: iPr
Scheme 3. Dehalogenation of the neutral complexes 2, formation of the complex cations 3.

M. Ahlmann, O. Walter / Journal of Organometallic Chemistry 689 (2004) 3117–3131
3123
complex 2b; the cationic complex 3b shows two strong
absorptions at 1137 and 1109 cmꢀ1. These IR spectro-
scopic observations are in agreement with the results ob-
tained from X-ray analyses proving the coordination of
the acetal O-atom to the Rh-centre in the complex cati-
ons 3a–3d (Fig. 6 and Table 3).
acting as bidentate ligands via P,O-coordination (Fig.
6). The Rh–C-bond lengths for the C-atoms in trans-
positions to the O-atoms are determined to be 10 pm
shorter than the Rh–C-distances to the p-bound C-at-
oms trans to the P-atom. As for the complexes 2 this
observation is in good agreement with other complexes
of this type and is a consequence of the higher p-accep-
tor character of phosphorus compared to oxygen [13].
All the phenyl substituents on the dioxolane or dioxane
rings for all the structures reported here are in axial po-
sitions except for 3c where the phenyl substituent is
placed in the more favoured equatorial position on
the dioxane ring. This causes some larger ring torsions
which effects the resulting Rh–O distance. Correspond-
ingly the Rh–O distances in 3 are determined to be 212–
215 pm, except for 3c (220.9 pm) where it is found to be
significantly longer.
Single crystals of the complexes 3a, b PF or 3c,
*
d BF were obtained either by extraction with diethyl
6
*
4
ether or by diffusion of pentane into a dichloromethane
solution containing the complexes. The details of the
X-ray analyses are given in Table 3 and show that only
3a PF crystallises with half a molecule of dichloro-
*
methane per unit located on the inversion centre of the
6
unit cell.
The complex cations (3a–3d) show, like the neutral
complexes 2, a distorted square planar coordination at
the Rh-centre. The coordination sphere of the Rh-cen-
tres in 3 is formed by the COD ligand occupying two
neighbouring positions and the phosphine ligands of 1
For the complexes 3c, d BF the confirmed solid
*
state structures were found also to exist in solution.
4
C8
O2
C4
C1
C5
C6
C4
O2
C5
C9
C9
C3
C2
C3
C7
C6
C2
O1
C8
H7
C7
H7
C1
O1
C15
C26
C13
P1
Rh1
Rh1
P1
C11
C20
C27
C21
C22
C16
C14
C11
C23
C21
C12
C13
C14
C24
C19
C12
C10
C28
C19
C15
C29
C16
C23
C20
C18
C22
C17
C15
C14
C23
C15
C26
C22
C16
C24
C21
C27
C20
C13
C12
C19
C25
C24
C20
C14
C11
C29
C16
C13
C18
C11
C12
C21
C22
C17
C17
P1
Rh1
P1
C18
Rh1
C23
O1
C7
C1
C5
C2
C2
C4
C1
H7
C10
C9
O2
O1
C8
C6
C3
C3
C6
C9
C7
H7
C10
O2
C4
C8
C5
Fig. 6. View of the molecular structures of the complex cations 3a (top left), 3b (top right), 3c (bottom left), 3d (bottom right) determined by X-ray
diffraction. Selected bond distances (pm) and torsion angles (ꢁ) for 3a: O1–C7 147.4(3) pm, O2–C7 139.1(3) pm, H7–C7–C6–C5 59.0ꢁ; 3b: O1–C7
145.6(3) pm, O2–C7 139.5(3) pm, H7–C7–C6–C5 77.0ꢁ; 3c: O1–C7 146.1(4) pm, O2–C7 139.9(5) pm, H7–C7–C6–C1 ꢀ172.4ꢁ; 3d: C7–O1 144.1(4)
pm, C7–O2 140.0(4) pm, H7–C7–C6–C5 72.7ꢁ.

Table 3
Crystallographic data of the cationic complexes 3
Compound
3a PF6 0.5CH2Cl2
*
3b PF6
*
3c BF4
*
3d BF4
*
*
Empirical formula
Formula weight
Crystal size (mm3)
Crystal system
Space group
Unit cell dimensions
a (pm)
C29.5H32ClF6O2P2Rh
732.85
C23H35F6O2P2Rh
622.36
C30H33BF4O2PRh
646.25
C24H37BF4O2PRh
578.23
0.30 · 0.30 · 0.35
Monoclinic
P21/c (No. 14)
0.30 · 0.40 · 0.15
Triclinic
0.2 · 0.1 · 0.2
Monoclinic
P21/c (No. 14)
0.2 · 0.15 · 0.1
Triclinic
ꢀ
ꢀ
P1 (No. 2)
P1 (No. 2)
1391.37(7)
1089.86(6)
1054.90(4)
1074.45(4)
1097.28(6)
1315.97(7)
1030.34(4)
1092.32(5)
b (pm)
c (pm)
2023.1(1)
90.0
1417.33(5)
83.4202(6)
1931.3(1)
90.0
1359.30(6)
76.970(1)
a (ꢁ)
b (ꢁ)
105.764(1)
90.0
68.2027(6)
61.9296(5)
1312.59(8) · 106
2
1.575
96.659(1)
90.0
68.781(1)
62.777(1)
1264.94(9) · 106
2
1.518
c (ꢁ)
Volume (pm3)
Z
2952.5(3) · 106
2770.0(3) · 106
4
1.646
200
4
1.550
200
Dcalc (g/cm3)
Temperature (K)
h-Range (ꢁ)
Scan (ꢁ)
200
200
1.52 6 h 6 28.28
x-Scan, Dx = 0.3
ꢀ17 6 h 6 17, ꢀ14 6 k 6 14,
ꢀ26 6 l 6 26
1.55 6 h 6 28.30
x-Scan, Dx = 0.3
ꢀ13 6 h 6 13, ꢀ14 6 k 6 14,
ꢀ18 6 l 6 18
1.87 6 h 6 28.28
x-Scan, Dx = 0.45
ꢀ14 6 h 6 14, ꢀ17 6 k 6 17,
ꢀ25 6 l 6 25
1.61 6 h 6 28.30
x-Scan, Dx = 0.3
ꢀ13 6 h 6 13, ꢀ14 6 k 6 14,
ꢀ18 6 l 6 18
Index ranges
Number of
Reflections measured
Unique reflections
Reflections observed
Parameters refined
Residual electron density (e/pm3)
Corrections
29,805
7188
14,081
6295
29,506
6798
13,701
6102
6081 (I > 2r)
389
1.387 · 10ꢀ6
Lorentz and polarisation,
experimental absorption
correction [20]
5342 (I > 2r)
322
0.594 · 10ꢀ6
Lorentz and polarisation,
experimental absorption
correction [20]
3922 (I > 2r)
361
0.669 · 10ꢀ6
Lorentz and polarisation,
experimental absorption
correction [20]
4450 (I > 2r)
313
0.733 · 10ꢀ6
Lorentz and polarisation,
experimental absorption
correction [20]
Structure solution
Structure refinement
Programs used
Direct methods
Full-matrix least-square on F2
SHELX-97 [21], XPMA [22],
WINRAY [23]
Direct methods
Full-matrix least-square on F2
SHELX-97 [21], XPMA [22],
WINRAY [23]
Direct methods
Full-matrix least-square on F2
SHELX-97 [21], XPMA [22],
WINRAY [23]
Direct methods
Full-matrix least-square on F2
SHELX-97 [21], XPMA [22],
WINRAY [23]
R indices
R1 = 0.0382 (I > 2r)
Rw = 0.1086 (all data on F2)
R1 = 0.0288 (I > 2r)
Rw = 0.0736 (all data on F2)
R1 = 0.0457 (I > 2r)
Rw = 0.1100 (all data on F2)
R1 = 0.0498 (I > 2r)
Rw = 0.1044 (all data on F2)
Standard deviations are given in parentheses.

M. Ahlmann, O. Walter / Journal of Organometallic Chemistry 689 (2004) 3117–3131
3125
On the basis of two-dimensional NOESY experiments
relevant intramolecular NOEs between the different lig-
ands at the Rh-centres were identified and confirm that
in solution no conformational changes of the complexes
occur.
Furthermore temperature dependent 1H NMR exper-
iments showed that the phenyl substituents at the 2-po-
sition of the dioxane ring in 3c, 3d keep their positions
showing no ring inversion of the dioxane rings.
In agreement with the IR spectroscopic data, the re-
cation 3c is an exception; the corresponding torsion an-
gle (7.6ꢁ) is small and has a similar value to the values
found in complexes 2. This observation is an effect of
the substitution pattern on the dioxane ring in 3c where
the phenyl substituent is found in a more favoured ax-
ial position. This allows the phenyl ring and the diox-
ane ring of 3c to occupy perpendicular positions to
one another, which is preferred on the grounds of ster-
ics but results in the elongation of the Rh–O bond
length.
sults from the X-ray analyses of the complexes 3 anions
*
The coordination behaviour of the ligands 1 in the
complex cations 3 show coordination properties flexible
enough for the stabilisation of free coordination sites at
a metal centre possibly formed as intermediates in a cat-
alytic cycle.
The complexes described here act as model com-
pounds for complexes bound to a polyvinylalcohol resin
with the polymer linkage to be used for an effective cat-
alyst recycling. Therefore, the Rh-complexes 2 and the
salts of the complex cations 3 were tested towards their
catalytic selectivity in the hydroformylation of octene
(Table 4).
The general selectivities in the hydroformylation of
octene of the complexes 2 and the salts of the complex
cations 3 are very similar to each other and comparable
to other systems with no large phosphine excess in-
volved [17]. The overall selectivity to the aldehydes is
high and the complexes do not show high activity in
the hydrogenation of octene or the aldehydes produced.
All the pre-catalysts show isomerisation activity, trans-
forming 1-octene into 2-octene, 3-octene and 4-octene
which then are also hydroformylated by the catalysts.
As the hydroformylation activity of 1-octene is higher
than of its isomers, the most important products, repre-
senting 90% of the selectivity, are n-nonanal and 2-meth-
yloctanal, which are formed in a 1.25:1 ratio. This n/iso
ratio is typical for hydroformylation reactions carried
out in the absence of large amounts of phosphine [17].
The very similar selectivity in the catalytic experiments
of the neutral pre-catalysts 2 compared to their cationic
show significant changes in the bond lengths between
the acetal C-atoms and the two acetal O-atoms. Gener-
ally the bond distances between the acetal C-atom and
the coordinated O-atom (144–147 pm) were determined
to be at least 3 pm longer than their corresponding dis-
tances to the non coordinated O-atom which were deter-
mined to be 139–140 pm. Comparing these values with
the corresponding values observed in the complexes 2
or the free ligands 1, it appears that the acetal C–O-dis-
tance of the coordinated O-atom is elongated where the
one of the non-coordinated O-atom is shortened. This is
an effect of coordination to the metal centre which is al-
so observed in other complexes with coordinated 1,3-di-
oxolanes [14] or 1,3-dioxanes [12,15], even if in some
cases this tendency seems to be only marginal [16].
A comparison of the rotational positions of the di-
oxolane or dioxane rings in the 3 anion to the com-
*
plexes 2 can be performed on the basis of the torsion
angle comprised of the acetal proton, the acetal C-atom
itself, the carbon atom of the phenyl ring bound to the
acetal C-atom, and one of its neighbouring C-atoms in
the phenyl ring. The values of the complexes 2 were
found to be less than 10ꢁ (Fig. 3) demonstrating the
nearby perpendicular position of the different ring sys-
tems involved. For the complex cations 3a, b, d these
torsion angles were determined to be 59.0ꢁ for (3a)
and 77.0ꢁ for (3b) which are much higher than those de-
termined for complexes 2, showing that coordination of
the acetal O-atoms results in a rotation of about 60ꢁ
around the axis described by the acetal C-atom and
the C-atom of the phenyl ring it is bound to. Complex
analogues 3 anion might indicate that during the catal-
*
ysis the chloro ligands in 2 leave the coordination sphere
Table 4
Selectivity (%) of the complexes 2 and 3 anion in the hydroformylation of octene
*
Catalyst
Nonanal
2-Methyl-octanal
2-Ethyl-heptanal
2-Propyl-hexanal
Olefins/octane
Alcohols
2a
2b
2c
2d
50.9
51.6
49.0
52.8
52.1
52.4
47.7
52.8
38.4
37.9
38.7
37.0
39.7
40.1
41.3
38.4
7.9
7.5
8.9
7.5
5.9
5.8
5.5
6.5
2.5
2.4
2.9
2.4
1.5
1.4
1.6
2.1
0.2
0.5
0.5
0.3
0.6
0.2
0.3
0.2
0
0
0
0
3a PF6
*
3b PF6
*
3c BF4
*
3d BF4
*
0.2
0
3.6
0
Experiments performed with 0.02 mmol catalyst per 5 mmol octene in 50 ml dichloromethane at 65 ꢁC and about 50 bar syngas pressure during 15 h.
Selectivity is based on conversion reported on the base of GC/MS data.

3126
M. Ahlmann, O. Walter / Journal of Organometallic Chemistry 689 (2004) 3117–3131
of the metal so that independently from the neutral or
ionic nature of the starting complex similar intermedi-
ates can be formed finally causing the observed compa-
rable selectivity in the catalysis [10]. Whether during the
catalysis g2-P,O-coordination of the ligands 1 occurs
can not be determined on the basis of the present data
as in situ spectroscopic investigations actually have not
been performed.
The data obtained from these catalytic experiments
will form the basis for the evaluation of the results on
catalytic transformations performed with the Rh loaded
modified polyvinylalcohol.
ane [5] were synthesised from the literature procedures.
Solvents were dried and purified by standard methods.
NMR-spectra were recorded on a 250 MHz Bruker
AVANCE or on a Varian Unity INOVA 400 MHz spec-
trometer at 25 ꢁC and referenced to the residual proton
signal of the solvent (1H NMR spectra) or its carbon fre-
quency (13C NMR spectra) or to H3PO4 as external
standard (31P NMR spectra). The heteronuclear spectra
were recorded with proton decoupling. The variable tem-
perature NMR measurements were performed in d8 tol-
uene instead of CDCl3 due to its higher boiling point.
The two-dimensional NMR spectra were recorded in
CDCl3 due to the higher solubility of the complexes in
it. The NOESY spectra were recorded at mixing times
of 450 ms using 1 K of data points in f2 dimension and
performing 512 experiments in f1 with 48 transients per
experiment. The mass spectra were obtained on a Hewl-
ett–Packard LC MSD Serie 1100, ionisation method API-
ES from methanol solutions of the compounds contain-
ing NH4OAc. Infrared spectra and FIR spectra were re-
corded on a BIORAD FT spectrometer. The elemental
analyses were performed on a Vario EL CHN-analyser.
For the details of the single crystal X-ray diffraction
measurements see Tables 1–3 and Section 5. The X-ray
analyses were performed with an irradiation time of
10 s per frame collecting a full sphere of data. For search-
es on single crystal X-ray diffraction data the Cambridge
Structural Database has been used [19].
3. Conclusions and outlook
The syntheses of the ligands 1 as well as their corre-
sponding complexes 2 presented here is straightforward
and proceed in good yields. With their 1,3-dioxanyl or
1,3-dioxolanyl residues representing a small part of the
polymer backbone they act as model compounds for
via trans acetalation on a polyvinylalcohol matrix
immobilised systems in terms of characterisation and
evaluation of the catalytic behaviour.
The complexes 2 and the cationic complexes 3 are cat-
alysts for the hydroformylation of 1-octene and on the
basis of an analysis of the product distribution it seems
to be very probable that in the catalysis both complexes
form similar intermediates as generally the product dis-
tribution is equal. If during the catalysis g2-P,O-coordi-
nation of the ligands to the metal centre proceeds cannot
be determined.
4.1. 2-(Ortho-diisopropylphosphinophenyl)-1,3-dioxo-
lane, 1b
Investigations are ongoing on the pre-catalysts bound
to PVA concerning their transformations during the ca-
talysis via the identification of the complexes on the pol-
ymer after the catalysis. The long term behaviour of the
PVA bound pre-catalysts in terms of Rh-leaching and
the stability of the acetales is of essential interest and ob-
jective of present research as well the development of
complexes which will show a higher selectivity in the
hydroformylation of 1-octene. However, the complexes
described here act as the first simple models for the char-
acterisation of pre-catalysts which are via acetalation
bound to a PVA resin and therefore contribute to the
development of this system.
7.8 ml of a 2.7 N n-BuLi solution in heptane (21.06
mmol) was added dropwise to a solution of 4.80 g
(21.0 mmol) 2-(ortho-bromophenyl)-1,3-dioxolane in
50 ml THF at ꢀ78 ꢁC. After stirring for another hour
at ꢀ78 ꢁC, 3.12 g (21.0 mmol) chlorodiisopropylphos-
phine was added and the reaction mixture was al-
lowed to warm up to room temperature. After
hydrolysis, phase separation and drying of the organic
phase the solvent was removed in vacuo. The low
melting-point residue was recondensed at 1 mbar
and 120–150 ꢁC (oil bath temperature) yielding
4.12 g (15.5 mmol, 74%) 1b with a melting point of
50–51 ꢁC.
IR (KBr)/cmꢀ1: 3063 (w), 2979, 2958, 2949, 2916 (s),
1473, 1437 (m), 1389, 1383, 1364, 1361, 1129 (s), 1082,
1058 (ss), 762, (ss).
4. Experimental
MS (m/z): 265, (M ꢀ H)+, 2%, 237, C13H18POþ, 66%,
2
All reactions were performed under an inert gas at-
mosphere using standard Schlenk techniques. Chlorodi-
isopropylphosphine purchased from Aldrich and
chlorodiphenylphosphine from Fluka were degassed
and stored under an inert atmosphere before use. TlPF6
was purchased from Fluorochem. [(COD)RhCl]2
[18],and 2-(ortho-bromophenyl)-1,3-dioxolane or -diox-
152, C7H5POþ2 , 100%, 110, C6H7P+, 84%.
1H NMR (CDCl3): d = 0.92 (dd, JHH = 6.8 Hz,
3
3JHP = 12.4 Hz, 6H, CH3), 1.16 (dd, JHH = 7.0 Hz,
3
3JHP = 15.3 Hz, 6H, CH3), 2.15 (m (br), 2H, PCH),
4.07 (m, 2H, OCHH), 4.17 (m, 2H, OCHH), 6.67 (d,
4JHP = 6.8 Hz, 1H, CHO2), 7.34–7.71 (m, 4H, Ar–H).
31P NMR (CDCl3): d = ꢀ8.67 (s).

M. Ahlmann, O. Walter / Journal of Organometallic Chemistry 689 (2004) 3117–3131
3127
2
13C NMR (CDCl3): d = 18.75 (d, JCP = 8.9 Hz, 2C,
CH3), 19.38 (d, JCP = 18.6 Hz, 2C, CH3), 23.37 (d,
ature. After hydrolysis, phase separation and drying of
the organic phase, the solvent was removed in vacuo.
The oily residue was recondensed at 140–170 ꢁC and 1
mbar yielding 3.13 g (11.2 mmol, 80%) of 1d as colourless
crystals with a melting point of 82 ꢁC.
2
1JCP = 10.5 Hz, 2C, PCH), 64.69 (s, 2C, OCH2),
3
100.46 (d, JCP = 30.8 Hz, 1C, O2C), 125. 64 (s, 1C,
Ar–C), 127.65 (s, 1C, Ar–C), 128.27 (s, 1C, Ar–C),
1
131.27 (s, 1C, Ar–C), 142.89 (d, JCP = 19.4 Hz, 1C,
Ar–C)
IR (KBr)/cmꢀ1: 3090 (w), 3072 (w), 3057 (m), 2986
(s), 2965 (ss), 2950 (ss), 2895 (s), 2865 (ss), 2847 (ss),
1589 (w), 1568 (w), 1519 (w), 1467 (ss), 1459 (ss), 1448
(m), 1437 (m), 1387 (ss), 1371 (ss), 1364 (ss), 1362 (ss),
1248 (m), 1233 (s), 1149 (ss), 1125 (m), 1101 (ss), 1007
(ss), 992 (ss), 963 (ss), 759 (ss), 657 (m), 606 (m), 532
(m), 506 (s).
1b (C15H23O2P): C, 67.01 (67.65 calc.); H, 9.15 (8.70
calc.).
4.2. 2-(Ortho-diphenylphosphinophenyl)-1,3-dioxane, 1c
5.7 ml of a 2.7 normal n-BuLi solution in heptane
(15.39 mmol) was added added dropwise to a solution
of 3.77 g (15.5 mmol) 2-(ortho-bromophenyl)-1,3-diox-
ane in 50 ml THF at ꢀ78 ꢁC. After stirring for another
hour at ꢀ78 ꢁC 3.42 g (15.5 mmol) chlorodiphenylphos-
phine was added and the reaction mixture was allowed
to warm up to room temperature. After hydrolysis,
phase separation and drying of the organic phase the
solvent was removed in vacuo. The residue was resolved
in dichloromethane and the solvent removed in vacuo
and the resulting oily residue was recrystallised from
pentane yielding 4.52 g (13.0 mmol, 84%) 1c with a melt-
ing point of 96 ꢁC.
FIR (PE): 471 (s), 460 (s), 417 (s), 390 (m), 377 (m),
359 (s), 292 (m).
3
1H NMR (CDCl3): d = 0.91 (dd, JH,H = 7.0 Hz,
3
3JH,P = 12.4 Hz, 6H, CH3), 1.14 (dd, JH,H = 7.0 Hz,
2
3JH,P = 14.9 Hz, 6H, CH3), 1.44 (dpsept, JH,H = 13.4
3
Hz, JHeq,Hax = 2.0 Hz, JHeq,Heq = 1.0 Hz, 1H,
3
(OCH2)2CHHeq), 2.13 (m, 2H, PCH), 2.25 (pqt,
3
3
2JH,H = 13.4 Hz, JHax,Hax = 12.4 Hz, JHeq,Heq = 5.0
2
Hz, 1H, (OCH2)2CHHax), 4.05 (ptd, JH,H = 11.7 Hz,
3
3JHax,Hax = 12.4 Hz, JHax,Heq = 2.0 Hz, 2H, OCHHax),
2
4.22 (ddd, JH,H = 11.7 Hz, JHeq,Hax = 5.0 Hz, JHeq,-
3
3
4
OCHHeq), 6.42 (d, JH,P = 7.2 Hz, 1H,
Heq = 1.0 Hz, 2H,
CHO2), 7.30–7.78 (m, 4H, Ar).
31P NMR (CDCl3): d = ꢀ7.5 (s).
IR (KBr)/cmꢀ1: 3065 (m), 3054 (m), 2972 (s), 2953 (s),
2853 (m), 1591 (w), 1583 (m), 1568 (w), 1477 (s), 1466
(s), 1460 (m), 1437 (s), 1432 (s), 1392 (m), 1376 (m),
1129 (m), 1098 (ss), 1027 (m), 1002 (ss), 759 (ss), 748
(ss), 698 (ss), 546 (s), 520 (s), 507 (s), 488 (s).
13C NMR (CDCl3): d = 18.6 (s, 2 C, CH3), 19.0 (d,
1
2JC,P = 16.9 Hz, 2 C, CH3), 23.0 (d, JC,P = 11.3 Hz,
2C, PCH), 24.8 (s, 1C, (OCH2)2CH2), 66.2 (s, 2C,
3
OCH2), 98.4 (d, JC,P = 31.9 Hz, 1C, CHO2), 125.2–
FIR (PE): 467 (m), 423 (m), 414 (m), 397 (m), 386 (m).
MS (m/z): 349,(M + H)+, 100%.
130.8 (m, 6C, Ar).
MS (m/z): 281, (M + H)+, 100%.
1d (C16H25O2P): C, 68.43 (68.55 calc.); H, 8.93 (8.99
calc.).
2
1H NMR (CDCl3): d = 1.36 (d (br), JH,H = 13.4 Hz,
1H, (OCH2)2CHHeq), 2.16 (pqt, JH,H = 13.4 Hz,
2
3
3JHax,Hax = 12.8 Hz, JHax,Heq = 5.1 Hz, 1H, (OCH2)2-
2
3
CHHax), 3.87 (dpt, JH,H = 11.1 Hz, JHax,Hax
=
4.4. {Chloro(COD)[2-(ortho-diphenylphosphinophenyl)-
1,3-dioxolane]rhodium(I)}, 2a
3
12.8 Hz, JHax,Heq = 2.3 Hz, 2H, OCHHax), 4.07 (dd,
2JH,H = 11.1 Hz,3JHeq,Hax = 5.1 Hz, 2H, OCHHeq),
4
6.13 (d, JH,P = 5.8 Hz, 1H, CHO2), 6.94–7.75 (m,
14H, Ar).
0.174 g (0.35 mmol) [(COD)RhCl]2 was dissolved in
10 ml dichloromethane and after addition of 0.236 mg
(0.7 mmol) 2-(ortho-diphenylphosphinophenyl)-1,3-di-
oxolane (1a) the solution was stirred for 60 min at room
temperature. The solvent was removed in vacuo and the
residue was extracted with refluxing pentane for 50 h
yielding 0.33 g (0.6 mmol, 81%) 2a.
IR (KBr)/cmꢀ1: 3059, 3043 (w) 2951, 2937, 2884,
2871, 1480, 1437, 1433 (m) 1123 (m), 1092 (ss), 761,
746, 740 (m), 694 (s).
31P NMR (CDCl3): d = ꢀ16.1 (s).
13C NMR (CDCl3): d = 25.0 (s, 1C, (OCH2)2CH2),
66.6 (s, 2C, OCH2), 99.5 (d, JC,P = 26.3 Hz, 1C,
3
CHO2), 125. 3–142.3 (m, 18C, Ar).
1c (C22H21O2P): C, 74.99 (75.85 calc.); H, 6.08 (6.04
calc.).
4.3. 2-(Ortho-diisopropylphosphinophenyl)-1,3-dioxane,
1d
FIR (PE): 283 (s, m(Rh–Cl)).
1H NMR (CDCl3): d = 1.96 (s, br, 2H, CH2 (COD)),
2.05(s, br, 2H, CH2 (COD)), 2.41 (s, br, 4H, CH2
(COD)), 3.34 (s, br, 2H, CH (COD)), 3.95 (m, 2H,
OCHH), 4.20 (m, 2H, OCHH), 5.59 (s, br, 2H, CH
(COD)), 7.26–7.81 (m, 14H, Ar–H), 7.49 (m, 1H,
CHO2).
3.396 g (14.0 mmol) 2-(ortho-bromophenyl)-1,3-diox-
ane was dissolved in 50 ml THF at ꢀ78 ꢁC. After dropwise
addition of 5.2 ml of a 2.7 N n-BuLi solution in heptane
and stirring for 1 h at this temperature 2.132 g (14.0
mmol), chlorodiisopropylphosphine was added and the
reaction mixture was allowedto warm up toroom temper-
1
31P NMR (CDCl3): d = 23.40 (d, JPRh = 146.5 Hz).

3128
M. Ahlmann, O. Walter / Journal of Organometallic Chemistry 689 (2004) 3117–3131
13C NMR (CDCl3): d = 27.94 (s, 2C, CH2 (COD)),
31.95 (s, 2C, CH2 (COD)), 64.63 (s, 2C, OCH2), 70.19
FIR (PE): 493 (s), 467 (w), 419 (s), 385 (s), 341 (w),
284 (s).
1H NMR (CDCl3): d = 1.26 (dd (br), 2JH,H = 13.2 Hz,
3JHeq,Hax = 1.4 Hz, 1H, (OCH2)2CHHeq), 1.95 (m, 2H,
CH2 (COD)), 2.10 (m, 1H, CH2 (COD), 2.15 (pqt,
3
(s, br, 2C, CH (COD)), 101.01 (d, JCP = 15.0 Hz, 1C,
HCO2), 102.67 (s, 2C, CH (COD)), 127.10–134.27 (m,
18C, Ar).
MS/ESI (m/z): 545, (M ꢀ Cl)+, 100%.
2a (C29H31ClO2PRh): C, 60.14 (59.96 calc.); H, 5.88
(5.38 calc.).
3
3
2JH,H = 13.2 Hz, JHax,Hax = 12.1 Hz, JHax,Heq = 4.9
Hz, 2H, (OCH2)2CHHax), 2.44 (m, 4H, CH2 (COD)),
3.24 (s (br), 2H, CH (COD)trans to Cl), 3.45 (dpt,
3
3
2JH,H = 11.3 Hz, JHax,Hax = 12.1 Hz, JHax,Heq = 1.4
2
Hz, 2H, OCHHax), 3.96 (dd, JH,H = 11.3 Hz,
4.5. {Chloro(COD)[2-(ortho-diisopropylphosphinophe-
nyl)-1,3-dioxolane]rhodium(I)}, 2b
3JHeq,Hax = 4.9 Hz, 2H, OCHHeq), 5.57 (s (br), 2H, CH
4
(COD)trans to P), 5.92 (d, JH,P = 2.1 Hz, 1H, CHO2),
7.28–7.97 (m, 14H, Ar–H).
190.8 mg (0.39 mmol) [(COD)RhCl]2 was dissolved in
10 ml dichloromethane and after addition of 207 mg
(0.78 mmol) 2-(ortho-diisopropylphosphinophenyl)-1,3-
dioxolane (1b) it was stirred for 30 min at room temper-
ature. The solvent was removed in vacuo and the residue
was extracted with refluxing pentane for 12 h yielding
0.336 g (0.65 mmol, 84%) 2b as a crystalline solid.
IR (KBr)/cmꢀ1: 3097, 3061, 3040 (w), 2963 (s), 2883
(s), 1471, 1439, 1431 (m), 1129 (m), 755 (s).
31P NMR (CDCl3): d = 24.4 (d, JP,Rh = 150.2 Hz).
1
13C NMR (CDCl3): d = 24.5 (s, 1C, (OCH2)2CH2),
27.9 (s, 2C, CH2 (COD)), 32.0 (s, 2C, CH2 (COD)),
1
66.4 (s, 2C, OCH2), 70.6 (d, JC,Rh = 13.1 Hz, 2C, CH
1
(COD)trans to Cl), 98.9 (d, JC,Rh = 9.4 Hz, 2C, CH
(COD)trans to P), 103.2 (s, 1C, CHO2), 127.2–140.8 (m,
18C, Ar).
MS/ESI (m/z): 559 (M ꢀ Cl)+, 100%, 349
FIR (PE): 285 (m, m(Rh–Cl)).
(C22H22O2P+, 19%).
MS/ESI (m/z): 477, (M ꢀ Cl)+, 100%.
2c (C30H33ClO2PRh): C, 60.55 (60.57 calc.); H, 5.74
(5.59 calc.).
3
1H NMR (CDCl3): d = 1.32 (dd, JHH = 7.0 Hz,
3
3JHP = 15.0 Hz, 6H, CH3), 1.32 (dd, JHH = 7.0 Hz,
3JHP = 13.4 Hz, 6H, CH3) 1.97 (m, 4 H, CH2 (COD)),
2.38 (m, 4H, CH2 (COD)), 2.56 (s, br, 2H, PCH), 3.50
(s, br, 2H, CH (COD)), 4.19 (m, 2H, OCHH), 4.30
(m, 2H, OCHH), 5.38 (s, br, 2H, CH (COD)), 7.65 (d,
4JHP = 3.8 Hz, 1H, CHO2), 7.35–7.82 (m, 4H, Ar–H).
4.7. {Chloro(COD)[2-(ortho-diisopropylphosphinophe-
nyl)-1,3-dioxane]rhodium(I)}, 2d
To a solution of 120.3 mg (0.24 mmol) [Rh(COD)Cl]2
in 5 ml dichloromethane, 137.4 mg (0.49 mmol) 2-(or-
tho-diisopropylphosphinophenyl)-1,3-dioxane (1d) was
added. After stirring for 45 min the solvent was removed
in vacuo, the residue extracted with pentane for 15 h
yielding 200.6 mg (0.38 mmol, 78%) of 2d as yellow
crystals.
IR (KBr)/cmꢀ1: 3060 (w), 2989 (m), 2973 (s), 2956
(m), 2939 (m), 2869 (s), 2833 (m), 1567 (w), 1520 (w),
1467 (sh) (m), 1430 (m), 1391 (m), 1385 (s), 1369 (m),
1364 (m), 1250 (m), 1233 (m), 1145 (s), 1123 (m), 1095
(ss), 994 (ss), 982 (ss), 948 (s), 759 (ss), 650 (m), 615
(m), 525 (s).
1
31P NMR (CDCl3): d = 25.91 (d, JPRh = 144.7 Hz).
13C NMR (CDCl3): d = 18.51 (s, 2C, CH3), 19.24 (s,
2C, CH3), 23.12 (d, JCP = 18.8 Hz, 2C, PCH), 27.60
(s, 2C, CH2 (COD)), 31.95 (s, 2C, CH2 (COD)), 64.69
1
1
(s, 2C, (OCH2)2), 69.78 (d, JCRh = 11.3 Hz, 2C, CH
1
(COD)), 100.67 (d, JCRh = 15.0 Hz, 2C, CH (COD)),
101.10 (s, 1C, HCO2), 127.45 (s, 1C, Ar–C), 128.16 (s,
1C, Ar–C), 129.04 (s, 1C, Ar–C), 129.58 (s, 1C, Ar–C),
140. 97 (s, 1C, Ar–C).
2b (C23H35ClO2PRh): C, 53.57 (53.86 calc.); H, 7.29
(6.88 calc.).
FIR (PE): 472 (s), 432 (m), 409 (m), 389 (m), 378 (s),
334 (w), 282 (s).
4.6. {Chloro(COD)[2-(ortho-diphenylphosphinophenyl)-
1,3-dioxane]rhodium(I)}, 2c
3
1H NMR (CDCl3): d (ppm = 1.24 (dd, JH,H = 7.0
Hz, JH,P = 13.4 Hz, 6H, CH3), 1.50 (dd, JH,H = 7.3 Hz,
3
3
2
To a solution of 150.3 mg (0.3 mmol) [Rh(COD)Cl]2
in 5 ml dichloromethane, 213.4 mg (0.6 mmol) 2-(ortho-
diphenylphosphinophenyl)-1,3-dioxane (1c) was added.
After stirring for 45 min the solvent was removed in va-
cuo and the resulting powder extracted with pentane for
3 days. 297.1 mg (0.5 mmol, 83%) of 2c as yellow crys-
tals was isolated.
IR (KBr)/cmꢀ1: 3053 (w), 2960 (m), 2938 (m), 2916
(m), 2872 (m), 2829 (m), 1586 (w), 1571 (w), 1480 (m),
1467 (m), 1435 (m), 1123 (m), 1099 (ss), 998 (s), 759
(m), 749 (m), 695 (s), 546 (w), 529 (s), 516 (s), 510 (s).
3JH,P = 15.1 Hz, 6H, CH3), 1.52 (dd, JH,H = 15.5 Hz,
3JHeq,Hax = 1.3 Hz, 1H, (OCH2)2CHHeq), 1.93 (m, 4H,
2
CH2(COD)), 2.36 (pqt, JH,H = 15.1 Hz, JHax,-
3
3
Hax = 12.0 Hz, JHax,Heq = 4.7 Hz, (OCH2)2CHHax),
2.38 (m, 4H, CH2 (COD), 2.59 (s (br), 2H, PCH), 3.31
2
(s (br), 2H, CH (COD)trans to Cl), 4.26 (dd, JH,H = 11.2
3
Hz, JHeq,Hax = 4.7 Hz, 2H, OCHHeq), 4.40 (ptd,
3
3
2JH,H = 11.2 Hz, JHax,Hax = 12.0 Hz, JHax,Heq = 1.3
Hz, 2H, OCHHax), 5.42 (s (br), 2H, CH (COD)trans to P),
4
7.29–7.92 (m, 4H, Ar), 7.36 (d, JH,P = 3.6 Hz, 1H,
CHO2).

M. Ahlmann, O. Walter / Journal of Organometallic Chemistry 689 (2004) 3117–3131
3129
1
31P NMR (CDCl3): d = 25.5 (d, JP,Rh = 143.8 Hz).
isolated as a yellow powder. Single crystals of 3b PF
*
6
were obtained by extraction of the product with reflux-
13C NMR (CDCl3): d (ppm = 19.1 (s, 4C, CH3)2),
23.8 (d, JC,P = 16.9 Hz, 2C, PCH), 25.1 (s, 1C,
1
ing diethyl ether for 1 day.
(OCH2)2CH2), 27.5 (s, 2C, CH2 (COD)), 31.9 (s, 2C,
CH2 (COD)), 66.4 (s, 2C, OCH2), 70.4 (s, 2C, CH
3
(COD)trans to Cl), 98.9 (d, JC,P = 15.0 Hz, 1C, CHO2),
IR (KBr)/cmꢀ1: 3062 (w), 2963, 2924, 2879, 1471,
1439, 1435, 1462, 1387, 1364, 1137, 1109, 1090, 1060
(m), 839 (ss), 766 (m ), 558 (ss).
100.6 (s, 2C, CH (COD)trans to P), 127.1–141.8 (m, 6C,
Ar).
MS/ESI (m/z): 477, (M ꢀ PF6)+, 100%.
3
1H NMR (CD2Cl2): d = 1.26 (dd, JHH = 6.9 Hz,
MS/ESI (m/z): 491, ((M ꢀ Cl)+, 100%), 281
3JHP = 14.6 Hz, 12H, CH3), 2.14 (s (br), 2H, CH2
(COD)), 2.16 (s (br), 2H, CH2 (COD)), 2.29 (s (br),
2H, PCH), 2.57 (m, 4H, CH2 (COD)), 3.93 (m, 2H,
OCHH), 4.04 (s (br), 2H, CH (COD)), 4.09 (s (br),
2H, OCHH), 5.28 (s (br), 2H, CH (COD)), 7.29 (s,
1H, CHO2), 7.53–7.70 (m, 4H, Ar–H).
(C16H26O2P)+, 36%.
2d (C24H37ClO2PRh): C, 55.14 (54.71 calc.); H, 7.00
(7.08 calc.).
4.8.
{(COD)[g2-P,O-2-(ortho-diphenylphosphinophe-
nyl)-1,3-dioxolane]rhodium(I)} hexafluoro-phosphate,
1
31P NMR (CD2Cl2): d = 22.18 (d, JPRh = 141.7 Hz),
1
3a PF
*
ꢀ144.24 (sept., JPF = 711.4 Hz).
6
13C NMR (CD2Cl2): d = 18.22 (s, 2C, CH3), 19.26 (s,
2C, CH3), 25.80 (s (br), 2C, PCH), 27.64 (s, 2C, CH2
(COD)), 32.61 (s, 2C, CH2 (COD)), 66.20 (s, 2C,
(OCH2)2), 72.01 (s (br), 2 C, CH (COD)), 104.39 (s
0.228 g (0.46 mmol) [(COD)RhCl]2 and 0.301 g (0.93
mmol) 2-(ortho-diphenylphosphinophenyl)-1,3-dioxo-
lane were dissolved in 5 ml dichloromethane and stirred
at room temperature for 30 min. 0.324 mg (0.93 mmol)
TlPF6 was added and it was stirred for 1 h. The resulting
precipitate was filtered off from the reaction mixture and
discarded. The remaining solution was layered with
THF and pentane and after two days at room tempera-
ture, 0.567 g (0.77 mmol, 83%) orange crystals of
4
(br), 2 C, CH (COD)), 104.81 (d, JCP = 5.6 Hz, 1C,
CHO2), 123.77 (d, JCP = 30.0 Hz, 1C, Ar), 125.54 (d,
JCP = 7.5 Hz, 1C, Ar), 129.92 (d, JCP = 3.8 Hz, 1C,
Ar), 131.64 (s, 1C, Ar), 141.14 (d, JCP = 9.4 Hz, 1C, Ar).
3b PF (C H F O P Rh): C, 43.82 (44.39 calc.); H,
6
*
5.84 (5.67 calc.).
6
23 35
2 2
3a PF 0.5 dichloromethane were isolated.
*
*
6
IR (KBr)/cmꢀ1: 3049 (m), 2968, 2946, 2920, 2885 (m),
1437, 1435 (ss), 1114 (s), 1094 (ss), 841, 742, 700, 695
(ss), 558 (ss).
4.10. {(COD)[g2-P,O-2-(ortho-diphenylphosphinophe-
nyl)-1,3-dioxane]rhodium(I)} tetrafluoro-borate, 3c BF
*
4
MS/ESI (m/z): 545 (M ꢀ PF6)+, 100%, 335
To
[(COD)2Rh]BF4 in 10 ml THF, 57.5 mg (0.16 mmol)
2-(ortho-diphenylphosphinophenyl)-1,3-dioxane (1c)
a
solution of 67.0 mg (0.16 mmol)
(C21H20O2P)+, 13%.
1H NMR (CD2Cl2): d = 1.99 (m, 2H, CH2 (COD)),
2.15 (m, 2H, CH2 (COD)), 2.53 (m, 4H, CH2 (COD),
3.26 (s, br, 2H, ‚CH (COD)), 4.13 (m, 2H, OCHH),
4.20 (m, 2H, OCHH), 5.50 (s, br, 2H, ‚CH (COD)),
5.57 (s, 1H, CHO2), 7.34–7.77 (m, 14H, Ar–H).
was added. After stirring for 2 h at 67 ꢁC the solvent
was removed in vacuo and the residue was washed twice
with 20 ml pentane. The orange solid was dissolved in
dichloromethane and layered successively with THF
and pentane. After 24 h, 79.2 mg (0.12 mmol, 77%) of
3c BF was isolated as orange crystals.
1
31P NMR (CD2Cl2): d = 21.96 (d, JPRh = 146.7 Hz),
1
ꢀ143.69 (sept., JPF = 711.4 Hz).
*
4
13C NMR (CD2Cl2): d = 28.67 (s, 2C, CH2 (COD)),
32.86 (s, 2C, CH2 (COD)), 68.14 (s, 2C, OCH2), 72.40
IR (KBr)/cmꢀ1: 3055 (w), m(Ar–H), 2977 (w), 2955
(w), 2933 (w), 2875 (w), 2834 (w), m(C–H), 1584 (w),
1571 (w), 1480 (m), 1464 (w), 1452 (w), 1437 (m),
1368 (w), m(C‚C) and d(C–H), 1167 (m), 1152 (m),
1133 (m), 1101 (ss), 1067 (ss), 1037 (ss), m(C–O) and
m(B–F), 755 (sh) (ss), 702 (s), qwag(Ar–H), 525 (s),
512 (s).
1
(d, JCRh = 12.2 Hz, 2C, CH (COD)), 104.46 (d,
3JCP = 12.2 Hz, 1C, CHO2), 108.36 (s, 2C, CH
(COD)), 125.69–138.97 (m, 18C, Ar–C).
3a PF 0.5 dichloromethane (C29.5H32ClF6O2P2Rh):
*
C, 48.65 (48.35 calc.); H, 4.56 (4.40 calc.).
*
6
2
1H NMR (CDCl3): d = 1.83 (d (br), JH,H = 14.3 Hz,
4.9. {(COD)[g2-P,O-2-(ortho-diisopropylphosphinophe-
nyl)-1,3-dioxolane]rhodium(I)} hexa-fluorophosphate,
1H, (OCH2)2CHHeq), 2.04 (m, 2H, CH2 (COD)), 2.11
(m, 2H, CH2 (COD)), 2.24 (m, 1H, (OCH2)2CHHax),
2.56 (s (br), 4H, CH2 (COD)), 3.25 (s (br), 2H, CH
3b PF
*
6
2
(COD)trans to O), 3.93 (dd (br), JH,H = 12.0 Hz,
0.203 g (0.58 mmol) TlPF6 was dissolved in 5 ml di-
chloromethane. To the resulting suspension 0.117 g
(0.23 mmol) 2 was added and the mixture was stirred
for 2 h at room temperature. After filtration and remov-
al of the solvent, 0.113 g (0.18 mmol, 79%) 3b PF was
3JHeq,Hax = 3.5 Hz, 2H, OCHHeq), 4.15 (pt (br),
2JH,H = 3JHax,Hax = 12.0 Hz, 2H, OCHHax), 5.53 (s
(br), 2H, CH (COD)trans to P), 5.74 (s, 1H, CHO2), 7.35–
7.70 (m, 14H, Ar–H).
1
31P NMR (CDCl3): d = 28.2 (d, JP,Rh = 147.0 Hz).
*
6

3130
M. Ahlmann, O. Walter / Journal of Organometallic Chemistry 689 (2004) 3117–3131
13C NMR (CDCl3): d = 27.4 (s, 1C, (OCH2)2CH2),
27.6 (s, 2C, CH2 (COD)), 32.6 (s, 2C, CH2 (COD)),
(1b), 222146 (1c), 222145 (1d), 161582 (2b), 222148
(2c), 222147 (2d), 161583 (3a), 161584 (3b), 222149
(3c), 222150 (3d). Copies of this information may be ob-
tained free of charge from: The Director, CCDC, 12 Un-
ion Road, Cambridge CB2 1EZ, UK (fax: +44-1223-
336033, e-mail: deposit@ccdc.cam.ac.uk or www:www.
ccdc.cam.ac.uk).
1
70.6 (d, JC,Rh = 15.5 Hz, 2C, CH (COD)trans to O), 71.6
3
(s, 2C, OCH2), 106.5 (d, JC,P = 5.2 Hz, 1C, CHO2),
1
2
108.5 (dd, JC,Rh = 6.9 Hz, JC,P = 9.2 Hz, 2C, CH
(COD)trans to P), 124.2–140.8 (m, 18C, Ar).
MS/ESI (m/z): 559, M+, 100%, 349 (C22H22O2P)+,
11%.
3c BF (C30H33BF4O2PRh): C, 55.47 (55.72 calc.);
*
H, 5.44 (5.15 calc.).
4
Acknowledgements
4.11. {(COD)[g2-P,O-2-(ortho-diisopropylphosphino-
We thank Mr. E. Dornberger and Prof. B. Kan-
ellakopulos for their support of the preparative chem-
istry and the Institute of Inorganic Chemistry,
University of Karlsruhe, for carrying out the Elemen-
tal analyses. We are also very grateful to Mr. G.
Zwick for the measurements of the MS data. Further-
more we thank the Forschungszentrum Karlsruhe for
the financial and Prof. E. Dinjus for the general sup-
port of this work.
phenyl)-1,3-dioxane]rhodium(I)}
3d BF
tetrafluoro-borate,
*
4
To a solution of 189.0 mg (0.47 mmol) [(COD)2Rh]BF4
in 20 ml THF, 131.5 mg (0.47 mmol) 2-(ortho-dii-
sopropylphosphinophenyl)-1,3-dioxane (1d) was added.
After refluxing for 2 h the volume of solvent was reduced
in vacuo to 3 ml. 3d BF was precipitated by addition of
*
4
40 ml pentane. After filtration, the solid was washed three
times with 10 ml of pentane. The residue was dissolved in
dichloromethane and layered successively with THF and
References
pentane. After 48 h, 189.2 mg (0.33 mmol, 70%) of 3d BF
*
4
as orange crystals were isolated.
[1] (a) S. Pitter, E. Dinjus, B. Jung, H. Go¨rls, Zeitsch. Naturforsch.
B 51 (1996) 934;
IR (KBr)/cmꢀ1: 3021 (w), 2963 (m), 2936 (m), 2925
(m), 2976 (m), 2832 (m),, 1591 (w), 1530 (w), 1480 (w),
1470 (m), 1461 (m), 1451 (m), 1437 (m), 1430 (m),
1386 (m), 1135 (m), 1097 (ss), 1055 (ss), 1032 (ss), 762
(m), 711 (m), 652 (m), 528 (m).
(b) S. Pitter, E. Dinjus, J. Mol. Catal. B 125 (1997) 39;
(c) S. Pitter, N. Holzhey, E. Dinjus, DE-PS 19 725 735
(1.12.1998);
(d) A. Jansen, S. Pitter, Monatsh. Chem. 130 (1999) 783.
[2] (a) A. Bader, E. Lindner, Coord. Chem. Rev. 108 (1991) 27;
(b) E. Lindner, S. Pautz, M. Haustein, Coord. Chem. Rev. 155
(1996) 145.
1H NMR (CDCl3): d = 1.10 (d, JH,H = 6.7 Hz, 6H,
3
3
CH3), 1.16 (d, JH,H = 6.4 Hz, 6H, CH3), 1.82 (d (br),
2JH,H = 13.9 Hz, 1H, (OCH2)2CHHeq), 2.06 (s (sh),
5H, CH2(COD), (OCH2)2CHHax), 2.22 (s (br), 2H,
PCH), 2.53 (s (br), 4H, CH2 (COD)), 4.00 (s (br), 2H,
CH (COD)trans to O), 4.26 (s (br), 4H, OCH2), 5.31 (s
(br), 2H, CH (COD)trans to P), 7.26 (s, 1H, CHO2),
7.38–7.82 (m, 4H, Ar).
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1
31P NMR (CDCl3): d = 23.7 (d, JP,Rh = 143.3 Hz).
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27.6 (s, 2C, CH2 (COD)), 32.9 (s, 2C, CH2 (COD)),
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99.9 (d, JC,P = 8.6 Hz, 1C, CHO2), 106.2 (s (br), 2C,
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MS/ESI (m/z): 491, M+, 100%, 281 (C16H16O2P)+,
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2
*
H, 6.45 (6.45 calc.).
4
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4
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