Beruflich Dokumente
Kultur Dokumente
www.elsevier.com/locate/ica
Institut fu
r Anorganische Chemie, Universita
t Erlangen-Nu
rnberg, Egerlandstrasse 1, D-91058 Erlangen, Germany
Anorganisch-Chemisches Institut, Universita
t Heidelberg, Im Neuenheimer Feld 276, D-69121 Heidelberg, Germany
Received 23 September 2002; accepted 30 December 2002
Dedicated to Prof. Martin A. Bennett
Abstract
The preparation of optically pure ((R )-3-phenylbutanol)Ru(II) complexes is described. Depending on the reaction conditions and
the co-ligands, the chiral alcohol side chain may dangle free at the periphery of the h6-co-ordinated arene ligand or be co-ordinated
to the metal to result in a h6:h1-chelate ligand system. A key molecule is the dimeric complex [(h6-(R )-3-phenylbutanol)RuCl2]2 (2)
with dangling side chains. It is accessible in good yield either by oxidation and COD ligand exchange of the Ru(0) species
[(COD)(h6-(R )-3-phenylbutanol)Ru] (1) (COD /1,5-cyclooctadiene) or by complexation and dehydrogenation of (R )-3-cyclohexa(1,4-dien-1-yl)-butanol (5). 5 is thus accessible in good yield in two steps from a commercially available starting material. Dimer 2
can be split into mononuclear complexes by heating alcohol solutions to afford tethered [(h6:h1-(R )-3-phenylbutanol)RuCl2] (6), or
by reaction with an additional ligand L (L /PR3, P(OR)3, pyridine) to furnish [(h6-(R )-3-phenylbutanol)(L)RuCl2] (7a /f). If 7a /d
are reacted with silver salts, the side chain is strapped through chloride elimination to form the diastereomeric salts [(h6:h1-(R )-3phenylbutanol)(L)RuCl] X (8X) (X /BF4, PF6). The absolute molecular structures of the complexes have been determined in the
solid state. Especially the side chains exhibit interesting conformational features. The CD spectra of 2, 6, and 7a are reported.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Chiral complexes; Arene complexes; Alcohol complexes; Ruthenium complexes; Crystal structures
1. Introduction
First examples of configurationally stable chiral-atmetal arene ruthenium half-sandwich complexes have
been created by Brunner in 1978 [2,3]. Several studies
about synthesis and application of asymmetric arene
ruthenium complexes followed thereafter [4 /7]. One
reason for a still increasing interest in this class of
compounds is their importance in catalysis. Arene
ruthenium complexes can be used in catalytic Diels-
0020-1693/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0020-1693(03)00136-1
189
Scheme 1.
Scheme 2.
190
Scheme 3.
191
2.274(4) A
(Fig. 3).
The crystal structure of 7e consists of two independent molecules in the unity cell. Since they show similar
features, only one is described here. The pyridine ligand
is situated almost opposite to the bond C1 /C2 (N1 /
Ru1 /C1, 152.2(3)8; N1 /Ru1 /C2, 157.0(3)8). As assumed, there is no significant trans elongation for the
Ru /Carene bonds (Fig. 4).
2.3. Tethering the side chain by chloride elimination
192
Table 1
Analytical and spectroscopic data for compounds [(h6-(R )-3-phenylbutanol)(L)RuCl2] (7a /f)
Compound
(L)
a
[a]RT
D /
(8)
NMR data c
31
HL
4.06 (m, 1H, CH H /O); 3.74 (m, 1H, CHH /O); 3.25
(pseudosext, 1H, CHbenzyl, J/7.04); 2.52 (s, 1H, OH ); 2.19 /
2.09 (m, 1H, CH /CH H); 1.87 /1.75 (m, 1H, CH /CHH );
1.34 (d, 3H, CH3, J/7.0)
4.08 /3.95 (m, 1H, CHH /O); 3.75 /3.61 (m, 1H, CH H /O);
3.19 /3.03 (m, 1H, CHbenzyl); 2.12 /1.90 (m, 1H, CH /CH H);
1.85 /1.69 (m, 1H, CH/CHH ); 1.29 (d, 3H, CH3, J/7.0)
4.07 /3.87 (m, 1H, CHH /O); 3.78 /3.60 (m, 1H, CH H /O);
3.12 /2.95 (m, 1H, CHbenzyl); 2.42 (s, 1H, OH ); 2.01 /1.90 (m,
1H, CH/CH H); 1.85 /1.69 (m, 1H, CH/CHH ); 1.29 (d, 3H,
CH3, J/6.8)
3.90 /375 (m, 1H, CHH /O); 3.78 /3.60 (m, 1H, CH H /O);
3.03 /2.85 (m, 1H, CHbenzyl); 2.17 (s, 1H, OH ); 1.97 /1.85 (m,
1H, CH/CH H); 1.81 /1.75 (m, 1H, CH/CHH ); 1.32 (d, 3H,
CH3, J/7.0)
3.87 (m, 1H, CHH /O); 3.69 (br, 1H, CH H/O); 3.08
(pseudosext, 1H, CHbenzyl, J/6.4); 2.12 /1.97 (m, 1H, CH /
CH H); 1.81 /1.68 (m, 1H, CH/CHH ); 1.56 (s, 1H, OH ); 1.33
(d, 3H, CH3, J/7.0)
3.87 (br, 1H, CHH /O); 3.69 (br, 1H, CH H/O); 3.08
(pseudosext, 1H, CHbenzyl, J/6.1); 2.11 /1.99 (m, 1H, CH /
CH H); 1.78 /1.73 (m, 1H, CH /CHH ); 1.33 (d, 3H, CH3, J/
7.0)
Harene
a (PPh3)
/10.0
b (PEt3)
/43.0
c (PMe3)
/37.0
d (P(OMe)3) /36.7
C: 35.01 (34.99);
H:5.57 (5.19)
e (py)
/34.1
C: 44.71 (44.90); H: /
4.91 (4.77); N: 3.27
(3.49)
f (b-pic)
/30.0
C: 45.99 (46.27); H: /
5.35 (5.10); N: 3.16
(3.37)
8.85 /8.83 (m, 2H, Ha); 7.59 (d, 5.57 /5.37 (m, 5H)
2H, Hg, J/8.0); 7.25 /7.22 (dd,
1H, Hb, J/6.1, 7.6); 2.35 (s,
3H, CH3)
a
b
c
123.6 (s)
Hchain
P{1H}L
193
Fig. 2. Molecular structures of the two rotamers of [(h6-(R )-3phenylbutanol)(PPh3)RuCl2] 7a? (a) and 7a?? (b) in the solid state.
Solvent molecules are omitted for clarity. Hydrogen atoms have been
also omitted, with the exception of H1O and H2O. Selected bond
distances are given in Table 4.
Fig. 4. Molecular structure of one of the two rotamers of [(h6-(R )-3phenylbutanol)(py)RuCl2] (7e) in the solid state. Hydrogen atoms have
been omitted, with the exception of H1A. Selected bond distances are
given in Table 4.
194
Scheme 4.
Table 2
Diastereomeric excesses of tethered complexes
Compound
31
P{1H} (d )
Integral ratio
d.e. (%)
8a
8b
8c
8d
33.20; 32.95
33.22; 31.44
11.02; 8.99
120.42; 120.02
1:1.40
1:3.57
1:3.57
1:1.58
17
56
56
22
3. Conclusions
As demonstrated in this paper, chiral ((R )-3-phenylbutanol)Ru(II) complexes are accessible as optically
pure compounds by different routes. Depending on
4. Experimental details
All reactions involving organometallic compounds
were carried out under a dry nitrogen or argon atmosphere, using conventional Schlenk-tube techniques.
195
Fig. 8. CD spectra of 2 (MeCN, 1/10 4 M), 6 (MeOH, 3/10 4 M), and 7 (MeOH, 1/10 4 M).
196
13
3.81 /3.76 (m, 1H, CHH /O); 3.00 (s, 1H, OH ); 2.47 /
2.40 (pseudosext, 1H, CHbenzyl, 3JHH /6.96 Hz); 2.18 /
2.02 (m, 2H, CH /CH2); 1.34 (d, 3H, CH3, 3JHH /6.95
Hz).
13
C NMR (67.8 MHz, CD2Cl2, d): 99.41 (Carene, ipso );
89.5 (Carene); 86.2 (Carene); 82.0 (Carene); 77.0 (Carene);
72.21 (Carene); 66.0 (C H2O); 36.4 and 36.0 (ArC HCH2/
ArCHC H2); 21.6 (C H3).
Elemental analysis: Anal. Found: C, 37.56; H, 5.01.
Calc. for C10H14Cl2ORu: C, 37.28; H, 4.38%.
MS (FD, 2 kV, m /z): 536 (100%, [(areneH)2Ru2Cl] ).
RT
/[a]
D / //1.88 (MeOH, c /0.1).
4.4. [(h6-(R )-3-phenylbutanol)(PPh3)RuCl2] (7a)
To a suspension of 2 (359 mg, 1.1 mmol) in
acetonitrile (10 ml), a solution of triphenylphosphane
(299 mg, 1.1 mmol) in 5 ml of the same solvent was
added and the mixture was stirred overnight at room
temperature. After that, the solvent was evaporated and
the residue was washed several times with hexane and
diethyl ether to give 7 as a red powder (636 mg, 98%).
Recrystallization from hot ethanol gave crystals suitable
for X-ray analysis.
13
C NMR (67.8 MHz, CDCl3, d ): 134.1 (d, JCP /9.3
Hz, Cphenyl); 133.3 (d, JCP /47.8 Hz, Cphenyl, ipso); 130.4
(d, JCP /2.5 Hz, Cphenyl); 128.1 (d, JCP /10.5 Hz,
Cphenyl); 118.3 (d, JCP /9.3 Hz, Carene, ipso); 90.3 (d,
JCP /7.5 Hz, Carene); 86.7 (d, JCP /2.4 Hz, Carene);
85.8 (Carene); 85.7 (Carene); 82.6 (Carene); 59.5 (C H2O);
37.7 (C HCH2); 32.0 (CHC H2); 21.8 (C H3).
MS (FD, 2 kV, m /z): 584 [M ]; 536 [(areneH)2Ru2Cl ]; 262 (100%, PPh3). For more data see
Table 1.
4.5. [(h6-(R )-3-phenylbutanol)(PEt3)RuCl2] (7b)
Prepared as 7a, yield 72%, for data see Table 1.
C NMR (75.5 MHz, CDCl3, d): 118.5; 90.1; 85.0;
83.4; 81.6; 77.4; 59.1; 37.5; 31.8; 21.7; 17.8 (d); 7.7.
13
197
198
Table 3
Crystallographic data for 6, 7a /0.5EtOH, 7b, 7e, 8aBF4 /MeOH, 8b(PF6)0.5(H2PO4)0.5
Empirical formula
Formula weight
Color, form
Crystal size (mm)
Crystal system
Space group
)
a (A
)
b (A
)
c (A
a (8)
b (8)
g (8)
3)
V (A
Z
rcalc (g cm3)
m (mm 1)
T (K)
Absorption correction
Tmin; Tmax
No. of refined parameters
F (0 0 0)
Reflections measured
Independent reflections
Observed reflections a
Goodness-of-fit on F2
R1a
wR2 (all data)
Max.; min. residual den 3)
sity (e A
Absolute structural
parameter [26]
a
7a/0.5EtOH
7b
7e
8aBF4 /MeOH
8b(PF6)0.5(H2PO4)0.5
C10H14Cl2ORu
322.18
red, irregular
0.55 /0.45 /
0.18
triclinic
P1
7.563(1)
8.747(1)
9.075(1)
106.37(1)
102.04(1)
97.15(1)
552.5(1)
2
1.937
1.865
210
psi-scan
0.257; 0.345
337
C29H32Cl2O1.5PRu
607.49
red, plates
0.74/0.68/0.06
C15H19Cl2NORu
401.28
yellow, plates
0.56/0.26/
0.08
orthorhombic
P 212121
7.259(1)
13.065(2)
31.719(4)
90.0
90.0
90.0
3008.2(7)
8
1.772
1.392
200
psi-scan
0.284; 0.333
365
C30H37BClF4O3PRu
699.90
orange, prism
0.68/0.52/0.36
C16H30ClF3O3P2Ru
525.86
red, prism
0.46/0.44/0.22
monoclinic
P 21
12.416(1)
13.553(1)
16.766(2)
90.0
107.54(1)
90.0
2690.1(4)
4
1.500
0.864
210
none
/
627
C16H29Cl2OPRu
440.33
red, irregular
0.28/0.20/
0.14
monoclinic
P 21
7.436(1)
10.868(1)
11.909(2)
90.0
104.02(1)
90.0
933.7(2)
2
1.566
1.208
210
none
/
190
monoclinic
P 21
12.680(1)
19.287(1)
13.002(1)
90
93.34(1)
90
3174.4(4)
4
1.464
0.681
210
none
/
768
triclinic
P1
8.437(1)
15.801(2)
16.377(2)
83.08(1)
88.56(1)
86.24(1)
2162.4(5)
4
1.615
1.035
200
psi-scan
0.336; 0.390
999
320
5211
5210
4979
1.078
0.0217
0.0534
0.627; /0.894
1244
12791
11766
9750
1.023
0.0508
0.1303
0.962; /0.990
452
4123
3612
3282
1.058
0.0384
0.0981
1.079; /0.892
1616
7471
6567
5113
1.018
0.0510
0.1164
0.864; /0.552
1432
14910
13889
12713
1.057
0.0345
0.0815
0.554; /0.512
1072
18864
18864
13986
1.018
0.0542
0.1137
0.691; /0.575
0.01(4)
/0.02(4)
0.04(5)
/0.05(7)
0.00(2)
0.01(4)
F0 ]/4s (F ).
5. Supplementary material
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC numbers 193800, 193801, 199541,
199543, 193802 and 199542 for compounds 6, 7a, 7b, 7e,
(8aBF4 /MeOH), and (8b(PF6)0.5(H2PO4)0.5), respectively. Copies of this information may be obtained free
of charge from The Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK (fax: /44-1233-336-033; email deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
Table 4
) and angles (8) for 6, 7a/0.5EtOH, 7b, 7e, 8aBF4 /MeOH, 8b(PF6)0.5(H2PO4)0.5
Selected bond distances (A
7a/0.5EtOH
7b
8aBF4 /MeOH
7e
8b(PF6)0.5(H2PO4)0.5
2.130(6)
2.148(6)
2.160(6)
2.200(6)
2.169(5)
2.138(5)
2.163(4)
2.3903(14)
2.4198(16)
2.195(5)
2.158(6)
2.151(7)
2.167(6)
2.175(6)
2.139(5)
2.173(4)
2.3876(15)
2.4216(16)
Ru1/C1
Ru1/C2
Ru1/C3
Ru1/C4
Ru1/C5
Ru1/C6
Ru1/P1
Ru1/Cl1
Ru1/Cl2
Ru2/C41
Ru2/C42
Ru2/C43
Ru2/C44
Ru2/C45
Ru2/C46
Ru2/P2
Ru2/Cl3
Ru2/Cl4
2.173(6)
2.208(7)
2.176(7)
2.167(7)
2.231(7)
2.264 (6)
2.3392(13)
2.405(2)
2.4367(17)
2.257(7)
2.173(8)
2.201(7)
2.198(8)
2.192(7)
2.299(6)
2.3502(14)
2.4116(17)
2.398(2)
Ru1/C1
Ru1/C2
Ru1/C3
Ru1/C4
Ru1/C5
Ru1/C6
Ru1/P1
Ru1/Cl1
Ru1/Cl2
2.272(6)
2.166(6)
2.199(8)
2.183(7)
2.178(6)
2.274(4)
2.3392(13)
2.4206(15)
2.4148(16)
Ru1/C1
Ru1/C2
Ru1/C3
Ru1/C4
Ru1/C5
Ru1/C6
Ru1/N1
Ru1/Cl1
Ru1/Cl2
2.183(8)
2.211(8)
2.166(7)
2.167(8)
2.187(7)
2.215 (7)
2.118(6)
2.4158(19)
2.4250(19)
Ru1/C1
Ru1/C2
Ru1/C3
Ru1/C4
Ru1/C5
Ru1/C6
Ru1/P1
Ru1/O1
Ru1/Cl1
Ru2/C41
Ru2/C42
Ru2/C43
Ru2/C44
Ru2/C45
Ru2/C46
Ru2/P2
Ru2/O2
Ru2/Cl2
2.192(4)
2.213(4)
2.189(4)
2.162(5)
2.218(4)
2.236(3)
2.3649(9)
2.152(3)
2.3863(11)
2.239(4)
2.229(5)
2.177(4)
2.175(4)
2.210(4)
2.200(4)
2.3623(9)
2.136(3)
2.3826(11)
Ru1/C1
Ru1/C2
Ru1/C3
Ru1/C4
Ru1/C5
Ru1/C6
Ru1/P1
Ru1/O1
Ru1/Cl1
2.193(9)
2.159(9)
2.165(10)
2.230(9)
2.250(9)
2.191(9)
2.344(2)
2.154(8)
2.395(2)
Angles
O1/Ru1/Cl1
O1/Ru1/Cl2
Cl1/Ru1/Cl2
O2/Ru2/Cl3
O2/Ru2/Cl4
Cl3/Ru2/Cl4
83.11(12)
83.26(13)
89.02(6)
84.22(13)
82.62(13)
88.65(6)
P1/Ru1/Cl1
P1/Ru1/Cl2
Cl1/Ru1/Cl2
P2/Ru2/Cl3
P2/Ru2/Cl4
Cl3/Ru2/Cl4
86.66(6)
90.43(5)
88.46(7)
87.33(6)
89.39(6)
87.44(7)
P1/Ru1/Cl1
P1/Ru1/Cl2
Cl1/Ru1/Cl2
86.37(5)
86.44(6)
89.55(6)
N1/Ru1/Cl1
N1/Ru1/Cl2
Cl1 /Ru1/Cl2
86.30(18)
87.76(19)
85.78(7)
P1/Ru1/Cl1
O1/Ru1/Cl1
O1/Ru1/P1
P2/Ru2/Cl2
O2/Ru2/Cl2
O2/Ru2/P2
87.30(4)
83.59(8)
89.83(8)
86.38(4)
84.28(8)
87.26(8)
P1/Ru1/Cl1
O1/Ru1/Cl1
O1/Ru1/P1
87.72(9)
83.4(2)
87.1(2)
Distances
Ru1/C1
Ru1/C2
Ru1/C3
Ru1/C4
Ru1/C5
Ru1/C6
Ru1/O1
Ru1/Cl1
Ru1/Cl2
Ru2/C11
Ru2/C12
Ru2/C13
Ru2/C14
Ru2/C15
Ru2/C16
Ru2/O2
Ru2/Cl3
Ru2/Cl4
199
200
Acknowledgements
We thank the Deutsche Forschungsgemeinschaft
(SFB 583) and the Fonds der Chemischen Industrie
for financial support. Prof. Dr. P. Gmeiner (E. Fischer
Zentrum-Lehrstuhl fur Pharmazeutische Chemie und
Lebensmittelchemie, Erlangen) is thanked for providing
CD spectroscopic facilities.
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