Supported organometallic complexes Part 31: Diaminediphosphineruthenium(II) precursor complexes for parallel synthesis in interphases

Article abstract of DOI:10.1016/S0020-1693(02)00749-1

The hemilabile, triethoxysilyl functionalized ether-phosphine ligand 4(T^o) was obtained by reaction of PhP(H)CH₂CH ₂OCH₃ (2) with 4-fluorobenzylamine in 1,1′- dimethoxyethane in the presence of potassium and subsequent treatment of the resulting coupling product 3 with (EtO)₃Si(CH₂) ₃NCO in dichloromethane. The modified ligand 4(T^o) was used in the synthesis of a matrix of T-silyl functionalized ruthenium(II) complexes Cl₂Ru(P～O)₂(diamine) [6a(T ^o)-6g(T^o)] by addition of a series of aliphatic and aromatic diamines a-g to the bis(chelated) precursor complex Cl ₂Ru(P～O)₂ [5(T^o)]. The corresponding monocationic ruthenium(II) complexes [ClRu(P∩O)(P～O)(diamine)][BF ₄] [7a(T^o)-7g(T^o)] were available by chloride abstraction from 6a(T^o) to 6g(T^o) with AgBF₄ or TlPF₆ in dichloromethane. Only in the case of 6a(T^o) it was possible to partially abstract both chlorides to give the dicationic complex [Ru(P∩O)₂(diamine)] [PF₆]₂ [8a(T^o)] in low yields. Complexes 6a(T^o)-6g(T ^o) and 7a(T^o)-7g(T^o) can be regarded as valuable precursors for sol-gel processing to carry out parallel synthesis in interphases in the field of catalysis.

Full text of DOI:10.1016/S0020-1693(02)00749-1

Inorganica Chimica Acta 334 (2002) 113ꢀ121
/
www.elsevier.com/locate/ica
Supported organometallic complexes Part 31:
diaminediphosphineruthenium(II) precursor complexes for parallel
synthesis in interphasesꢀ
Ekkehard Lindner *, Samer Al-Gharabli, Hermann A. Mayer
Institut fur Anorganische Chemie der Universitat Tubingen, Auf der Morgenstelle 18, D-72076 Tubingen, Germany
¨ ¨ ¨ ¨
Received 12 September 2001; accepted 10 December 2001
Dedicated to Professor Andrew Wojcicki
Abstract
The hemilabile, triethoxysilyl functionalized etherꢀ
/
phosphine ligand 4(To) was obtained by reaction of PhP(H)CH2CH2OCH3 (2)
with 4-fluorobenzylamine in 1,1?-dimethoxyethane in the presence of potassium and subsequent treatment of the resulting coupling
product 3 with (EtO)3Si(CH2)3NCO in dichloromethane. The modified ligand 4(To) was used in the synthesis of a matrix of T-silyl
functionalized ruthenium(II) complexes Cl2Ru(Pꢀ
diamines aꢀg to the bis(chelated) precursor complex Cl2Ru(Pꢀ
complexes [ClRu(PS O)(Pꢀ
O)(diamine)][BF4] [7a(To)ꢀ7g(To)] were available by chloride abstraction from 6a(To) to 6g(To) with
AgBF4 or TlPF6 in dichloromethane. Only in the case of 6a(To) it was possible to partially abstract both chlorides to give the
dicationic complex [Ru(PS
O)2(diamine)] [PF6]2 [8a(To)] in low yields. Complexes 6a(To)ꢀ6g(To) and 7a(To)ꢀ7g(To) can be
regarded as valuable precursors for solꢀgel processing to carry out parallel synthesis in interphases in the field of catalysis. # 2002
Elsevier Science B.V. All rights reserved.
/
O)2(diamine) [6a(To)ꢀ
/
6g(To)] by addition of a series of aliphatic and aromatic
/
/
O)2 [5(To)]. The corresponding monocationic ruthenium(II)
/
/
/
/
/
/
/
Keywords: Ruthenium complexes; Diamine ligands; Hemilabile ligands; Interphase chemistry
1. Introduction
successfully employed in the catalytic hydrogenation of
unsaturated ketones with high diastereo- and enantios-
An intermediate step between combinatorial chemis-
try and traditional synthesis is parallel synthesis with
commonly one compound per well [2,3], coupled to
automated screens. Recently this technique was trans-
electivity (Scheme 1) [11ꢀ15]. Subsequent investigations
/
concentrate on the combination of interphase chemistry
and parallel synthesis. Interphase catalysts demonstrate
a great importance since they are able to combine the
advantages of homogeneous and heterogeneous cataly-
sis with a marked reduction of notorious drawbacks like
leaching and reduced catalytic activity of the reactive
centers [16].
Here we wish to present the preparation and char-
acterization of a variety of diamine-bis(ether-phosphi-
ne)ruthenium(II) complexes which function as suitable
precursors for parallel synthesis in interphases. An
imperative prerequisite to meet these conditions is the
generation of a novel phosphine which is provided with
an adequate spacer carrying a triethoxysilyl group (T-
silyl) at the periphery of the ligand system and the
utilization of a series of different and easily accessible
diamines as co-ligands to establish an array of ruthe-
ferred to heterogeneous [4ꢀ7] and homogeneous [8,9]
/
catalysis. In a recent paper [10], we reported on a
synthetic route to a set of neutral and cationic diamine-
bis(ether-phosphine)ruthenium(II) complexes and their
complete structural characterization. Compounds of
this type are potential candidates for the application of
parallel methods. Diaminediphosphineruthenium(II)
complexes with classical phosphine ligands were already
ꢀ For Part 30, see Ref. [1].
* Corresponding author. Tel.: ꢁ49-7071-297 2039; fax: ꢁ49-7071-
295 306.
E-mail address: ekkehard.lindner@uni-tuebingen.de (E. Lindner).
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 0 - 1 6 9 3 ( 0 2 ) 0 0 7 4 9 - 1

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E. Lindner et al. / Inorganica Chimica Acta 334 (2002) 113ꢀ121
/
2.2. Preparation of compound 1
Phenylphosphinic acid (180.0 g, 1.32 mol) was heated
in a simple distillation apparatus equipped with an air-
cooling condenser. By controlling the internal tempera-
ture, the acid melts at about 82 8C and by gradual
heating it started to decompose at 220 8C. The tem-
perature should not exceed 260 8C. The crude product
was dried with Na2SO4 to eliminate water which was
formed together with benzene as a by-product. The
phosphine 1 was distilled to yield 50 g (38%) of a
colorless air sensitive oil. B.p. 433 K. 31P{1H} NMR
Scheme 1.
nium(II) complexes for the mentioned purpose. To
increase the catalytic activity by producing empty
coordination sites also cationic forms of the complexes
are prepared. The ether moieties incorporated into the
phosphine ligands play a significant role, because they
protect empty coordination sites at the metal center and
hence the stability of these complexes is increased
[17,18]. Such systems with T-silyl functions are suited
(CDCl3): d (ppm) ꢃ
/
120.0 (s). 1H NMR (CDCl3): d
201 Hz, PH2), 7.40ꢀ7.75 (5H,
1
(ppm) 4.22 (d, JPH
C6H5).
ꢂ
/
/
to be subjected in a further step to a solꢀgel process [16]
in the presence of appropriate co-condensation agents to
achieve highly mobile stationary phases.
/
2.3. Preparation of compound 2 [20]
A solution of n-BuLi in n-hexane (60.28 ml of a 1.6 M
solution) was added dropwise to a solution of phenyl-
phosphine (10.0 g, 90.8 mmol) in THF (100 ml). The
yellow solution consisting of C6H5PHLi was stirred 30
min at ambient temperature. Then a solution of
ClCH2CH2OCH3 (8.7 g, 91.85 mmol) in THF (50 ml)
was added dropwise within 10 min. Subsequently the
solution was stirred for another 30 min under reflux to
complete the reaction and then it was cooled to 20 8C.
To the colorless mixture a degassed aqueous solution
saturated with NH4Cl (250 ml) was added and the
organic layer was separated. The solution was dried with
Na2SO4 and separated from the solid residue. After
evaporation of the volatile materials under vacuum the
crude product was distilled to yield 10.82 g (70%) of 2 as
2. Experimental
2.1. General comments
All experiments were carried out under an atmosphere
of dry argon by use of standard Schlenk techniques.
Solvents were dried with appropriate reagents, distilled,
degassed, and stored under argon.
RuCl3×/3H2O was purchased from ChemPur, 1,8-
diaminonaphthaline, ClCH2CH2OCH3, n-BuLi, p-
fluorobenzylamine, and AgBF4 were available from
Fluka. 3-(Triethoxysilyl)propyl isocyanate was obtained
from Aldrich. 1,2-Diaminoethane, 1,2-diaminopropane,
1,3-diaminopropane, 1,2-phenylenediamine, 2,2?-bipyr-
idine, 1,10-phenanthroline were purchased from Merck,
and TlPF6 was bought from Strem. The precursor
complex RuCl2(PPh3)3 was prepared according to the
literature [19]. Elemental analyses were performed with
an Elementar Vario EL analyzer. Mass spectra were
acquired on a Finnigan MAT 711A modified by AMD
(8 kV, 303 K) and reported as mass/charge (m/z). ESI
FTICR MS measurements were carried out with a
passively shielded 4.7 T APEXTMII ESI MALDI
FTICR mass spectrometer (Bruker Daltonik GmbH,
Bremen, Germany). High resolution 31P{1H} and
13C{1H} NMR spectra were recorded on a Bruker
DRX 250 spectrometer at 298 K. Frequencies and
standards are as follows: 31P{1H} NMR 101.25 MHz,
13C{1H} 62.90 MHz. 13C chemical shifts were measured
relative to deuterated solvent peaks, which are reported
relative to TMS. 31P chemical shifts were measured
a colorless air sensitive oil. B.p. 333 K (5 mbar). 31P{1H}
1
61.6 (s). H NMR (CDCl3):
d (ppm) 1.89 (m, 2H, PCH2), 3.09 (s, 3H, OCH3), 3.27
NMR (CDCl3): d (ppm) ꢃ
/
1
(m, 2H, PCH2CH2), 4.03 (d, JPH
ꢂ
/
205 Hz, PH), 7.04ꢀ
/
7.38 (5H, C6H5). 13C{1H} NMR (CDCl3): d (ppm) 23.1
1
(d, JPC
ꢂ
/
14.2 Hz, PCH2), 57.7 (s, OCH3), 70.5 (d,
7.1 Hz, PCH2CH2).
2JPC
ꢂ
/
2.4. Preparation of compound 3
Small pieces of metallic potassium (1.16 g, 29.8 mmol)
were added to a solution of PhP(H)CH2CH2OCH3 (2) (5
g, 29.8 mmol) in 1,1?-dimethoxyethane (DME) (50 ml).
The reaction started immediately evolving molecular
hydrogen and the corresponding potassium phosphide
was formed. After the potassium had been consumed
the red solution of C6H5PK(CH2CH2OCH3) was added
dropwise within 3 h to a solution of p-fluorobenzyla-
mine (3.9 g, 31.24 mmol) in DME (150 ml). The color of
the solution changed gradually to deep green. The
reaction mixture was stirred for 6 h at ambient
temperature, then another 6 h at 50 8C followed by
reflux for 24 h. The solvent was evaporated under
relative to 85% H3PO4 (dꢂ0). The assignment of the
/
13C NMR data is based on the 135 DEPT experiment
and the comparison of the appropriate starting com-
pound. IR data were obtained on a Bruker IFS 48 FT-
IR spectrometer.

E. Lindner et al. / Inorganica Chimica Acta 334 (2002) 113ꢀ
/
121
115
reduced pressure and the yellowish residue was washed
with water (100 ml). The crude product was dried and
isolated by distillation under vacuum to produce 5.3 g
was evaporated to dryness to give 9.5 g (100%) of 3.
M.p. 117 8C. MS (EI): m/z 520 [Mꢁ]. Anal. Calc. for
C26H41N2O5PSi (520.67): C, 59.98; H, 7.94; N, 5.38.
Found: C, 59.76; H, 7.65; N, 5.36%. 31P{1H} NMR
(65%) of 2. B.p. 471 K (10ꢃ3 mbar). MS (EI): m/z 273.2
1
[Mꢁ]. 31P{1H} NMR (CDCl3): d (ppm) ꢃ
/
22.2 (s). H
2
(CDCl3): d (ppm) ꢃ
22.1 (s). 1H NMR (CDCl3): d
/
NMR (CDCl3): d (ppm) 1.27 (s, 2H9), 2.26 (t, JHH
ꢂ
/
(ppm) 0.64 (m, 2H14), 1.22 (t, 3JHH
ꢂ
7.0 Hz, 9H16), 1.61
/
7.5 Hz, 2H3), 3.17 (s, 3H1), 3.42 (m, 2H2), 3.71 (s, 2H8),
(m, 2H13), 2.37 (t, JHH
ꢂ
7.6 Hz, 2H3), 3.17 (m, 2H12),
/
3
3
7.10ꢀ
/
7.23 (m, H5, H6), 7.25ꢀ
/
7.65 (m, H11, H12, H13).
3.21 (s, 3H1), 3.50 (q, JHH
ꢂ
/
7.6 Hz, 2H2), 3.86 (q,
7.0 Hz, 6H15), 4.34 (d, 3JHH 5.9 Hz, 2H8), 4.94
6.1 Hz, 1H11), 5.14 (t, JHH 5.9 Hz, 1H9),
7.50 (m, C6H4, C6H5). 13C{1H} NMR (CDCl3): d
13C{1H} NMR (CDCl3): d (ppm) 29.2 (d, JPC
ꢂ
/
12.8
23.6
3JHH
ꢂ
(t, JHH
/
ꢂ
/
1
Hz, C3), 46.6 (s, C8), 58.9 (s, C1), 70.2 (d, JPC
ꢂ
/
ꢂ
/
ꢂ
/
2
3
3
Hz, C2), 127.6 (d, 4JPC
ꢂ
/
7.4 Hz C6), 128.8 (m, C12, C13),
7.20ꢀ
/
1
136.6 (d, JPC
1
ꢂ
/
12.3 Hz, C4), 138.9 (d, JPC
ꢂ
/
12.8 Hz,
(ppm) 7.7 (s, C14), 18.4 (s, C16), 23.8 (s, C13), 28.9 (d,
C10), 132.7 (C5, C11), 146.9 (s, C7). IR (KBr, cmꢃ1):
n(NH2) 3378, nas(C2O) 1109.
1JPC
ꢂ
/
12.8 Hz, C3), 43.0 (s, C12), 44.1 (s, C8), 53.8 (s,
C15), 58.8 (s, C1), 69.9 (d, JPC
ꢂ
23.6 Hz, C2), 127.6 (d,
/
2
3JPC
ꢂ
/
6.7 Hz, C6), 128.7 (d, JPC
ꢂ
/
6.7 Hz, C19), 128.8
3
(s, C20), 132.7 (d, JPC
ꢂ
/
16.8 Hz, C5), 133.0 (d, JPC
ꢂ
/
2
2
2.5. Preparation of ligand 4(To) (see Scheme 2)
17.5 Hz, C18), 137.0 (d, JPC
ꢂ
12.1 Hz, C4), 138.4 (d,
/
1
1JPC
ꢂ
/
12.1 Hz, C17), 140.5 (s, C7), 158.5 (s, C10). IR
O) 1597, nas(C2O) 1111,
To a solution of compound 3 (5.0 g, 18.29 mmol) in
dichloromethane (250 ml) a solution of 3-(triethoxysi-
lyl)propyl isocyanate (4.5 g, 18.29 mmol) in CH2Cl2 (20
ml) was added dropwise. The reaction mixture was
stirred at room temperature (r.t.) for 24 h. The solvent
(KBr, cmꢃ1): n(NH) 3329, n(CÄ
n(SiO) 1077.
/
2.6. Preparation of 5(To)
A solution of 4(To) (3.3 g, 6.29 mmol) in dichlor-
omethane (15 ml) was added to solution of
a
RuCl2(PPh3)3 (3.0 g, 3.15 mmol) in the same solvent
(15 ml). The reaction mixture was stirred for 3 h, then
the product was precipitated from the solvent by adding
dropwise diethyl ether (100 ml). This procedure was
repeated two times and the solvent was removed by
decanting. The pink-colored precipitate was collected by
filtration (P3) and washed three times with diethyl ether
(50 ml). Then the product was dried under vacuum to
yield 3.6 g (95%) of 5(To). MS (FAB, NBA, 50 8C): m/z
1213 [Mꢁ]. Anal. Calc. for C26H41N2O5PSi (1213.32):
C, 51.48; H, 6.81; N, 4.62. Found: C, 51.49; H, 6.74; N,
1
4.48%. 31P{1H} NMR (CDCl3): d (ppm) ꢃ
/
68.6 (s). H
NMR (CDCl3): d (ppm) 0.56 (m, 4H14), 1.3 (t, JHH
6.9 Hz, 18H16), 1.53 (m, 4H13), 2.82 (m, 4H3), 3.09 (m,
4H12), 3.65ꢀ3.85 (m, 6H1ꢁ12H15), 3.9ꢀ4.44 (m, 4H2ꢁ
4H8), 5.51 (m, 2H11), 5.61 (t, 3JHH 5.8 Hz, 2H9), 6.78ꢀ
ꢂ
/
3
/
/
/
/
ꢂ
/
/
7.30 (m, C6H4, C6H5). 13C{1H} NMR (CDCl3): d (ppm)
7.8 (s, C14), 18.5 (s, C16), 23.9 (s, C13), 31.4 (m, C3), 43.1
(s, C12), 43.5 (s, C8), 58.6 (s, C15), 62.4 (s, C1), 72.6 (s,
C2), 133.0 (m, C18), 142.1 (s, C7), 159.2 (s, C10), 125ꢀ
/
160
(C6H5, C6H4). IR (KBr, cmꢃ1): n(NH) 3352, n(CÄ
O)
1558.
/
2.7. General procedure for the preparation of the neutral
complexes 6a(To)ꢀ6g(To)
/
To a stirred solution of 2 in 25 ml of dichloromethane
was added dropwise the corresponding diamine aꢀg (5%
/
excess) dissolved in 25 ml of dichloromethane. The
solution was stirred for 45 min at r.t. and concentrated
to about 5 ml under reduced pressure. Addition of 80 ml
Scheme 2.

116
E. Lindner et al. / Inorganica Chimica Acta 334 (2002) 113ꢀ121
/
of diethyl ether caused a precipitation of a solid which
was filtered off (P3), washed three times with 25 ml of
diethyl ether and dried under vacuum.
NMR (CDCl3): d (ppm) 7.8 (s, C14), 18.3 (s, C16), 20.1
(s, NH2CHCH3), 24.0 (s, C13), 26.2 (m, C3), 43.0 (s,
C12), 43.2 (s, C8), 49.5 (s, NH2CH2), 49.5 (s, NH2CH),
58.0 (s, C1), 58.4 (s, C15), 69.2 (s, C2), 133.0 (m, C18),
2.7.1. Preparation of 6a(To)
141.4 (s, C7), 159.4 (s, C10), 125ꢀ
(KBr, cmꢃ1): n(NH) 3339, n(CÄ
O) 1556.
/
160 (C6H5, C6H4). IR
5(To) (300 mg, 0.247 mmol) was reacted with the
diamine a (17.4 ml, 0.289 mmol) to give 290 mg (92%) of
6a(To) as a yellow powder. FT ICR MS: m/z 1237.5
/
2.7.4. Preparation of 6d(To)
[Mꢁ Ã
/
Cl]. Anal. Calc. for C54H90Cl2N6O10P2RuSi2
(1273.42): C, 50.93; H, 7.12; N, 6.60. Found: C, 50.91;
5(To) (300 mg, 0.247 mmol) was reacted with the
diamine d (28.1 mg, 0.260 mmol) to give 314 mg (96%)
of 6d(To) as a brown powder. FT ICR MS: m/z 1286.5
H, 7.12; N, 6.50%. 31P{1H} NMR (CDCl3): d (ppm)
38.7 (s). 1H NMR (CDCl3): d (ppm) 0.58 (m, 4H14), 1.3
[Mꢁ Ã
/Cl]. Anal. Calc. for C58H90Cl2N6O10P2RuSi2
3
(t, JHH
ꢂ
/
6.9 Hz, 18H16), 1.56 (m, 4H13), 2.3 (m, 4H3),
(1321.46): C, 52.72; H, 6.86; N, 6.36. Found: C, 52.88;
H, 6.77; N, 6.63%. 31P{1H} NMR (CD2Cl2): d (ppm)
40.9 (s). 1H NMR (CDCl3): d (ppm) 0.64 (m, 4H14), 1.20
2.6ꢀ
/
2.9 (br, 8H, CH2NH2), 3.00 (s, 6H1), 3.0ꢀ
4H2), 3.73 (q, 3JHH 6.9 Hz, 12H15), 4.1ꢀ
7.6 (m, 18H,
/3.2 (m,
4H12ꢁ
/
ꢂ
/
/4.4 (br,
4H8), 5.5 (br, 2H11), 5.83 (br, 2H9), 6.9ꢀ
/
(t, 3JHH
ꢂ
7.0 Hz, 18H16), 1.61 (m, 4H13), 2.47 (m, 4H3),
/
C6H4, C6H5). 13C{1H} NMR (CDCl3): d (ppm) 7.8 (s,
C14), 18.4 (s, C16), 23.9 (s, C13), 25.9 (m, C3), 43.0 (s,
C12), 43.5 and 43.5 (2s, C8, CH2NH2), 58.5 (s, C15), 58.2
(s, C1), 69.2 (s, C2), 133.0 (m, C18), 141.1 (s, C7), 159.0 (s,
3.11 (s, 6H1), 3.16 (m, 4H12), 3.31 (m, 4H2), 3.80 (q,
3JHH 7.0 Hz, 12H15), 4.3 (br, 4H8), 4.5 (br, 4H,
C6H4(NH2)2), 6.0 (br, 2H11) 6.4 (br, 2H9), 6.87ꢀ
7.0
7.6 (m, 18H, C6H4, C6H5), 13C{1H}
ꢂ
/
/
(m, 4H, C6H4), 7.0ꢀ
/
C10), 125ꢀ
3339, n(CÄ
/
160 (C6H5, C6H4). IR (KBr, cmꢃ1): n(NH)
O) 1558.
NMR (CDCl3): d (ppm) 8.0 (s, C14), 18.6 (s, C16), 24.3
(s, C13), 26.6 (m, C3), 43.3 (s, C12), 43.5 (s, C8), 58.4 (s,
C1), 58.7 (s, C15), 69.5 (s, C2), 116.5 (s, C2-amine), 120.0
(s, C3-amine) 131.9 (m, C2-amine), 133.8 (m, C18), 141.0
/
2.7.2. Preparation of 6b(To)
5(To) (300 mg, 0.247 mmol) was reacted with the
diamine b (21.7 ml, 0.292 mmol) to give 172 mg (54%) of
6b(To) as a yellow powder. FT ICR MS: m/z 1251.5
(s, C7), 159.6 (s, C10), 125ꢀ
/160 (C6H5, C6H4, and C-
amine). IR (KBr, cmꢃ1): n(NH) 3308, n(CÄ
/O) 1556.
[Mꢁ Ã
/
Cl]. Anal. Calc. for C55H92Cl2N6O10P2RuSi2
(1287.45): C, 51.31; H, 7.20; N, 6.53. Found: C, 51.08;
2.7.5. Preparation of 6e(To)
5(To) (300 mg, 0.247 mmol) was reacted with the
diamine e (41.1 mg, 0.260 mmol) to give 309 mg (91%)
of 6e(To) as a brown powder. FT ICR MS: m/z 1335.5
H, 6.91; N, 6.13%. 31P{1H} NMR (CD2Cl2): d (ppm)
1
40.0 (s). H NMR (CDCl3): d (ppm) 0.58 (m, 4H14), (t,
3JHH
2.75ꢀ
6H1), 3.06ꢀ
12H15), 4.1ꢀ
6.9ꢀ
ꢂ
/
7.0 Hz, 18H16), 1.56 (m, 4H13), 2.4 (m, 4H3),
[Mꢁ Ã
/
Cl]. Anal. Calc. for C62H92Cl2N6O10P2RuSi2
/
2.97 (br m, 10H, CH2CH2CH2(NH2)2), 3.05 (s,
(1371.52): C, 54.30; H, 6.76; N, 6.13. Found: C, 54.03;
H, 6.35; N, 6.08%. 31P{1H} NMR (CD2Cl2): d (ppm)
3
/
3.32 (m, 4H12ꢁ
4.6 (br, 4H8), 5.3 (br, 2H9), 5.9 (br, 2H11),
7.6 (m, 18H, C6H4, C6H5). 13C{1H} NMR (CDCl3):
/
4H2), 3.8 (q, JHH
ꢂ/7.0 Hz,
1
/
44.0 (s). H NMR (CD2Cl2): d (ppm) 0.51 (m, 4H14),
3
1.08 (t, JHH
/
ꢂ
7.0 Hz, 18H16), 1.49 (m, 4H13), 2.25 (m,
/
d (ppm) 8.1 (s, C14), 18.7 (s, C16), 24.4 (s, C13), 26.5 (m,
C3), 29.9 (s, NH2CH2CH2), 39.7 (s, NH2CH2CH2), 43.4
(s, C12), 43.6 (s, C8), 58.2 (s, C1), 58.5 (s, C15), 69.6 (s,
4H3), 2.84 (s, 6H1), 2.9ꢀ
/
3.34 (m, 4H12ꢁ
/
4H2), 3.69 (q,
3JHH 7.0 Hz, 2H15), 4.0ꢀ
ꢂ
/
/
5.5 (br, 4H8, NH2 (4H)), 6.0
(br, 2H11), 6.4 (br, 2H9), 6.2ꢀ
/
7.0 (m, 6H-amine), 7.0ꢀ7.6
/
C2), 133.0 (m, C18), 141.7 (s, C7), 159.6 (s, C10), 125ꢀ
/
160
O)
(m, 18H, C6H4, C6H5). 13C{1H} NMR (CDCl3): d
(C6H5, C6H4). IR (KBr, cmꢃ1): n(NH) 3320, n(CÄ
/
(ppm) 8.2 (s, C14), 18.7 (s, C16), 24.4 (s, C13), 26.0 (m,
1569.
C3), 43.3 (br, C12ꢁC8), 58.3 (s, C1), 58.7 (s, C15), 69.6 (s,
/
C2), 111.6 (s, C2-amine), 119.5 (s, C4-amine) 121.4 (s,
C3-amine), 136.9 (s, C1-amine), 133.8 (m, C18), 141.0 (s,
2.7.3. Preparation of 6c(To)
5(To) (300 mg, 0.247 mmol) was reacted with the
diamine c (22.2 ml, 0.292 mmol) to give 127 mg (40%) of
6c(To) as a yellow powder. FT ICR MS: m/z 1251.5
C7), 159.8 (s, C10), 125ꢀ
/
160 (C6H5, C6H4, and C-amine).
O) 1561.
IR (KBr, cmꢃ1): n(NH) 3307, n(Cꢂ
/
[Mꢁ Ã
/
Cl]. Anal. Calc. for C55H92Cl2N6O10P2RuSi2
(1287.45): C, 51.31; H, 7.20; N, 6.53. Found: C, 51.06;
2.7.6. Preparation of 6f(To)
5(To) (300 mg, 0.247 mmol) was reacted with the
diamine f (40.5 mg, 0.259 mmol) to give 193 mg (57%) of
6f(To) as a brown powder. FT ICR MS: m/z 1334.5
H, 7.06; N, 6.77%. 31P{1H} NMR (CD2Cl2): d (ppm)
39.8 (s). 1H NMR (CDCl3): d (ppm) 0.60 (m, 4H14), 1.0
3
(m, 3H, CHCH3), 1.17 (t, JHH
ꢂ
/
6.9 Hz, 18H16), 1.58
[Mꢁ Ã
/
Cl]. Anal. Calc. for C62H90Cl2N6O10P2RuSi2
(m, 4H13), 2.8 (s, 1H, CHCH3), 3.05 (s, 6H1), 2.2ꢀ
(br, CH2NH2 (4H)ꢁ
4H3), 3.0ꢀ3.3 (m, 4H12ꢁ4H2), 3.8
6.9 Hz, 12H15), 4.3 (br, 4H8), 6.0 (br, 2H9),
6.4 (br, 2H11), 6.9ꢀ7.6 (m, 18H, C6H4, C6H5). 13C{1H}
/
3.0
(1369.51): C, 54.37; H, 6.62; N, 6.14. Found: C, 53.98;
1
/
/
/
H, 6.35; N, 5.98%. P{1H} NMR (CD2Cl2): d (ppm)
27.3 (s). H NMR (CD2Cl2): d (ppm) 0.48 (m, 4H14),
3
1
(q, JHH
ꢂ
/
3
/
1.07 (t, JHH
ꢂ
7.0 Hz, 18H16), 1.44 (m, 4H13), 2.67 (m,
/

E. Lindner et al. / Inorganica Chimica Acta 334 (2002) 113ꢀ
/
121
117
1
4H3), 2.95 (s, 6H1), 2.9ꢀ
3JHH 7.0 Hz, 12H15), 4.0ꢀ
6.0 (br, 2H9), 7.0ꢀ
7.8 (m, 18H, C6H4, C6H5), 7.8ꢀ
(m, 6H, (2H1ꢁ2H3ꢁ2H4, amine)), 13C{1H} NMR
(CD2Cl2): d (ppm) 8.0 (s, C14), 18.6 (s, C16), 24.3 (s,
/
3.3 (m, 4H12ꢁ
4.4 (br, 4H8), 5.7 (br, 2H11)
8.7
/
4H2), 3.68 (q,
39 Hz, h1-Pꢀ
4H14), 1.1 (m, 18H16), 1.52 (m, 4H13), 2.3ꢀ
4H12ꢁ4H2ꢁCH2NH2 (8H)), 3.08 (s, 3H1), 3.5 (s, 3H1),
3.7 (m, 12H15), 3.9ꢀ4.5 (br, 4H8), 6.1ꢀ6.4 (br, 2H11ꢁ
2H9), 6.9ꢀ7.6 (m, 18H, C6H4, C6H5). 13C{1H} NMR
/
O). H NMR (CDCl3): d (ppm) 0.54 (m,
ꢂ
/
/
/3.2 (br m,
/
/
/
/
/
/
/
/
/
/
C13), 26.4 (m, C3), 43.3, 43.4 (2s, C12ꢁ
/
C8), 58.3 (s, C1),
(CD2Cl2): d (ppm) 7.8 (s, C14), 18.4 (s, C16), 23.9 (s,
C13), 31.1 (m, C3), 43.0, 43.5, and 43.46 (m, C12, C8,
CH2NH2), 58.6 (s, C15), 58.2 (s, C1), 68.5 (s, C2), 69.3 (s,
58.7 (s, C15), 69.6 (s, C2), 121.2 (s, C2-amine), 122.5 (s,
C4-amine), 137.3 (s, C4-amine), 149.5 (s, C1-amine),
158.8 (s, C5-amine), 136.9 (s, C1-amine), 133.8 (m, C18),
C2), 133.0 (m, C18), 141.0 (s, C7), 158.0 (s, C10), 125ꢀ
/
160
O)
141.0 (s, C7), 159.4 (s, C10), 125ꢀ
/
160 (C6H5, C6H4, C-
O) 1560.
(C6H5, C6H4). IR (KBr, cmꢃ1): n(NH) 3340, n(CÄ
/
amine). IR (KBr, cmꢃ1): n(NH) 3345, n(CÄ
/
1558. For this and the following complexes the H and
13C NMR data for only one diastereoisomer is given.
1
2.7.7. Preparation of 6g(To)
5(To) (300 mg, 0.247 mmol) was reacted with the
diamine g (46.7 mg, 0.259 mmol) to give 285 mg (83%)
of 6g(To) as a red powder. FT ICR MS: m/z 1357.5
2.8.2. Preparation of 7b(To)
6b(To) (300 mg, 0.233 mmol) was reacted with AgBF4
(48 mg, 0.247 mmol) to give 202 mg (65%) of 7b(To) as a
[Mꢁ Ã
/
Cl]. Anal. Calc. for C64H90Cl2N6O10P2RuSi2
(1393.52): C, 55.16; H, 6.51; N, 6.03. Found: C, 54.82;
yellow powder. FT ICR MS: m/z 1251.5 [Mꢁ Ã
/
BF4].
Anal. Calc. for C55H92BClF4N6O10P2RuSi2 (1338.8): C,
49.34; H, 6.93; N, 6.28. Found: C, 49.14; H, 6.90; N,
6.10%. 31P{1H} NMR (CD2Cl2): d (ppm) 2 diastereo-
H, 6.39; N, 6.01%.31P{1H} NMR (CD2Cl2): d (ppm)
27.3 (s). 1H NMR (CD2Cl2): d (ppm) 0.47 (m, 4H14), 1.2
3
(t, JHH
ꢂ
/
6.9 Hz, 18H16) 1.4 (m, 4H13), 2.5ꢀ
/
3.8 (m,
3
mers, 53.5 (d, 2JPP
ꢂ
/
36 Hz, h2-PS
/
O), 52.9 (d, 2JPP
ꢂ37
/
4H3ꢁ
/
6H1ꢁ
/
4H12ꢁ
/
4H2), 2.97 (s, 6H1), 3.8 (q, JHH
ꢂ
/
Hz, h2-PS
/
O), 45.7 (d, 2JPP
ꢂ
/
36 Hz, h1-Pꢀ
/
O), 45.1 (d,
6.9 Hz, 12H15), 3.8ꢀ
/
4.4 (br, 4H8), 5.8 (br, 2H11), 6.2 (br,
2JPP
ꢂ
/
37 Hz, h1-Pꢀ
/
O). H NMR (CDCl3): d (ppm)
1
2H9), 6.7ꢀ
/
8.4 (m, 24H, C6H4, C6H5ꢁ
/
(2H2ꢁ
/
2H3ꢁ
/
2H4,
0.57 (m, 4H14), (m, 18H16), 1.5 (m, 4H13), 2.1 (br m,
2H3), 2.3ꢀ3.3 (br, 2H3ꢁ4H12ꢁ4H2ꢁ
CH2CH2CH2-
(NH2)2 (10H)), 3.05 (s, 3H1), 3.7 (br, 3H1ꢁ12H15),
8.2
amine)), 8.9 (m, (2H1, amine)), 13C{1H} NMR
/
/
/
/
(CD2Cl2): d (ppm) 8.1 (s, C14), 18.7 (s, C16), 24.4 (s,
/
C13), 26.6 (m, C3), 43.3 (br, C12ꢁ
/
C8), 58.4 (s, C1), 58.7
4.0ꢀ
/
4.6 (br, 4H8), 5.3 (br, 2H9), 6.3 (br, 2H11), 6.7ꢀ
/
(s, C15), 69.6 (s, C2), 123.4 (s, C2-amine), 126.5 (s, C4-
amine), 134.7 (s, C3-amine), 149.5 (s, C1-amine), 158.8
(s, C6-amine), 133.8 (m, C18), 141.0 (s, C7), 159.4 (s,
(m, 18H, C6H4, C6H5). 13C{1H} NMR (CDCl3): d
(ppm) 8.0 (s, C14), 18.6 (s, C16), 24.3 (s, C13), 26.3 (m,
C3), 28.5 (s, NH2CH2CH2), 30.6 (m, C3), 40.6 (s,
NH2CH2CH2), 42.9 (s, C12), 43.3 (s, C8), 58.4 (s, C1),
58.6 (s, C15), 60.9 (s, C1), 68.3 (s, C2), 73.9 (s, C2), 133.0
C10), 125ꢀ
/
160 (C6H5, C6H4, and C-amine). IR (KBr,
O) 1555.
cmꢃ1): n(NH) 3350, n(CÄ
/
(m, C18), 141.0 (s, C7), 159.2 (s, C10), 125ꢀ
/160 (C6H5,
2.8. General procedure for the preparation of the cationic
complexes 7a(To)ꢀ7g(To)
C6H4). IR (KBr, cmꢃ1): n(NH) 3313, n(CÄ
/O) 1576.
/
2.8.3. Preparation of 7c(To)
AgBF4 or TlPF6 (5% excess) was added to a solution
of the neutral complexes in 25 ml of dichloromethane
and stirred for 4 h. After filtration through silica gel the
solution was concentrated to about 5 ml under reduced
pressure. The cationic complex was precipitated by
addition of 100 ml of diethyl ether, filtered off (P3)
and washed three times with 25 ml of diethyl ether and
dried under vacuum.
6c(To) (300 mg, 0.233 mmol) was reacted with AgBF4
(48 mg, 0.247 mmol) to give 218 mg (70%) of 7c(To) as a
yellow powder. FT ICR MS: m/z 1251.5 [Mꢁ Ã
Anal. Calc. for C55H92BClF4N6O10P2RuSi2 (1338.8): C,
49.34; H, 6.93; N, 6.28. Found: C, 49.10; H, 6.80; N,
/
BF4].
6.20%. 31P{1H} NMR (CD2Cl2): d (ppm) 58.0 (d,
2JPP
PS
Pꢀ
0.64 (br, 3H, CHCH3), 1.18 (m, 18H16), 1.48 (m, 4H13),
2.8ꢀ3.0 (br, CHCH3ꢁCH2(NH2)2 (6H)ꢁ
3H1ꢁ4H3ꢁ
4H12ꢁ4H2), 3.6 (br m, 3H1ꢁ12H15), 4.2 (br s, 4H8),
6.2 (br m, 2H9ꢁ2H11), 6.8ꢀ
8.3 (m, 18H, C6H4, C6H5).
ꢂ
/
36 Hz, h2-PS
/
O), 56.3 (d, JPP
ꢂ
/
37 Hz, h2-
2
2
/
O), 56.1 (d, JPP
ꢂ
/
37 Hz, h2-PS
/
O), 46.0 (m, h1-
1
/
O). H NMR (CD2Cl2): d (ppm) 0.51 (m, 4H14),
2.8.1. Preparation of 7a(To)
6a(To) (300 mg, 0.235 mmol) was reacted with AgBF4
(48 mg, 0.247 mmol) to give 237 mg (76%) of 7a(To) as a
/
/
/
/
/
/
/
yellow powder. FT ICR MS: m/z 1237.5 [Mꢁ Ã
/BF4].
/
/
Anal. Calc. for C54H90BClF4N6O10P2RuSi2 (1324.77):
C, 48.96; H, 6.85; N, 6.34. Found: C, 48.52; H, 6.48; N,
6.25%. 31P{1H} NMR (CDCl3): d (ppm) diastereomers
13C{1H} NMR (CD2Cl2): d (ppm) 8.0 (s, C14), 18.6 (m,
C16), 19.7 (s, NH2CHCH3), 24.3 (s, C13), 30.2 (m, C3),
32.1 (m, C3), 43.3 (s, C12), 43.6 (s, C8), 51.2 (s,
NH2CH2), 53.6 (s, NH2CH), 58.2 (s, C1), 58.7 (s, C15),
a and b: (90%) 56.5 (d, 2JPP
ꢂ
/
37 Hz, h2-PS
/
O), 56.6 (d,
36 Hz, h1-Pꢀ
O), diastereomer c:
2JPP
O), 47.0 (d, JPP
ꢂ
/
36 Hz, h2-PS
/
ꢂ
/
/
60.6 (d, 3JPC
140.4 (s, C7), 158.3 (s, C10), 125ꢀ
(KBr, cmꢃ1): n(NH) 3333, n(CÄ
O) 1572.
ꢂ
/
22.4 Hz, C2), 69.2 (s, C2), 133.0 (m, C18),
2
O), 47.2 (d, JPP
2
ꢂ
/
37 Hz, h1-Pꢀ
39 Hz, h2-PS
/
/
160 (C6H5, C6H4). IR
2
(10%) 57.4 (d, JPP
2
O), 50.7 (d, JPP
ꢂ
/
/
ꢂ
/
/

118
E. Lindner et al. / Inorganica Chimica Acta 334 (2002) 113ꢀ121
/
2.8.4. Preparation of 7d(To)
2H1ꢁ
(ppm) 8.0 (s, C14), 18.6 (s, C16), 24.2 (s, C13), 28.0 (d,
1JPC 29 Hz, C3), 32.4 (m, C3), 44.3, 44.6 (2s, C12ꢁC8),
59.3 (s, C1), 59.7 (s, C15), 62.4 (s, C1), 69.2 (s, C2), 75.0
(s, C2), 120ꢀ157 (C6H5, C6H4, C10H11N2), 152.2 (s, C1-
amine) 158.8 (s, C5-amine), 140.0 (s, C7), 159.2 (s, C10),
125ꢀ
160 (C6H5, C6H4, and C-amine). IR (KBr, cmꢃ1):
n(NH) 3418, n(CÄO) 1568.
/
2H3ꢁ
/
2H4, amine). 13C{1H} NMR (CD2Cl2): d
6d(To) (300 mg, 0.227 mmol) was reacted with AgBF4
(47 mg, 0.241 mmol) to give 249 mg (80%) of 7d(To) as a
ꢂ
/
/
brown powder. FT ICR MS: m/z 1286.5 [Mꢁ Ã
/BF4].
Anal. Calc. for C58H90BClF4N6O10P2RuSi2 (1372.8): C,
50.74; H, 6.61; N, 6.12. Found: C, 50.34; H, 6.53; N,
6.01%. 31P{1H} NMR (CDCl3): d (ppm) 38.6 (m, h2-
/
/
PS
/
O), 35.0 (d, 2JPP
ꢂ
/
30 Hz, h1-Pꢀ
/
O), 34.8 (d, 2JPP
ꢂ
/
/
31 Hz, h1-Pꢀ
/O). H NMR (CDCl3): d (ppm) 0.53 (m,
1
4H14), 1.13 (m, 18H16), 1.5 (m, 4H13), 2.6ꢀ
4H3ꢁ3H1ꢁ4H12ꢁ4H2), 3.5 (m, 3H1), 3.7 (m, 12H15),
4.3 (br, 4H8), 6.1ꢀ 2H11ꢁ
6.8 (br, C6H4(NH2)2 (4H)ꢁ
2H9), 6.8ꢀ
8.0 (br, 22H, C6H4 (amine), C6H4, C6H5).
13C{1H} NMR (CDCl3): d (ppm) 8.1(s, C14), 18.7 (s,
C16), 23.8 (s, C13), 24.3 (m, C3), 43.6 (br, Cꢁ
C8ꢁC12),
58.4 (s, C1), 58.8 (s, C15), 61.5 (s, C1), 59.5 (s, C2), 68.1
(s, C2), 123ꢀ
136 (C6H5, C6H4, C6H4(NH2)2), 159.5 (s,
C10), 125ꢀ
160 (C6H5, C6H4, and C-amine). IR (KBr,
cmꢃ1): n(NH) 3336, n(CÄ
O) 1558.
/
3.2 (br m,
2.8.7. Preparation of 7g(To)
/
/
/
6g(To) (300 mg, 0.215 mmol) was reacted with TlPF6
(80 mg, 0.229 mmol) to give 224 mg (61%) of 7g(To) as a
/
/
/
/
red powder. FT ICR MS: m/z 1357.5 [Mꢁ Ã
/
PF6]. Anal.
Calc. for C64H90ClF6N6O10P3RuSi2 (1503.0): C, 51.14;
H, 6.04; N, 5.59. Found: C, 50.82; H, 5.84; N, 5.28%.
31P{1H} NMR (CD2Cl2): d (ppm) diastereomer a: (12%)
/
/
2
2
/
45.7 (d, JPP
h1-Pꢀ
h2-PS
O), 41.1 (d, JPP
(CD2Cl2): d (ppm) 0.52 (m, 4H14), 1.1 (m, 18H16), 1.5
(m, 4H13), 2.3ꢀ3.2 (br m, 4H3ꢁ3H1ꢁ4H12ꢁ4H2), 3.7
(m, 12H15ꢁ3H1), 3.8ꢀ4.6 (m, 4H8), 6.2 (m, 2H11), 6.4
(m, 2H9), 6.7ꢀ 2H2ꢁ
8.4 (m, C6H4 (8H)ꢁC6H5 (10H)ꢁ
2H3ꢁ2H4, amine) 8.6 (m, 2H1, amine). 13C{1H} NMR
(CD2Cl2): d (ppm) 7.9 (s, C14), 18.6 (s, C16), 24.3 (s,
ꢂ
/
34 Hz, h2-PS
/
O), 39.9 (d, JPP
ꢂ
/
34 Hz,
34 Hz,
2
/
/
O), diastereomer b: (88%) 44.5 (d, JPP
ꢂ
/
2
1
/
/
ꢂ
/
34 Hz, h1-Pꢀ
/
O), H NMR
2.8.5. Preparation of 7e(To)
/
/
/
/
6e(To) (300 mg, 0.219 mmol) was reacted with AgBF4
(45 mg, 0.231 mmol) of to give 242 mg (78%) of 7e(To)
/
/
/
/
/
/
as a brown powder. FT ICR MS: m/z 1335.5 [Mꢁ Ã
/
/
BF4]. Anal. Calc. for C62H92BClF4N6O10P2RuSi2
(1422.9): C, 52.34; H, 6.52; N, 5.91. Found: C, 51.96;
H, 6.50; N, 5.93%. 31P{1H} NMR (CD2Cl2): d (ppm)
C13), 29.3 (d, JPC
ꢂ
/
25.0 Hz, C3), 31.1 (d, JPC
ꢂ29.0
/
1
1
Hz, C3), 43.4 (s, C12), 43.2 (s, C8), 58.2 (s, C1), 58.7 (s,
C15), 61.4 (s, C1), 68.0 (m, C2), 73.9 (s, C2), 126.5 (s, C4-
amine), 134.7 (s, C3-amine), 149.6 (s, C1-amine), 159.2
(s, C6-amine), 133.8 (m, C18), 141.0 (s, C7), 159.7 (s,
61.5 (m, h2-PS
/
O), 51.1 (m, h1-Pꢀ
/
O), 49.1 (m, h1-Pꢀ
/
O). H NMR (CD2Cl2): d (ppm) 0.44 (m, 4H14), 1.08
1
(m, 18H16), 1.36 (m, 4H13), 2.3ꢀ
4H12ꢁ4H2), 3.69 (m, 15H15ꢁ3H1), 3.85ꢀ
6.0 (br, 2H11), 6.4 (br, 2H9), 6.1ꢀ
6.8 (br, C10H6(NH2)2
(4H)ꢁ 7.6 (m, C10H6(NH2)2 (6H)ꢁ
2H11ꢁ2H9), 7.0ꢀ
C6H4 (8H)ꢁ
C6H5 (10H)). 13C{1H} NMR (CDCl3): d
(ppm) 8.0 (s, C14), 18.6 (s, C16), 24.1 (s, C13), 26.7 (m,
C3), 30.9 (m, C3), 43.3 (br, C12ꢁC8), 58.3 (s, C1), 58.8 (s,
C15), 62.6 (s, C1), 69.6 (s, C2), 72.3 (s, C2), 120ꢀ
(C6H5, C6H4, C10H6(NH2)2), 159.17 (s, C10), 125ꢀ
/
3.0 (br, 4H3ꢁ
/
3H1ꢁ
/
/
/
/
4.4 (br, 4H8),
C10), 125ꢀ
/
160 (C6H5, C6H4, and C-amine). IR (KBr,
O) 1557.
/
cmꢃ1): n(NH) 3412, n(CÄ
/
/
/
/
/
/
2.9. Preparation of the dicationic complex 8a(To)
/
6a(To) (300 mg, 0.235 mmol) was added to TlPF6
(1.235 g, 3.54 mmol) in 25 ml of dichloromethane and
the mixture was refluxed for 24 h. After filtration
through silica gel the solvent was reduced under vacuum
to 5 ml. The dicationic complex was precipitated by
addition of 100 ml of diethyl ether, filtered off (P3) and
washed three times with 25 ml of diethyl ether. FT ICR
/138
/160
(C6H5, C6H4, and C-amine). IR (KBr, cmꢃ1): n(NH)
3351, n(CÄ
/
O) 1569.
2.8.6. Preparation of 7f(To)
6f(To) (300 mg, 0.219 mmol) was reacted with TlPF6
(81 mg, 0.232 mmol) to give 232 mg (63%) of 7f(To) as a
MS: m/z 601 [M2ꢁ Ã
/
2PF6]. 31P{1H} NMR (CD2Cl2): d
(ppm) dicationic complex 8a(To) (75%), 50.5 (d, JPP
ꢂ
/
2
brown powder. FT ICR MS: m/z 1334.5 [Mꢁ Ã
Anal. Calc. for C62H90ClF6N6O10P3RuSi2 (1479.02): C,
/PF6].
36 Hz, h2-PS
/
O), 50.7 (d, JPP
ꢂ
/
35 Hz, h2-PS
/
O), 51.5
ꢂ
36 Hz, h2-
/
2
2
(d, JPP
2
O), 64.1 (d, JPP
36 Hz, h2-PS
ꢂ
/
35 Hz, h2-PS
/
/
50.35; H, 6.13; N, 5.68. Found: C, 49.93; H, 5.82; N,
5.25%. 31P{1H} NMR (CD2Cl2): d (ppm) diastereomer
PS
/
O), 65.0 (d, 2JPP
ꢂ
/
/
O), 65.1 (d, 2JPP
ꢂ
35 Hz, h2-PS
/
O), 6a(To): (25%) 38.2 (s).
2
a: (16%) 45.1 (d, JPP
ꢂ
/
33 Hz, h2-PS
/O), 39.7 (d,
2JPP
ꢂ
/
33 Hz, h1-Pꢀ
(d, JPP
33 Hz, h2-PS
Pꢀ
O). H1 NMR (CD2Cl2): d (ppm) 0.58 (m, 4H14),
1.07 (m, 18H16), 1.44 (m, 4H13), 2.3ꢀ3.4 (m, 4H3ꢁ
3H1ꢁ4H12ꢁ4H2), 3.68 (m, 12H15ꢁ3H1), 3.75 (m,
15H15ꢁ3H1), 4.0ꢀ4.5 (br, 4H8), 5.5ꢀ6.6 (br, 2H11ꢁ
2H9), 6.6ꢀ
7.9 (m, 18H, C6H4, C6H5), 7.9ꢀ8.7 (m,
/O), diastereomer b: (84%) 44.8
2
2
ꢂ
/
/
O), 40.5 (d, JPP
ꢂ
/
33 Hz, h1-
3. Results and discussion
/
/
/
3.1. Synthesis of the ligand 4(To)
/
/
/
/
/
/
/
Starting compound is the phenylphosphine 1 which is
easily obtained by thermolysis of phenylphosphinic acid
/
/

E. Lindner et al. / Inorganica Chimica Acta 334 (2002) 113ꢀ
/
121
119
[21] (Scheme 2). With some modifications the synthesis
of the etherꢀphosphine 2 was carried out according to a
/
known procedure [20]. Reaction of 2 with potassium in
diethoxyethane affords the corresponding phosphide,
which in the presence of 4-fluorobenzylamine is trans-
formed, to the etherꢀphosphine ligand 3. Slow addition
/
of the intermediate potassium phosphide to 4-fluoro-
benzylamine at 50 8C reduces the formation of by-
products. The fluorine atom in the para-position of the
benzylamine enhances the nucleophilic substitution at
the aromatic ring [22]. Compound 3 is obtained as a
colorless air sensitive liquid in high yields. The amine
group provides an excellent substituent to introduce a
spacer unit with a terminal T-silyl function. This step is
realized if the etherꢀphosphine 3 is treated with 3-
/
(triethoxysilyl)propylisocyanate in dichloromethane.
The modified phosphine 4(To) is isolated as colorless
solid which readily dissolves in medium polar organic
solvents and is sensitive to air and moisture.
Both the intermediate 3 and the ligand 4(To) were
completely characterized by NMR, IR, and mass
spectroscopy. In the 31P{1H} NMR spectra a singlet
each at dꢂ
/
ꢃ
/
22.2 and ꢃ22.1 is observed. This indicates
/
that the para-positioned spacer function exerts nearly
1
no influence on the 31P chemical shift. In the H NMR
spectrum of 3 a characteristic peak at dꢂ1.26 is
/
assigned to the amino group. It disappears in the case
3
Scheme 3.
of 4(To) and because of JHH coupling two new triplets
5(To) in CH2Cl2 displays a singlet at dꢂ
markedly downfield shifted compared with that of the
/
68.6 which is
at dꢂ
functions of the urea linkage. The 13C{1H} NMR
spectrum of 4(To) reveals a singlet at dꢂ
159.0 which
/
4.9 and 5.1 occur which correspond to the NH
ligand 4(To). Such a behavior is typical for a phosphorus
atom, which is incorporated into a five-membered ring
/
is attributed to the carbonyl group of the spacer unit.
For a complete assignment of the 1H and 13C signals 2D
1H COSY, 13C{1H} DEPT, and 1H,13C{1H} HMQC
NMR spectra were recorded (see Experimental). A
characteristic absorption at 3378 cmꢃ1 in the IR
spectrum of 3 is assigned to the NH2 substituent.
Concerning the ligand 4(To) two bands at 3329 and
1
[23]. For the same reason the H (dꢂ
/
3.7 ppm) and 13C
1
72.6) resonance of the OCH3 group in the H and
(dꢂ
/
13C{1H} NMR spectrum, respectively, is also shifted to
lower field.
Complex 5(To) is provided with two weak
rutheniumÃ/oxygen bonds, which are easily cleaved by
1624 cmꢃ1 are assigned to the NH and CÄ
/
O stretching
the strong nitrogen donors of the bidentate diamine
ligands. If the bis(chelate)ruthenium(II) complex 5(To)
is treated with a slight excess of the corresponding
vibrations, respectively. The composition of the T-silyl
functionalized ligand 4(To) was corroborated by its EI
mass spectrum, showing the molecular peak at m/zꢂ
/
diamine aꢀ
plexes 6a(To)ꢀ
[6a(To)ꢀ
/
g the h1-P coordinated mixed ligand com-
6g(To) are formed (Scheme 3). The yellow
6f(To)] and red [6g(To)]
520.2.
/
/
6c(To)], brown [6d(To)ꢀ
/
3.2. Synthesis and characterization of the Cl2Ru(Pꢀ
/
solids show similar solubility as 5(To). Electron spray
mass spectra were carried out and they give evidence of
the molecular composition. Expectedly the 31P singlets
O)2(diamine) complexes 6a(To)ꢀ6g(To)
/
According to Scheme 3 the chelated bis(ether-phos-
phine)ruthenium(II) complex 5(To) is synthesized by
addition of the ligand 4(To) to Cl2Ru(PPh3)3 in CH2Cl2.
The red air-sensitive solid 5(To) was obtained after
precipitation and separation of PPh3. It is soluble in
most organic media, but not in diethyl ether. A FAB
mass spectrum of 5(To) shows the isotopic distribution
of the molecular ion, which is in agreement with the
calculated spectrum. The 31P{1H} NMR spectrum of
in the 31P{1H} NMR spectra of 6d(To)ꢀ6g(To) are high
/
field shifted compared to 5(To) indicating that the
phosphines are monodentately coordinated via the P
atoms. These singlet peaks indicate that the phosphine
groups are chemically equivalent. In principle three
different structural isomers AꢀC are possible (Chart
/
1). From the NMR data presented here and the
literature it is concluded that only structure B is realized

120
E. Lindner et al. / Inorganica Chimica Acta 334 (2002) 113ꢀ121
/
Due to the existence of three chiral centers resulting
from the two different phosphorus atoms and the metal
center, eight isomers are to be expected. However, up to
three diastereomers can be distinguished in the 31P{1H}
NMR spectra. In all cases the resonances caused by the
chelated etherꢀ
/
posphine are downfield shifted com-
O bonded ligand. In
Chart 1.
pared with those of the h1-Pꢀ
/
particular this is the case for nuclei belonging to groups
which are in direct vicinity of the ruthenium coordinated
oxygen. Thus two sets of resonances are observed in the
in solution [10,11]. Since the spacer unit exerts nearly no
influence on the 31P chemical shift, the 31P{1H} NMR
spectra of 6a(To)ꢀ6g(To) are comparable with those of
the corresponding complexes without this spacer group
/
1H and 13C{H} NMR spectra of 7a(To)ꢀ7g(To) which
/
are caused by the CH2OCH3 moieties. Each diastereo-
mer give rise to an AX pattern in the 31P{1H} NMR
spectrum. The signals at lower field are attributed to the
phosphorus atom, which is incorporated into the five-
1
[10]. In the H NMR spectra of 6a(To)ꢀ6g(To) char-
/
acteristic sets of signals occur which are assigned to the
aliphatic and aromatic protons of the phosphine and
diamine ligands, respectively, (Section 2). Furthermore
the 1H signals of the methoxy protons experience a
considerable high field shift compared with 5(To) which
2
membered ring [24]. The size of the JPP coupling (35
Hz) indicates a cis-arrangement of the phosphine groups
[25].
is in agreement with an h1-Pꢀ
/
O coordination. The
Both of the 31P resonances for the two different
phosphorus atoms in 8a(To) are shifted to lower field
compared with 7a(To). Again each diastereomer is
characterized by an AX spin system with a 2JPP coupling
constant of 35 Hz which is typical for cis-phosphines.
13C{1H} NMR spectra are consistent with these find-
ings. As a typical example the 13C resonance of the
OCH3 substituent is also high field shifted compared
with 5(To). Altogether it is emphasized that all NMR
data are in close agreement with the analogous com-
plexes for the homogeneous phase.
These spectral data are consistent for two h2-PS
/O
bonded ligands. The molecular ion of the dicationic
complex 8a(To) was detected by electron spray mass
spectroscopy and gives evidence for the molecular
composition.
3.3. Synthesis and characterization of the mono and
dicationic ruthenium(II) complexes 7a(To)ꢀ
/
7g(To) and
8a(To), respectively
Complexes 6a(To)ꢀ
/
6g(To) react in dichloromethane
4. Conclusion
with different chloride scavengers such as AgBF4 or
TlPF6 to give solutions from which the mono- and
A small library of neutral and cationic diamine(ether-
phosphine)ruthenium(II) complexes was obtained. The
complexes are provided with T-silyl functions at the
periphery of a novel phosphine ligand system. By this
dicationic complexes 7a(To)ꢀ7g(To) and 8a(To) can be
isolated (Scheme 3). One chloride is abstracted with the
simultaneous formation of a five-membered ring via
/
ether coordination (h2-PS
/O coordination) by using an
means they can later be subjected to a solꢀgel process to
/
equivalent amount of one of the scavengers. Only in the
case of 6a(To) it was possible to abstract both chlorides
in the presence of a large excess of TIPF6 at 40 8C in
CH2Cl2. But the reaction did not proceed quantitatively
and the yield of 8a(To) was low. It was not possible to
transfer these reaction conditions to the other complexes
create new stationary phases for chemistry in inter-
phases. Complexes of this type represent potential
catalysts for the hydrogenation of conjugated ketones
[11]. Due to the reasonable effect of the co-ligand on the
catalytic activity of such complexes, a series of different
aliphatic and aromatic amines was selected to vary the
electronic and steric character of the metal center and
6b(To)ꢀ
species. Electron spray mass spectra were recorded for
7a(To)ꢀ7g(To) which are in agreement with the expected
values. In the transformation of compounds 6a(To)ꢀ
6g(To) to 7a(To)ꢀ7g(To) the advantage of etherꢀ
phos-
/
6g(To) due to the instability of the dicationic
the complex, respectively. By the employment of etherꢀ
/
/
phosphines the introduction of amines is kinetically
controlled and the formation of by-products is avoided.
/
/
/
The weak rutheniumÃ
/
oxygen bonds are easily cleaved
phines becomes obvious since they protect the vacant
coordination site. Hence further weakly coordinating
ligands like acetonitrile, THF, or acetone are not
necessary. In the solid state the cationic complexes
during the reaction with the amines. Three important
items were achieved with these investigations, (i) the
cationic complexes 7a(To)ꢀ7g(To) can be applied for the
/
parallel testing as homogeneous and heterogeneous
catalysts; (ii) the presence of hemilabile ligands is
responsible for a greater stability of coordinatively
unsaturated metal centers in protecting vacant coordi-
7a(To)ꢀ7g(To) are relatively insensitive while in solution
/
they decompose in the presence of air and moisture. Due
to their polar character they readily dissolve in solvents
of medium polarity like dichloromethane.
nation sites and (iii) the weak metalÃ/oxygen bond is

E. Lindner et al. / Inorganica Chimica Acta 334 (2002) 113ꢀ
/
121
121
[8] K. Burgess, H. Lim, A. Porte, G. Sulikowski, Angew. Chem, Int.
Ed. 35 (1996) 220.
easily cleaved to activate unsaturated molecules in the
hydrogenation process.
[9] X. Gao, H. Kagan, Chirality 10 (1998) 120.
[10] C. Nachtigal, S. Al-Gharabli, K. Eichele, E. Lindner, H.A.
Mayer, Organometallics 21 (2002) 105.
Acknowledgements
[11] R. Noyori, T. Ohkuma, Angew. Chem, Int. Ed. 40 (2001) 40.
[12] T. Ohkuma, H. Takeno, Y. Honda, R. Noyori, Adv. Synth.
Catal. 343 (2001) 369.
The support of this research by the Deutsche For-
schungsgemeinschaft (Graduiertenkolleg, Grant GK-
GRK 441/1-00), Bonn/Bad Godesberg, by the Fonds
der Chemischen Industrie, Frankfurt/Main, and by the
Wilhelm Schuler-Stiftung is gratefully acknowledged.
We also thank Dipl.-Chem. D. Schmid (Professor Jung),
[13] T. Ohkuma, D. Ishii, H. Takeno, R. Noyori, J. Am. Chem. Soc.
122 (2001) 6510.
[14] M. Yamakawa, H. Ito, R. Noyori, J. Am. Chem. Soc. 122 (2001)
1466.
[15] K. Mikami, T. Korenaga, T. Ohkuma, R. Noyori, Angew. Chem,
Int. Ed. 39 (2000) 3707.
[16] E. Lindner, T. Schneller, F. Auer, H.A. Mayer, Angew. Chem,
Int. Ed. 38 (1999) 2154.
University of Tubingen for the electron spray mass
¨
spectroscopic measurements.
[17] E. Lindner, S. Pautz, R. Fawzi, M. Steimann, J. Organomet.
Chem. 555 (1998) 247.
[18] A. Bader, E. Lindner, Coord. Chem. Rev. 108 (1991) 27.
[19] T.A. Stephenson, G. Wilkinson, J. Inorg. Nucl. Chem. 28 (1966)
945.
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