Neutral mono- And cationic Bis-aziridine d6-metal complexes of the type [(π-arene)M(Az)Cl2] and [(π-arene)M(Az) 2Cl]Cl (π-arene/M = η6-C6Me 6/Ru; η5-C5Me5/Rh, Ir)

Article abstract of DOI:10.1002/zaac.200700276

The synthesis of neutral mono- and cationic bis-aziridine complexes of ruthenium(II), rhodium(III) and iridium(III) are described. The dimeric complexes [MCl₂L]₂ (M = Ru^II, L = C ₆Me₆; M = Rh^III/Ir^III, L = C ₅Me₅) (1-3) react with a series of aziridines (Az = C ₂H₄NH, C₂H₃MeNH, C₂H ₂Me₂NH, C₂H₃EtNH, C ₂H₃PhNH) (a-e) in a 1:2 or 1:5 molar ratio to give the neutral mono-aziridine complexes [MCl₂L(Az)] (4e-6e) or cationic bis-aziridine complexes [MClL(Az)₂]Cl (7a-9d), respectively. After purifi cation, all of the complexes were fully characterized and the IR, MS, ¹H and ¹³C NMR spectra are reported and discussed. The single crystal structure analysis revealed a distorted octahedral structure for all complexes.

Full text of DOI:10.1002/zaac.200700276

DOI: 10.1002/zaac.200700276
Neutral Mono- and Cationic Bis-Aziridine d6-Metal Complexes of the Type
[(π-arene)M(Az)Cl2] and [(π-arene)M(Az)2Cl]Cl
(π-arene/M ؍ η6-C6Me6/Ru; η5-C5Me5/Rh, Ir)
Roman Bobka, J. Nicolas Roedel, Bernd Neumann, Christoph Krinninger, Peter Mayer, Stefan Wunderlich,
Alexander Penger, and Ingo-Peter Lorenz*
München, Ludwig Maximilians University, Department of Chemistry and Biochemistry
Received May 25th, 2007.
In memory of Professor Dr. Nils Wiberg
Abstract. The synthesis of neutral mono- and cationic bis-aziridine
complexes of ruthenium(II), rhodium(III) and iridium(III) are de-
scribed. The dimeric complexes [MCl2L]2 (M ϭ RuII, L ϭ C6Me6;
M ϭ RhIII/IrIII, L ϭ C5Me5) (1-3) react with a series of aziridines
cation, all of the complexes were fully characterized and the IR,
MS, 1H and 13C NMR spectra are reported and discussed. The
single crystal structure analysis revealed a distorted octahedral
structure for all complexes.
(Az
ϭ
C2H4NH, C2H3MeNH, C2H2Me2NH, C2H3EtNH,
C2H3PhNH) (a-e) in a 1:2 or 1:5 molar ratio to give the neutral
mono-aziridine complexes [MCl2L(Az)] (4e-6e) or cationic bis-aziri-
dine complexes [MClL(Az)2]Cl (7a-9d), respectively. After purifi-
Keywords: Aziridine; Coordination chemistry; Crystal structures;
Iridium; Rhodium; Ruthenium
Introduction
acyl complexes have been observed by Beck et al. and our
research group [22Ϫ24]. In addition Hillhouse et al. re-
ported the oxidative addition of N-tosylated aziridine to
nickel(0) complexes forming the corresponding azametalla-
cyclobutane complex, which was structurally investigated
using X-ray diffraction [25].
Research into the coordination chemistry of the aziridine
ligand dates back to 1958, when Hieber et al. first intro-
duced aziridine as a ligand [1]. In the following years, Ed-
wards et al. and Fritz et al. characterized various aziridine
transition metal halogenido complexes using elemental
analysis and IR spectroscopy [2Ϫ5]. Edwards et al. sub-
sequently reported the first X-ray structure analysis of an
aziridine rhodium complex in 1969 [6], and a series of publi-
cations on the coordination chemistry of aziridine from
various research groups followed, including the recent re-
ports on main group metal aziridine complexes by Gal et
al. [7Ϫ19].
Although aziridines are isolobal to oxiranes and thiiranes
(C2H4X; X ϭ NH, O, S), the complex formation of azirid-
ines differs strongly from the latter two. Oxiranes and thiir-
anes are both suitable oxidising agents for organometallic
compounds, whereby oxo or thio complexes result via ethyl-
ene elimination [20, 21]. The aziridines, however, usually re-
main intact as three-membered rings and coordinate via ni-
trogen atom. However, transition metal mediated ring
opening reactions, resulting in the formation of β-amino-
The opening of the aziridine ring, which occurs after pro-
tonation of the amino group and nucleophilic attack, is
mainly due to Baeyer [26] and Pitzer ring strain. The versa-
tility of the aziridine motif has resulted in widespread inter-
est in this heterocycle [27Ϫ30]. In addition to being import-
ant tools in organic chemistry, aziridine compounds have a
variety of synthetic applications, for example, as synthones
in natural synthesis [31, 32], monomers in macromolecular
chemistry [33, 34], or target molecules in organic synthesis
[35Ϫ37]. Another important factor is the biological ef-
ficiency of aziridines, whereby as expected, in vivo effects of
aziridine derivatives are mostly the result of ring opening
reactions. This results in the possible carcinogenic activity
of aziridine compounds. However, there are several azirid-
ine containing classes of compounds such as the mitosanes
(e.g. the well known anti tumor agent Mitomycin C), that
combine both selectivity and potency as alkylation agents
[28, 30, 38, 39].
* Prof. Dr. I.-P. Lorenz
Results and Discussion
Department Chemie und Biochemie
Ludwig-Maximilians-Universität München
Butenandtstraße 5?13 (Haus D)
D-81377 München, Germany
Fax: ϩ49-(0)89-2180-77867
Synthesis
The ligands aziridine (a), 2-methylaziridine (b), 2,2-dimeth-
ylaziridine (c), 2-ethylaziridine (d) and 2-phenylaziridine (e)
E-mail: ipl@cup.uni-muenchen.de
Z. Anorg. Allg. Chem. 2007, 633, 1985Ϫ1994
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1985

R. Bobka, J. N. Roedel, B. Neumann, C. Krinninger, P. Mayer, S. Wunderlich, A. Penger, I.-P. Lorenz
Scheme 1 Synthesis of the neutral mono-aziridine complexes 4e-6e by the reaction of [MCl2L]2 (1-3) with 2 equivalents of the aziridines a-e.
Scheme 2 Synthesis of the cationic bis-aziridine complexes 7a-9d by the reaction of [MCl2L]2 (1-3) with 5 equivalents of the aziridines a-e.
were prepared from β-amino-alcohols according to stand-
ard literature methods [40, 41].
Selected bond lengths and angles of compounds (4e-8e, 9d)
are summarized in Tables 4-6.
Scheme 1 shows the reactions of the dimeric complexes
[MCl2L]2 (1-3) with stoichiometric amounts (1:2) of the azi-
ridines (a-e) in dichloromethane to give the corresponding
neutral mono-aziridine complexes [MCl2L(Az)] (4e, 5b, 6a,
b, c, e).
The cationic bis-aziridine complexes [MClL(Az)2]Cl (7a,
c, d, e, 8a, c, e, 9a, c, d) were prepared by adding an excess
(1:5) of the aziridines (a-e) to a solution of [MCl2L]2 (1-3)
in dichloromethane (Scheme 2).
The X-ray structure analysis showed a distorted octa-
hedral structure for all obtained compounds (4e-9d). The
aromatic ligand L (C6Me6 or C5Me5) represents one octa-
hedral face, while the other three coordinating atoms (Cl or
N) form the opposite one. All MϪN (209Ϫ215 pm) and
MϪCl (239Ϫ244 pm) bond lengths are within a small range
and appear to vary only slightly with different metals. In
addition, the MϪN and MϪCl bond lengths are compar-
able with those in similar complexes [42Ϫ49].
All products 4e-9d were obtained in good yields
(77Ϫ99 %) and are soluble in polar solvents such as acetone
or dichloromethane, but insoluble in non-polar solvents
such as n-pentane.
In the mono-aziridine complexes 4e-6e, the aziridine li-
gand is always bent towards one chloride ligand, which
results in larger NϪMϪCl angles (87.5°Ϫ90.7°) in com-
parison to the other NϪMϪCl angles (82.0°Ϫ86.7°). The
difference between the two NϪMϪCl angles is dependent
on the substituent(s) in 2-position of the aziridine ring, and
therefore the biggest discrepancy (8.7°) is found in the 2,2-
dimethylaziridine complex 6c. All ClϪMϪCl angles are in
the range of 87.1° to 92.3° and differ only marginally from
those in related complexes [42Ϫ45].
The NϪMϪN angles (77.4°Ϫ87.2°) of the bis-aziridine
complexes 7a-9d are smaller than the NϪMϪCl angles
(86.8°Ϫ92.6°), because in the former, both aziridines are
bent towards the chloride ligand. However, this effect de-
pends on the steric demands of the aziridine ring, whereby
Crystal Structure Analysis
The molecular structures of compounds 4e-9d were deter-
mined using single crystal X-ray diffraction. Single crystals
were obtained by the isothermic diffusion of n-pentane into
acetone solutions of 9a and 9c, and by slow evaporation of
dichloromethane solutions of 4e-8e and 9d. Details of the
relevant data collection and refinement are summarized in
Tables 1-3. For each type of compound one molecular
structure (4e, 5b, 6a, 7c, 8a, 9d) is shown in Figures 1-6.
1986
www.zaac.wiley-vch.de
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 1985Ϫ1994

Neutral Mono- and Cationic Bis-Aziridine d6-Metal Complexes
Table 1 Crystal data and details of structural refinement for compounds 4e-6e
Compound
4e
5b
6a
6b
6c
6e
Formula
FW
C20H27Cl2NRu
453.41
C13H22Cl2NRh
366.13
C12H20Cl2IrN
441.39
C13H22Cl2IrN
455.44
C14H24Cl2IrN
469.44
C18H24Cl2IrN
517.48
Temperature /K
Wavelength /A
200
0.71073
200
0.71073
200
0.71073
200
0.71073
200
0.71073
200
0.71073
˚
Crystal system
Space group
monoclinic
Cc
orthorhombic
P212121
8.4918(17)
11.734(2)
15.726(3)
90
1566.9(5)
4
1.5521
orthorhombic
P212121
8.5290(17)
11.745(2)
14.142(3)
90
1416.7(5)
4
2.070
orthorhombic
P212121
15.7176(2)
8.5865(5)
11.6753(1)
90
1575.7(2)
4
1.9199
monoclinic
P21/n
13.502(3)
8.1135(2)
14.712(3)
93.34
1609.0(6)
4
1.938
monoclinic
P21/n
7.6823(2)
12.193(2)
19.736(4)
98.59(3)
1827.9(6)
4
1.880
˚
a /A
13.326(3)
21.549(4)
8.2392(16)
106.02(3)
2274.1(8)
4
1.5746
1.166
1097
˚
b /A
˚
c /A
β /°
3
˚
V /A
Z
ρcalc. /g cmϪ1
µ /mmϪ1
F(000)
1.411
744
9.777
840
8.793
872
8.614
904
7.593
1000
Crystal size /mm
θ range /°
Index Range
0.20 x 0.06 x 0.02
3.18 to 26.30
Ϫ16 Յ h Յ 16,
Ϫ26 Յ k Յ 26,
Ϫ10 Յ l Յ 10
8490
0.20 x 0.15 x 0.11
3.23 to 27.48
Ϫ8 Յ h Յ 11,
Ϫ13 Յ k Յ 15,
Ϫ20 Յ l Յ 20
14148
0.12 x 0.10 x 0.07
3.13 to 27.49
Ϫ10 Յ h Յ 10,
Ϫ15 Յ k Յ 13,
Ϫ18 Յ l Յ 18
12475
0.32 x0.11 x 0.07
2.17 to 27.98
Ϫ20 Յ h Յ 20,
Ϫ10 Յ k Յ 11,
Ϫ14 Յ l Յ 15
13620
0.30 x 0.22 x 0.20
2.11 to 27.91
Ϫ17 Յ h Յ 17,
Ϫ10 Յ k Յ 10,
Ϫ19 Յ l Յ 19
13401
0.18 x 0.15 x 0.07
1.97 to 25.88
Ϫ9 Յ h Յ 9,
Ϫ14 Յ k Յ 14,
Ϫ24 Յ l Յ 24
12659
Reflns collected
Independent reflns 4490
3544
3235
3766
3838
3507
Rint
0.0292
0.0755
0.0485
0.0811
0.0794
0.0587
Completeness to θ 99.6 %
Refinement method Full-matrix least
squares on F2
99.2 %
99.5 %
99.3 %
99.6 %
98.7 %
Full-matrix least
squares on F2
3544 / 0 / 182
Full-matrix least
squares on F2
3235 / 0/ 151
Full-matrix least
squares on F2
3766 / 0 / 152
Full-matrix least
squares on F2
3838 / 0 / 171
Full-matrix least
squares on F2
3507 / 0 / 205
Data / restraints /
parameters
4490 / 2 / 244
S on F2
1.030
1.069
1.082
1.024
0.990
1.034
Final R indices
[I>2 σ (I)]
Largest difference
peak/hole
R1 ϭ 0.0247,
wR2 ϭ 0.0521
0.497 and Ϫ0.234 e.A
R1 ϭ 0.0338,
wR2 ϭ 0.0751
0.362 and Ϫ0.653 e.A
R1 ϭ 0.0281,
wR2 ϭ 0.0626
1.898 and Ϫ2.245 e.A
R1 ϭ 0.0297,
wR2 ϭ 0.0674
1.158 and Ϫ1.272 e.A
R1 ϭ 0.0361,
wR2 ϭ 0.0870
3.923 and Ϫ3.408 e.A
R1 ϭ 0.0585,
wR2 ϭ 0.1473
10.399 and Ϫ3.038 e.A
Ϫ3
Ϫ3
Ϫ3
Ϫ3
Ϫ3
Ϫ3
˚
˚
˚
˚
˚
˚
CCDC number
652371
652745
652372
652375
652373
652374
Table 2 Crystal data and details of structural refinement for compounds 7a-7e
Compound
7a
7c
7d
7e
Formula
FW
C17H30Cl4N2Ru
505.31
C20H36Cl2N2Ru
476.49
C20H36Cl2N2Ru
476.49
C28H36Cl2N2Ru
572.57
Temperature /K
Wavelength /A
200
200
0.71073
monoclinic
P21/c
10.958(2)
15.339(3)
13.224(3)
200
200
0.71073
monoclinic
P21/c
18.741(4)
14.852(3)
9.4956(19)
˚
0.71073
triclinic
0.71073
triclinic
Crystal system
Space group
¯
¯
P1
P1
˚
a /A
8.7804(18)
10.028(2)
13.090(3)
73.42(3)
85.05(3)
79.31(3)
1084.8(4)
2
1.5470
0.965
516
9.985(2)
˚
b /A
12.347(3)
12.683(3)
101.67(3)
90.07(3)
108.94(3)
1444.6(5)
2
1.0954
0.732
496
˚
c /A
Ͱ /°
β /°
γ /°
96.12(3)
94.07
3
˚
V /A
2210.2(8)
4
1.4320
0.957
992
2636.4(9)
4
1.4426
0.816
1184
Z
ρcalc. /g cmϪ1
µ /mmϪ1
F(000)
Crystal size /mm
θ range /°
Index Range
0.16 x 0.09 x 0.06
3.25 to 27.51
Ϫ11 Յ h Յ 11,
Ϫ12 Յ k Յ 13,
Ϫ16 Յ l Յ 16
8929
0.24 x 0.20 x 0.14
3.25 to 27.47
Ϫ14 Յ h Յ 14,
Ϫ19 Յ k Յ 19,
Ϫ17 Յ l Յ 17
9770
0.24 x 0.17 x 0.10
4.10 to 26.06
Ϫ12 Յ h Յ 11,
Ϫ15 Յ k Յ 13,
Ϫ13 Յ l Յ 15
7608
0.18 x 0.13 x 0.10
3.27 Ϫ 25.04
Ϫ22 Յ h Յ 22,
Ϫ17 Յ k Յ 17,
Ϫ11 Յ l Յ 11
8977
Reflns collected
Independent reflns
Rint
4826
0.0219
5044
0.0126
5667
0.1067
4648
0.0204
Completeness to θ
Refinement method
96.9 %
99.7 %
99.1 %
99.7 %
Full-matrix least
squares on F2
4826 / 0 / 217
1.065
Full-matrix least
squares on F2
5044 / 0 / 226
1.054
Full-matrix least
squares on F2
5667 / 0 / 281
1.069
Full-matrix least
squares on F2
4648 / 0 / 298
1.136
Data / restraints / parameters
S on F2
Final R indices [I>2 σ (I)]
R1 ϭ 0.0293,
wR2 ϭ 0.0683
0.655 and Ϫ0.676 e.A
R1 ϭ 0.0269,
wR2 ϭ 0.0694
0.496 and Ϫ0.644 e.A
R1 ϭ 0.0781,
wR2 ϭ 0.1968
1.427 and Ϫ1.504 e.A
R1 ϭ 0.0360,
wR2 ϭ 0.0809
0.485 and Ϫ0.696 e.A
Ϫ3
Ϫ3
Ϫ3
Ϫ3
˚
˚
˚
˚
Largest difference peak/hole
CCDC number
652367
652368
652369
652370
Z. Anorg. Allg. Chem. 2007, 1985Ϫ1994
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1987

R. Bobka, J. N. Roedel, B. Neumann, C. Krinninger, P. Mayer, S. Wunderlich, A. Penger, I.-P. Lorenz
Table 3 Crystal data and details of structural refinement for compounds 8a-9d
Compound
8a
8c
8e
9a
9c
9d
Formula
FW
C14H25Cl2N2Rh
395.17
C18H33Cl2N2Rh
451.27
C26H33Cl2N2Rh
547.37
C14H25Cl2IrN2
484.48
C18H33Cl2IrN2
540.59
C18H33Cl2IrN2
540.59
Temperature /K
Wavelength /A
200
0.71073
200
0.71073
200
0.71073
200
0.71073
200
0.71073
200
0.71073
˚
Crystal system
Space group
monoclinic
C2/m
orthorhombic
Pbca
14.948(3)
13.185(3)
21.506(4)
monoclinic
P21/c
18.062(4)
15.146(3)
9.1475(2)
92.96(3)
2499.2(9)
4
1.4548
orthorhombic
Pna21
19.2782(6)
13.7418(5)
13.2466(3)
orthorhombic
Pbca
15.002(3)
13.161(3)
21.523(4)
monoclinic
P21/c
˚
a /A
14.652(3)
12.260(3)
11.516(2)
100.64(3)
2032.9(7)
4
1.5687
1.364
976
11.814(2)
10.483(2)
18.184(4)
108.24(3)
2138.9(7)
4
1.6788
6.494
1064
˚
b /A
˚
c /A
β /°
3
˚
V /A
4238.5(2)
8
1.4152
1.059
1872
3509.25(2)
8
1.834
7.904
1872
4249.6(2)
8
1.6899
6.537
2128
Z
ρcalc. /g cmϪ1
µ /mmϪ1
F(000)
0.913
1128
Crystal size /mm
θ range /°
Index Range
0.45 x 0.38 x 0.30
2.18 to 27.87
Ϫ19 Յ h Յ 19,
Ϫ15 Յ k Յ 16,
Ϫ15 Յ l Յ 14
8729
0.20 x 0.14 x 0.08
3.27 to 27.48
Ϫ19 Յ h Յ 19,
Ϫ17 Յ k Յ 17,
Ϫ27 Յ l Յ 27
9158
0.14 x 0.13 x 0.03
3.37 to 27.52
Ϫ23 Յ h Յ 23,
Ϫ19 Յ k Յ 19,
Ϫ11 Յ l Յ 11
11092
0.04 x 0.12 x 0.17
3.13 to 27.49
Ϫ25 Յ h Յ 22,
Ϫ17 Յ k Յ 17,
Ϫ14 Յ l Յ 16
32268
0.11 x 0.08 x 0.05
3.24 to 27.46
Ϫ19 Յ h Յ 19,
Ϫ17 Յ k Յ 17,
Ϫ27 Յ l Յ 27
9187
0.12 x 0.06 x 0.03
3.13 to 27.46
Ϫ15 Յ h Յ 15,
Ϫ13 Յ k Յ 13,
Ϫ23 Յ l Յ 23
9149
Reflns collected
Independent reflns
Rint
2522
0.1022
4841
0.0230
5714
0.0371
7505
0.089
4846
0.0218
4843
0.0360
Completeness to θ
99.3 %
99.8 %
99.5 %
97.7 %
99.8 %
99.0 %
Refinement method Full-matrix least
Full-matrix least
squares on F2
4841 / 0 / 208
Full-matrix least
squares on F2
5714 / 0 / 280
Full-matrix least
squares on F2
7505 / 0 / 343
Full-matrix least
squares on F2
4846 / 0 / 212
Full-matrix least
squares on F2
4843 / 0 / 216
squares on F2
Data / restraints /
parameters
2522 / 0 / 111
S on F2
1.063
1.052
1.026
1.00
1.067
1.026
Final R indices
[I>2 σ (I)]
Largest difference
peak/hole
R1 ϭ 0.0439,
wR2 ϭ 0.1117
1.299 and Ϫ1.937 e.A
R1 ϭ 0.0349,
wR2 ϭ 0.0832
0.947 and Ϫ0.806 e.A
R1 ϭ 0.0342,
wR2 ϭ 0.0739
0.561 and Ϫ0.680 e.A
R1 ϭ 0.0418,
wR2 ϭ 0.0792
0.95 and Ϫ1.49 e.A
R1 ϭ 0.0265,
wR2 ϭ 0.0554
1.168 and Ϫ1.381 e.A
R1 ϭ 0.0414,
wR2 ϭ 0.0987
1.616 and Ϫ1.737 e.A
Ϫ3
Ϫ3
Ϫ3
Ϫ3
Ϫ3
Ϫ3
˚
˚
˚
˚
˚
˚
CCDC number
652376
652381
652379
652359
652378
652377
˚
Table 4 Selected bond lengths /A and angles /° of compounds 4e, 5b, 6a-c, 6e
Compound
4e
5b
6a
6b
6c
6e
MϪN
2.137(2)
2.120(4)
2.123(4)
2.116(5)
2.123(4)
2.146(1)
MϪCl
2.4112(9) / 2.4391(9)
83.68(7) / 87.45(7)
88.29(4)
2.409(1) / 2.430(1)
86.7(1) / 89.9(1)
92.34(4)
2.401(1) / 2.436(1)
85.4(1) / 88.0(1)
89.40(5)
2.404(2) / 2.418(2)
84.8(2) / 88.7(2)
89.69(7)
2.412(1) / 2.429(1)
82.0(1) / 90.7(1)
87.14(6)
2.398(3) / 2.436(3)
84.3(3) / 88.2(3)
90.4(1)
NϪMϪCl
ClϪMϪCl
˚
Table 5 Selected bond lengths /A and angles /° of compounds 7a, c-e
Compound
7a
7c
7d
7e
MϪN
2.121(2) / 2.127(2)
2.4181(8)
2.138(2) / 2.153(2)
2.4188(7)
2.116(5) / 2.127(6)
2.414(2)
2.121(3) / 2.134(3)
2.413(1)
MϪCl
NϪMϪCl
NϪMϪN
86.80(6) / 87.42(7)
83.74(8)
89.41(5) / 90.37(6)
77.35(6)
88.6(2) / 89.4(2)
79.3(2)
88.55(8) / 89.03(8)
79.0(1)
˚
Table 6 Selected bond lengths /A and angles /° of compounds 8a, c, e, 9a, c-d
Compound
8a
8c
8e
9a
9c
9d
MϪN
2.101(2)
2.396(1)
90.05(9)
87.2(1)
2.126(2) / 2.140(2)
2.3998(9)
2.122(2) / 2.127(2)
2.3895(8)
2.119(8) / 2.125(9)
2.405(3)
2.130(3) / 2.141(3)
2.094(5) / 2.102(5)
MϪCl
2.405(1)
2.419(2)
NϪMϪCl
NϪMϪN
91.44(7) / 92.59(7)
78.76(9)
89.84(7) / 90.54(7)
80.87(9)
88.2(2) / 88.5(2)
86.4(3)
89.7(1) / 91.06(9)
77.9(1)
88.2(2) / 89.5(2)
86.6(2)
1988
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Z. Anorg. Allg. Chem. 2007, 1985Ϫ1994

Neutral Mono- and Cationic Bis-Aziridine d6-Metal Complexes
Figure 3 Molecular structure of 6a. The thermal ellipsoids are
drawn at the 30 % probability level. Hydrogen atoms are omitted
for clarity.
Figure 1 Molecular structure of 4e. The thermal ellipsoids are
drawn at the 30 % probability level. Hydrogen atoms and one di-
chloromethane molecule are omitted for clarity.
Figure 4 Molecular structure of 7c. The thermal ellipsoids are
drawn at the 30 % probability level. Hydrogen atoms and one di-
chloromethane molecule are omitted for clarity.
Figure 2 Molecular structure of 5b. The thermal ellipsoids are
drawn at the 30 % probability level. Hydrogen atoms and disorde-
red aziridine atoms are omitted for clarity.
Spectroscopy
The IR, 1H, 13C NMR and mass spectra of compounds
4e-9d were obtained.
The IR spectra of compounds 4e-9d show absorptions
for the NϪH stretching vibrations in the expected range of
3282 to 3004 cmϪ1, as well as the characteristic bands for
the deformation vibrations of the aziridine ring
(891Ϫ763 cmϪ1) [5]. As expected, the CϪH absorptions of
the alkyl moieties of the aziridine ligands are observed in
with more or larger substituents at the aziridine ring, the
NϪMϪN angle decreases and the NϪMϪCl angles in-
crease.
The endocyclic CϪC and CϪN bond lengths of the coor-
dinated aziridine ligands in all complexes investigated in
this work differ only slightly from those of the free aziridine
[50], and the endocyclic CϪCϪN and CϪNϪC angles are
found to be approximately 60°.
the range of 3091 to 2875 cmϪ1
.
In the mass spectra of the mono-aziridine complexes
4e-6e, the parent signals for the intact molecules were meas-
ured at m/z ϭ 453 (4e), 365 (5b), 441 (6a), 455 (6b), 469
Z. Anorg. Allg. Chem. 2007, 1985Ϫ1994
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1989

R. Bobka, J. N. Roedel, B. Neumann, C. Krinninger, P. Mayer, S. Wunderlich, A. Penger, I.-P. Lorenz
is hindered, generating a new chirality at the nitrogen atom
(N-chirality), if substituted aziridines (b-e) are used [14, 51,
52]. This and the use of racemic mixtures of the aziridines
d and e could lead to isomers. Therefore, up to four differ-
ent signals for each group were obtained. Just one mono-
aziridine complex (6c) forms an isomer with signals of
minor intensity. In particular for the bis-aziridine complexes
7d, 7e, 8e and 9d where the aziridine ligands are mono sub-
stituted in 2-position, many signals for the possible isomers
were detected.
1
In the H NMR spectra all of the signals corresponding
to the aziridine protons were more or less shifted to lower
field in comparison with the signals of the free aziridines a-e
[53Ϫ55]. The NH (1.60Ϫ5.59 ppm), ring protons Az-CH2
(1.30Ϫ2.78 ppm) and Az-CH (2.22Ϫ3.73 ppm) signals were
observed in the expected ranges and showed a larger low-
field shift than the signals of the exocyclic hydrogen atoms
Et-CH2 (1.21Ϫ2.16 ppm), CH3 (0.94Ϫ1.58 ppm) and
Ph-CH (7.23Ϫ7.66 ppm). Only in complexes 5b and 6b the
signals of the NH proton could not be localized, because
they are hidden by the signals of the ring protons. Due to
the N-coordination to the transition metal atom, not only
3J couplings between the ring protons of the alkyl moieties
were observed, but also between NH and Az-CH2 and
Az-CH. The values of the couplings range from 5.1 and
8.7 Hz. An additional 2J coupling of 1.0 Hz for the Az-CH2
group was detected in the spectrum of 4e.
Figure 5 Molecular structure of 8a. The thermal ellipsoids are
drawn at the 30 % probability level. Hydrogen atoms and two di-
chloromethane molecules are omitted for clarity.
In general, in the 13C NMR spectra of all compounds
the signals of the ring carbon atoms AzϪCH2
(19.04Ϫ33.34 ppm), AzϪCH (31.80Ϫ41.35 ppm) and
AzϪCq (39.39Ϫ41.63 ppm) were shifted to lower-field,
compared to the corresponding signals of the free aziridines
a-e [53Ϫ55]. The signals for the methyl (19.26, 19.40 ppm)
and ethyl groups (10.14Ϫ11.40 ppm; 23.82Ϫ26.34 ppm) of
the 2-methylaziridine and 2-ethylaziridine complexes differ
only slightly from those of the free azirdines b and d. For
the 2-phenylaziridine complexes 4e, 6e, 7e and 8e, the
aromatic Cq signals (135.12Ϫ137.54 ppm) are shifted to
higher field, whereas the aromatic CH signals
(126.22Ϫ129.13 ppm) are shifted to lower field. Due to the
coordination of the 2,2-dimethylaziridine c in complexes
6c-9c, the signals of the methyl groups are now not equiva-
lent. In comparison with the free aziridine c, the signals of
the methyl groups, which are turned away from the metal
atom, (20.15Ϫ21.44 ppm) were detected at higher field, and
the others (25.90Ϫ27.46 ppm) at lower field.
Figure 6 Molecular structure of 9d. The thermal ellipsoids are
drawn at the 30 % probability level. Hydrogen atoms are omitted
for clarity.
(6c) and 517 (6e). In all cases, fragmentation signals for the
cleavage of the aziridine ligand (Mϩ ϪAz), and the sub-
sequent separation of the chlorido ligand (MϩϪAzϪCl)
were detected. In the FABϩ spectra of the bis-aziridine
complexes 7a-9d the signals for the intact cations were ob-
tained: m/z ϭ 385 (7a), 441 (7c), 441 (7d), 537 (7e), 359
(8a), 415 (8c), 511 (8e), 449 (9a), 505 (9c), 506 (9d). The
fragmentation pattern resulting from the cleavage of one
and two aziridines (MϩϪn Az) (n ϭ 1, 2) were also ob-
served for these compounds.
Experimental Part
General Procedures: All experiments were performed under a dry
argon atmosphere using Schlenk line techniques. Aziridine, 2-mon-
omethylaziridine, 2,2-dimethylaziridine, 2-Ethylaziridine, 2-Phenyl-
aziridine, [RhCl2Cp*]2, [IrCl2Cp*]2, and [RuCl2(C6Me6)] were pre-
pared according to the literature methods [40, 41, 56, 57]. Dichloro-
methane was distilled from calcium hydride, and n-pentane and
n-hexane were distilled from sodium. All solvents were stored under
1
In the H and 13C NMR spectra signals of isomers for
a dry argon atmosphere with 3 A molecular sieve. 1H and 13C
˚
the complexes 6c, 7c-e, 8c, 8e and 9d were observed. On
coordination to the transition metal the nitrogen inversion
NMR spectra were measured on a Jeol Eclipse 270, Jeol Eclipse
1990
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Z. Anorg. Allg. Chem. 2007, 1985Ϫ1994

Neutral Mono- and Cationic Bis-Aziridine d6-Metal Complexes
400 and Jeol EX400 spectrometer. 1H and 13C chemical shifts were
determined relative to TMS as external standard. IR spectra (KBr)
were recorded using a Nicolet 520 FT-IR and Perkin Elmer Spec-
trum One FT-IR spectrometer. Mass spectra were obtained by a
Finnigan MAT 90, Joel MStation JMS 700, electron energy 70 eV
(EI), NBA matrix (FAB). Single crystal X-Ray diffraction data
were collected on a Nonius Kappa CCD diffractometer using
graphite-monochromated Mo-Kα radiation. Single crystal X-ray
structure analyses were performed by direct methods using the
SHELXS software and refined by full-matrix least-squares with
SHELXL-97 [58]. Tables 1Ϫ3 contain the crystal data and details
of the structural refinement of 4e-9d. Elemental analysis were per-
formed by the Microanalytical Laboratory of the Department of
Chemistry and Biochemistry, LMU Munich using a Heraeus Ele-
mentar Vario El.
[IrCl2(Cp*)(C2H4NH)] (6a):
Reagents: 184 mg (0.231 mmol) 3, 24.9 µL (0.462 mmol) a; reaction
time: 16 h.
Yield 93 %; deep yellow powder; decomposition
C12H20Cl2IrN (441.42); C 33.28 (calc. 32.65); H 4.58 (4.57); 2.85
(3.17) %.
> 211 °C;
IR (KBr): 3200 s, 3091 m, 3020 w, 3002 m, 2985 m, 2968 m, 2918 m, 2700 w,
2445 w, 1490 m, 1452 m, 1438 m, 1405 w, 1383 m, 1376 m, 1369 m 1358 w,
1228 m, 1158 w, 1136 w, 1123 w, 1108 m, 1091 w, 1081 w, 1032 m, 1023 m,
940 w, 887 s, 825 w, 794 w, 734 w, 616 w, 583 w, 535 w, 467 w, 452 w, 411 w
cmϪ1. MS (FAB-pos): m/z ϭ 441 (Mϩ, 15 %), 406 (Mϩ ϪCl, 83 %), 398
(Mϩ ϪAz, 25 %), 363 (Mϩ ϪCl ϪAz, 100 %). 1H NMR (CD2Cl2) δ ϭ 1.62
(s, 15 H, Cp*ϪCH3), 2.18 (br, 4 H, AzϪCH2), 4.37 (br, 1 H, NH). 13C NMR
(CD2Cl2) δ ϭ 8.68 (Cp*ϪCH3), 23.47 (AzϪCH2), 84.87 (Cp*ϪCq).
[IrCl2(Cp*)(C2H3MeNH)] (6b):
Reagents: 239 mg (0.300 mmol) 3, 42.8 µL (0.600 mmol) b; reaction
time: 30 min.
General method for the synthesis of the mono-
aziridine complexes
Yield 90 %; deep yellow powder; decomposition
> 208 °C;
C13H22Cl2IrN (455.44); C 34.98 (calc. 34.28); H 4.71 (4.87); 3.01
(3.08) %.
The synthesis of the mono-aziridine complexes 4e-6e was achieved
by dissolving [MCl2L]2 (1-3) in dichloromethane (20 mL), followed
by the addition of the aziridine (a-e) in a 1:2 molar ratio. After
stirring at room temperature, the solvent was removed in vacuo.
The residue was purified by stirring in dry n-hexane (20 mL) 12 h.
The n-hexane phase was subsequently removed by decantation, and
the powder was dried in vacuo.
IR (KBr): 3199 s, 3051 w, 2962 m, 2918 m, 2870 w, 1454 m, 1402 w, 1383 m,
1362 w, 1333 w, 1242 w, 1213 w, 1159 w, 1148 w, 1113 w, 1070 m, 1035 m,
962 w, 894 w, 844 m, 763 w, 617 w, 584 w, 540 w, 514 w, 464 w, 440 w, 407 w
cmϪ1. MS (EI): m/z ϭ 455 (Mϩ, 15 %), 398 (Mϩ ϪAz, 35 %), 363 (Mϩ ϪCl
ϪAz, 100 %). 1H NMR (CD2Cl2) δ ϭ 1.43 (d, 3J ϭ 5.8 Hz, 3 H, AzϪCH3),
1.60 (s, 15 H, Cp*ϪCH3), 1.94 (dd, 3J ϭ 5.2 Hz, 3J ϭ 8.0 Hz, 1 H,
AzϪHCH), 2.32 (dd, 3J ϭ 6.1 Hz, 3J ϭ 6.1 Hz, 1 H, AzϪHCH), 2.54-2.62
(m, 1 H, AzϪCH). 13C NMR (CD2Cl2) δ ϭ 9.00 (Cp*ϪCH3), 19.40
(AzϪCH3), 31.12 (AzϪCH2), 33.36 (AzϪCH), 85.06 (Cp*ϪCq).
[RuCl2(C6Me6)(C2H3PhNH)] (4e):
Reagents: 131 mg (0.196 mmol) 1; 45.6 µL (0.392 mmol) e; reaction
time: 12 h.
[IrCl2(Cp*)(C2H2Me2NH)] (6c):
Reagents: 251 mg (0.315 mmol) 3, 56.9 µL (0.630 mmol); reaction
time: 1 h.
Yield 98 %; deep yellow powder; decomposition
C14H24Cl2IrN (469.47); C 35.83 (calc. 35.82); H 5.17 (5.15); N
2.99 (2.98) %.
Yield 77 %; orange powder; decomposition
>
220 °C;
C20H27Cl2NRu (453.41); C 52.26 (calc. 52.98); H 5.86 (6.00); N
3.07 (3.09) %.
> 235 °C;
IR (KBr): 3282 w, 3026 m, 3010 m, 2921 m, 1605 m, 1501 m, 1301 w, 1235 w,
1188 w, 1137 s, 1092 w, 1072 m, 1023 m, 953 m, 887 s, 822 w, 761 vs, 554 w
cmϪ1. MS (FAB-pos): m/z ϭ 453 (Mϩ, 9 %), 418 (Mϩ ϪCl, 100 %), 382
(Mϩ Ϫ2 Cl, 10 %), 334 (Mϩ ϪAz, 26 %). 1H NMR (CD2Cl2) δ ϭ 1.60 (br,
1 H, NH), 2.02 (s, 18 H, C6Me6ϪCH3), 2.35 (ddd, 2J ϭ 1.0 Hz, 3J ϭ 5.1 Hz,
3J ϭ 8.6 Hz, 1 H, AzϪHCH), 2.41 (ddd, 2J ϭ 1.0 Hz, 3J ϭ 6.6 Hz, 3J ϭ
6.6 Hz, 1 H, AzϪHCH), 3.30 (ddd, 3J ϭ 5.1 Hz, 3J ϭ 5.8 Hz, 3J ϭ 6.1 Hz,
1 H, AzϪCH), 7.29-7.47 (m, 5 H, PhϪCH). 13C NMR (CD2Cl2) δ ϭ 15.58
(C6Me6ϪCH3), 30.91 (AzϪCH2), 38.49 (AzϪCH), 90.26 (C6Me6ϪCq),
126.60, 128.48, 129.13 (PhϪCH), 137.00 (PhϪCq).
IR (KBr): 3184 s, 3009 w, 2988 w, 2960 m, 2916 m, 2872 w, 1480 w, 1448 m,
1384 m, 1363 w, 1349 w, 1331 w, 1287 w, 1160 w, 1145 w, 1119 m, 1110 w,
1081 w, 1034 m, 978 w, 922 w, 812 m, 682 w, 615 w, 585 w, 530 w, 523 w,
462 w, 453 w, 436 w cmϪ1. MS (FAB-pos): m/z ϭ 469 (Mϩ, 12 %), 434 (Mϩ
ϪCl, 100 %), 398 (Mϩ ϪAz, 18 %), 363 (Mϩ ϪCl, ϪAz, 70 %).1H NMR
(CD2Cl2) δ ϭ 1.28, 1.35 (s, 3 H, AzϪCH3), 1.47, 1.56 (s, 3 H, AzϪCH3),
1.62, 1.74 (s, 15 H, Cp*ϪCH3), 1.76, 1.87 (d, 3J ϭ 8.6 Hz, 1 H, AzϪHCH),
2.15 (br, 1 H, NH), 2.17, 2.44 (d, 3J ϭ 6.1 Hz, 1 H, AzϪHCH). 13C NMR
(CD2Cl2) δ ϭ 9.16, 9.85 (Cp*ϪCH3), 21.11, 21.24 (AzϪCH3), 25.98, 26.94
(AzϪCH3), 31.96, 33.36 (AzϪCH2), 40.65, 41.66 (AzϪCq), 85.05, 86.55
(Cp*ϪCq).
[RhCl2(Cp*)(C2H3MeNH)] (5b):
Reagents: 252 mg (0.408 mmol) 2, 58.3 µL (0.816 mmol) b; reaction
time: 10 min.
[IrCl2(Cp*)(C2H3PhNH)] (6e):
Reagents: 275 mg (0.345 mmol) 3, 80.3 µL (0.690 mmol) e; reaction
time: 30 min.
Yield 99 %; deep yellow powder; decomposition
C18H24Cl2IrN (517.51); C 41.92 (calc. 41.78); H 4.50 (4.67); N
2.67 (2.71) %.
Yield 84 %; deep orange powder; decomposition
> 185 °C;
C13H22Cl2NRh (366.13); C 41.15 (calc. 42.65); H 6.05 (6.06); N
2.65 (3.83) %.
> 190 °C;
IR (KBr): 3190 vs, 3068 w, 3043 w, 2962 m, 2914 m, 1452 s, 1400 m, 1372 m,
1361 m, 1311 w, 1241 m, 1214 w, 1161 w, 1148 w, 1111 w, 1067 m, 1028 s,
962 m, 892 w, 845 s, 800 w, 766 w, 730 w, 696 w, 620 w, 587 w, 540 w, 503 w,
541 w, 442 w cmϪ1. MS (EI): m/z ϭ 365 (Mϩ, 9 %), 308 (Mϩ ϪAz, 59 %),
273 (Mϩ ϪAz ϪCl, 71 %), 236 (Mϩ ϪAz Ϫ2 Cl, 100 %). 1H NMR (CD2Cl2)
δ ϭ 1.37 (d, 3J ϭ 5.8 Hz, 3 H, AzϪCH3), 1.63 (s, 15 H, Cp*ϪCH3), 1.79
(dd, 3J ϭ 5.0 Hz, 3J ϭ 8.2 Hz, 1 H, AzϪHCH), 2.12 (dd, 3J ϭ 6.1 Hz, 3J ϭ
6.1 Hz, 1 H, AzϪHCH), 2.43 (m, 1 H, AzϪCH). 13C NMR (CD2Cl2) δ ϭ
8.90 (Cp*ϪCH3), 19.26 (AzϪCH3), 29.71 (AzϪCH2), 31.80 (AzϪCH), 93.26
(d, 1J (C, Rh) ϭ 10.8 Hz, Cp*ϪCq).
IR (KBr): 3226 m, 3062 m, 3034 m, 3011 m, 2983 m, 2965 m, 2919 m,
1603 w, 1498 m, 1457 s, 1406 w, 1383 m, 1356 w, 1300 w, 1240 w, 1183 w,
1148 m, 1141 m, 1079 w, 1032 m, 955 w, 927 w, 884 w, 852 w, 827 w, 770 vs,
745 w, 705 s, 618 w, 584 w, 574 w, 548 w, 464 w, 440 w, 407 w cmϪ1. MS
(FAB-pos): m/z ϭ 517 (Mϩ, 14 %), 482 (Mϩ ϪCl, 100 %), 398 (Mϩ ϪAz,
15 %), 363 (Mϩ ϪCl ϪAz, 92 %). 1H NMR (CD2Cl2) δ ϭ 1.59 (s, 15 H, Cp*
ϪCH3), 2.08 (br, 1 H, NH), 2.63 (dd, 3J ϭ 5.3 Hz, 3J ϭ 8.2 Hz, 1 H,
AzϪHCH), 2.78 (dd, 3J ϭ 6.5 Hz, 3J ϭ 6.5 Hz, 1 H, AzϪHCH), 3.68-3.73
Z. Anorg. Allg. Chem. 2007, 1985Ϫ1994
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1991

R. Bobka, J. N. Roedel, B. Neumann, C. Krinninger, P. Mayer, S. Wunderlich, A. Penger, I.-P. Lorenz
(m, 1 H, AzϪCH), 7.34-7.40 (m, 5 H, PhϪCH). 13C NMR (CD2Cl2) δ ϭ
8.78 (Cp*ϪCH3), 30.62 (AzϪCH2), 39.03 (AzϪCH), 85.01 (Cp*ϪCq),
127.14, 128.76, 129.10 (PhϪCH), 135.85 (PhϪCq).
AzϪHCH), 1.83-1.94, 1.96-2.06 (m, 4 H, AzϪCH2) 2.12, 2.14, 2.15 (s, 18 H,
C6Me6ϪCH3), 2.22-2.31, 2.35-2.43 (m, 2 H, AzϪCH) 4.00, 4.41, 4.74 (br,
2 H, NH). 13C NMR (CDCl3) δ ϭ 10.14, 10.21, 10.44, 10.51 (EtϪCH3),
14.82, 14.86, 14.92 15.00 (C6Me6ϪCH3), 23.82, 23.87, 24.81, 24.91
(EtϪCH2), 25.82, 26.00, 28.98, 29.45 (AzϪCH2), 32.87, 33.04, 37.90, 38.21
(AzϪCH), 89.24, 91.00 91.04, 91.11 (C6Me6ϪCq).
General method for the synthesis of the bis-aziridine
complexes
[RuCl(C6Me6)(C2H3PhNH)2]Cl (7e):
The synthesis of the bis-aziridine complexes 7a-9d was achieved by
dissolving [MCl2L]2 (1-3) in dichloromethane (20 mL), followed by
the addition of the aziridine (a-e) in a 1:5 molar ratio. After stirring
for 5 min to 2 h at room temperature, the solvent was removed in
vacuo. The residue was purified by stirring in dry n-hexane (20 mL)
overnight. The n-hexane phase was subsequently removed by de-
cantation, and the powder was dried in vacuo.
Reagents: 88 mg (0.132 mmol) 1, 76.6 µL (0.658 mmol) e; reaction
time: 12 h.
Yield 79 %; yellow powder; m.p. 169 °C; C28H36Cl2N2Ru (572.57);
C 56.50 (calc. 58.73); H 6.24 (6.34); N 4.80 (4.89) %.
IR (KBr): 3061 s, 3035 s, 2922 m, 1605 w, 1584 w, 1501 m, 1459 m, 1386 m,
1291 w, 1256 w, 1242 w, 1190 w, 1156 m, 1072 m, 1020 m, 965 w, 884 m,
763 vs, 701 vs, 594 w, 552 w, 548 w, 477 w, 458 w, 419 w cmϪ1. MS (FAB-
pos): m/z ϭ 537 (Mϩ, 64 %), 418 (Mϩ ϪAz, 100 %), 383 (Mϩ ϪAz ϪCl,
7 %), 299 (Mϩ Ϫ2 Az, 28 %). 1H NMR (CD2Cl2) δ ϭ 1.30, 1.96, 2.35 (dd,
3J ϭ 8.4 Hz, 3J ϭ 5.2 Hz, 2 H, AzϪHCH), 2.00, 2.02, 2.10 (s, 18 H,
C6Me6ϪCH3), 2.13-2.20 (m), 2.41, 2.52 (dd, 3J ϭ 6.2 Hz, 3J ϭ 6.2 Hz, 2 H,
AzϪHCH), 2.82, 2.88, 3.30, 3.59 (ddd, 3J ϭ 6.7 Hz, 3J ϭ 6.7 Hz, 3J ϭ
5.3 Hz, 2 H, AzϪCH) 5.15, 5.41 (br, 2 H, NH), 7.23-7.40, 7.43-7.51, 7.60-
7.66 (m, 10 H, PhϪCH). 13C NMR (CD2Cl2) δ ϭ 15.64, 15.83, 15.91
(C6Me6ϪCH3), 30.13, 30.81, 30.90, 32.87 (AzϪCH2), 35.32, 38.43, 40.91,
41.35 (AzϪCH), 90.25, 92.21, 92.27 (C6Me6ϪCq), 126.34, 126.58, 127.55,
127.93, 128.01, 128.28, 128.96, 129.10, (PhϪCH), 135.12, 137.43, 137.54
(PhϪCq).
[RuCl(C6Me6)(C2H4NH)2]Cl (7a):
Reagents: 113 mg (0.169 mmol) 1, 45.5 µL (0.845 mmol) a; reaction
time: 12 h.
Yield 80 %; yellow powder; decomposition
>
215 °C;
C16H28Cl2N2Ru (420.38); C 45.09 (calc. 45.71); H 6.43 (6.71); N
5.80 (6.66) %.
IR (KBr): 3226 s, 3083 m, 3031 s, 3012 s, 2997 s, 2923 m, 2724 w, 1445 m,
1432 m, 1386 s, 1344 w, 1258 w, 1226 m, 1141 w, 1096 m, 1089 m, 1070 m,
1024 w, 936 w, 884 vs, 818 w, 799 w, 515 w, 463 w cmϪ1. MS (FAB-pos):
m/z ϭ 385 (Mϩ, 36 %), 342 (Mϩ ϪAz, 100 %), 299 (Mϩ Ϫ2 Az, 50 %). 1H
NMR (CD2Cl2) δ ϭ 1.50 (ddd, 3J ϭ 5.9 Hz, 3J ϭ 6.3 Hz, 3J ϭ 6.6 Hz, 1 H,
AzϪHCH), 1.63 (ddd, 3J ϭ 7.8 Hz, 3J ϭ 7.8 Hz, 3J ϭ 5.8 Hz, 1 H,
AzϪHCH), 1.86-1.97 (m, 4 H, AzϪCH2), 2.05, 2.12 (s, 18 H, C6Me6ϪCH3),
2.15-2.19 (m, 1 H, AzϪHCH), 2.40 (ddd, 3J ϭ 7.5 Hz, 3J ϭ 7.5 Hz, 3J ϭ
5.2 Hz, 1 H, AzϪHCH), 4.36 (br, 2 H, NH). 13C NMR (CD2Cl2) δ ϭ 15.46
(C6Me6ϪCH3), 19.04, 22.82, 23.66 (AzϪCH2), 90.15, 91.96 (C6Me6ϪCq).
[RhCl(Cp*)(C2H4NH)2]Cl (8a):
Reagents: 299 mg (0.484 mmol) 2, 130 µL (2.42 mmol) a; reaction
time: 2 h.
Yield 93 %; pale orange powder; decomposition
C14H25Cl2N2Rh (395.18); C 42.33 (calc. 42.55); H 6.46 (6.38); N
6.92 (7.09) %.
> 167 °C;
IR (KBr): 3050 m, 3001 m, 2913 w, 2702 w, 1649 w, 1554 w, 1538 w, 1491 w,
1453 m, 1422 w, 1383 w, 1362 w, 1248 w, 1226 m, 1160 w, 1093 m, 1033 m,
955 w, 885 s, 798 w, 672 w, 652 w cmϪ1. MS (FAB-pos): m/z ϭ 359 (Mϩ,
24 %), 316 (Mϩ ϪAz, 100 %), 273 (Mϩ Ϫ2 Az, 40 %), 237 (Mϩ Ϫ2 Az ϪCl,
14 %). 1H NMR (CD2Cl2) δ ϭ 1.63 (ddd, 3J ϭ 6.2 Hz, 3J ϭ 6.2 Hz, 3J ϭ
6.2 Hz, 2 H, AzϪHCH), 1.74 (s, 15 H, Cp*ϪCH3), 1.75-1.79 (m, 2 H,
AzϪHCH), 1.99 (ddd, 3J ϭ 5.8 Hz, 3J ϭ 5.8 Hz, 3J ϭ 5.9 Hz, 2 H,
AzϪHCH), 2.34 (ddd, 3J ϭ 7.6 Hz, 3J ϭ 7.6 Hz, 3J ϭ 5.3 Hz, 2 H,
AzϪHCH), 4.81 (br, 2 H, NH). 13C NMR (CD2Cl2) δ ϭ 8.76 (Cp*ϪCH3),
19.36, 22.28 (AzϪCH2), 94.61 (d, 1J (C, Rh) ϭ 8.8 Hz, Cp*ϪCq).
[RuCl(C6Me6)(C2H2Me2NH)2]Cl (7c):
Reagents: 77 mg (0.115 mmol) 1, 51.9 µL (0.576 mmol) c; reaction
time: 12 h.
Yield 74 %; yellow powder; decomposition
C20H36Cl2N2Ru (476.49); C 48.19 (calc. 50.41); H 7.10 (7.62); N
5.58 (5.88) %.
>
235 °C;
IR (KBr): 3084 vs, 3072 vs, 3004 m, 2993 m, 2967 m, 2929 m, 1450 m, 1395 s,
1372 w, 1336 m, 1299 w, 1290 w, 1182 w, 1153 w, 1123 m, 1117 s, 1070 w,
1046 w, 1022 w, 992 m, 976 m, 919 w, 827 w, 813 w, 690 w, 658 w, 458 w
cmϪ1. MS (FAB-pos): m/z ϭ 441 (Mϩ, 13 %), 370 (Mϩ ϪAz, 100 %), 334
(Mϩ ϪAz ϪCl, 10 %), 299 (Mϩ Ϫ2 Az, 30 %). 1H NMR (CD2Cl2) δ ϭ 1.30,
1.38 (s, 6 H, AzϪCH3), 1.46, 1.58 (s, 6 H, AzϪCH3), 1.53, 1.59 (d, 3J ϭ
8.7 Hz, 2 H, AzϪHCH), 1.63, 1.86 (d, 3J ϭ 6.1 Hz, 2 H, AzϪHCH), 1.97,
2.07, 2.19 (s, 18 H, C6Me6ϪCH3), 4.55 (br, 2 H, NH). 13C NMR (CD2Cl2)
δ ϭ 15.69, 15.90, 16.62 (C6Me6ϪCH3), 20.15, 21.11 (AzϪCH3), 26.00, 27.46
(AzϪCH3), 31.55, 33.25 (AzϪCH2), 40.28 (AzϪCq), 89.60, 90.15, 91.85
(C6Me6ϪCq).
[RhCl(Cp*)(C2H2Me2NH)2]Cl (8c):
Reagents: 320 mg (0.517 mmol) 2, 189 µL (2.10 mmol) c; reaction
time: 2 h.
Yield 91 %; pale orange powder; decomposition
> 190 °C;
C18H33Cl2N2Rh (451.32); C 47.24 (calc. 47.90); H 7.17 (7.39); N
5.84 (6.21) %.
IR (KBr): 3049 s, 2996 m, 2963 m, 2917 m, 1450 m, 1394 m, 1380 m, 1336 m,
1300 w, 1289 w, 1261 w, 1183 w, 1153 w, 1119 s, 1080 w, 1025 m, 994 w,
976 w, 930 w, 918 m, 825 m, 812 m, 692 w, 620 w, 586 w, 538 w, 526 w, 503 w,
430 w cmϪ1. MS (FAB-pos): m/z ϭ 415 (Mϩ, 5 %), 344 (Mϩ ϪAz, 100 %),
273 (Mϩ Ϫ2 Az, 34 %), 237 (Mϩ Ϫ2 Az ϪCl, 14 %). 1H NMR (CD2Cl2)
δ ϭ 1.36 (s, 6 H, AzϪCH3), 1.55 (s, 6 H, AzϪCH3), 1.71 (d, 3J ϭ 8.4 Hz,
2 H, AzϪHCH), 1.66, 1.77 (s, 15 H, Cp*ϪCH3), 1.88 (d, 3J ϭ 7.7 Hz, 2 H,
AzϪHCH), 4.92 (br, 2 H, NH). 13C NMR (CD2Cl2) δ ϭ 9.29, 9.93 (Cp*
ϪCH3), 21.44 (AzϪCH3), 26.17 (AzϪCH3), 32.22, 33.31 (AzϪCH2), 39.39
(AzϪCq), 95.01 (d, 1J (C, Rh) ϭ 8.5 Hz, Cp*ϪCq).
[RuCl(C6Me6)(C2H3EtNH)2]Cl (7d):
Reagents: 79 mg (0.116 mmol) 1, 51.6 µL (0.591 mmol) d; reaction
time: 12 h.
Yield 84 %; yellow powder; decomposition
C20H36Cl2N2Ru (476.49); C 49.04 (calc. 50.41); H 7.41 (7.62); N
5.57 (5.88) %.
>
215 °C;
IR (KBr): 3004 s, 2964 vs, 2932 s, 2875 m, 1456 s, 1390 s, 1264 w, 1232 w,
1151 w, 1104 w, 1076 s, 1021 s, 946 w, 912 m, 852 m, 806 m, 767 w, 659 w,
551 w, 486 w cmϪ1. MS (FAB-pos): m/z ϭ 441 (Mϩ, 21 %), 370 (Mϩ ϪAz,
100 %), 334 (Mϩ ϪAz ϪCl, 11 %), 299 (Mϩ Ϫ2 Az, 41 %). 1H NMR
(CDCl3) δ ϭ 0.94, 1.03 (t, 3J ϭ 8.0 Hz, 6 H, EtϪCH3), 1.21-1.33, 1.41-
1.45, 1.47-1.55 (m, 4 H, EtϪCH2), 1.58 (dd, 3J ϭ 6.3 Hz, 3J ϭ 6.3 Hz, 1 H,
[RhCl(Cp*)(C2H3PhNH)2]Cl (8e):
Reagents: 256 mg (0.414 mmol) 2, 193 µL (1.66 mmol) e; reaction
time: 2 h.
1992
www.zaac.wiley-vch.de
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 1985Ϫ1994

Neutral Mono- and Cationic Bis-Aziridine d6-Metal Complexes
Yield 93 %; pale orange powder; m.p. 187 °C; C18H33Cl2N2Rh
(547.12); C 55.55 (calc. 57.07); H 6.22 (6.09); N 4.87 (5.12) %.
References
IR (KBr): 3087 s, 3007 m, 2914 w, 1604 w, 1582 w, 1500 m, 1480 w, 1455 s,
1427 w, 1380 m, 1343 w, 1314 w, 1242 m, 1190 m, 1174 m, 1156 m, 1107 w,
1079 m, 1027 m, 963 m, 886 m, 878 m, 839 w, 776 s, 766 s, 701 s, 619 w,
585 w, 551 w, 537 w, 456 w, 439 w cmϪ1. MS (FAB-pos): m/z ϭ 511 (Mϩ,
7 %), 392 (Mϩ ϪAz, 100 %), 273 (Mϩ Ϫ2 Az, 23 %), 237 (Mϩ Ϫ2 Az ϪCl,
14 %). 1H NMR (CD2Cl2) δ ϭ 1.34-1.37 (m, 1 H, AzϪHCH), 1.59, 1.62,
1.68 (s, 15 H, Cp*ϪCH3), 2.11-2.19 (m, 2 H, AzϪCH2), 2.62-2.68 (m, 1 H,
AzϪHCH), 3.03-3.08 (m, 2 H, AzϪCH), 5.59 (br, 2 H, NH), 7.26-7.46, 7.56-
7.60 (m, 10 H, PhϪCH). 13C NMR (CD2Cl2) δ ϭ 8.96, 9.06, 9.16 (Cp*
ϪCH3), 29.73, 29.98, 31.54 (AzϪCH2), 35.64, 39.45, 39.89 (AzϪCH), 93.51,
94.99, 95.17 (d, 1J (C, Rh) ϭ 8.5 Hz, Cp*ϪCq), 126.22, 127.22, 128.16,
128.50, 129.98, 129.11 (PhϪCH), 137.13, 137.30 (PhϪCq).
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[IrCl(Cp*)(C2H4NH)2]Cl (9a):
Reagents: 109 mg (0.137 mmol) 3, 36.9 µL (0.684 mmol) a; reaction
time: 2 h.
Yield 99 %; pale yellow powder; m.p. 160 °C; C14H25Cl2IrN2
(484.49); C 34.64 (calc. 34.71); H 5.07 (5.20); N 5.78 (5.62) %.
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391Ϫ396.
IR (KBr): 3011 s, 2985 s, 2919 m, 2740 m, 2480 w, 2417 w, 2201 w, 1488 w,
1455 m, 1426 w, 1395 m, 1388 m, 1227 m, 1159 w, 1114 m, 1100 m, 1039 m,
956 w, 891 m, 615 w, 573 w, 539 w, 451 w cmϪ1. MS (FAB-pos): m/z ϭ 449
(Mϩ, 22 %), 406 (Mϩ ϪAz, 100 %), 363 (Mϩ Ϫ2 Az, 46 %). 1H NMR
(CD2Cl2) δ ϭ 1.69 (s, 15 H, Cp*ϪCH3), 1.69-1.81 (m, 4 H, AzϪCH2), 2.29
(ddd, 3J ϭ 5.5 Hz, 3J ϭ 5.5 Hz 3J ϭ 6.8 Hz, 2 H, AzϪHCH), 2.45 (ddd,
3J ϭ 7.7 Hz, 3J ϭ 7.7 Hz, 3J ϭ 5.3 Hz, 2 H, AzϪHCH), 5.27 (br, 2 H, NH).
13C NMR (CD2Cl2) δ ϭ 8.55 (Cp*ϪCH3), 19.37, 23.94 (AzϪCH2), 86.07
(Cp*ϪCq).
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[IrCl(Cp*)(C2H2Me2NH)2]Cl (9c):
Reagents: 97 mg (0.122 mmol) 3, 44.1 µL (0.609 mmol) c; reaction
time: 2 h.
Yield 99 %; pale yellow powder; m.p. 168 °C; C18H33Cl2IrN2
(540.59); C 39.46 (calc. 39.99); H 5.90 (6.15); N 4.94 (5.18) %.
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IR (KBr): 3081 s, 3005 s, 2974 m, 2962 m, 2920 m, 2755 w, 2655 w, 2586 w,
1454 m, 1396 m, 1381 m, 1335 m, 1304 w, 1294 w, 1261 w, 1188 w, 1160 m,
1119 s, 1082 w, 1034 m, 997 m, 978 m, 916 m, 826 m, 812 m, 687 w, 621 w,
599 w, 537 w, 516 w, 456 w, 421 w cmϪ1. MS (FAB-pos): m/z ϭ 505 (Mϩ,
13 %), 434 (Mϩ ϪAz, 100 %), 363 (Mϩ Ϫ2 Az, 37 %). 1H NMR (CD2Cl2)
δ ϭ 1.28 (s, 6 H, AzϪCH3), 1.55 (s, 6 H, AzϪCH3), 1.75 (s, 15 H, Cp*
ϪCH3), 1.76 (d, 3J ϭ 5.2 Hz, 2 H, AzϪHCH), 2.17 (d, 3J ϭ 5.9 Hz, 2 H,
AzϪHCH), 5.41 (br, 2 H, NH). 13C NMR (CD2Cl2) δ ϭ 9.83 (Cp*ϪCH3),
21.04 (AzϪCH3), 25.90 (AzϪCH3), 31.87 (AzϪCH2), 40.52 (AzϪCq), 86.52
(Cp*ϪCq).
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Reagents: 253 mg (0.467 mmol) 3, 134 µL (1.87 mmol) d; reaction
time: 2 h.
Yield 89 %; pale yellow powder; m.p. 206 °C; C18H33Cl2IrN2
(540.59); C 39.30 (calc. 39.99); H 6.13 (6.15); N 5.07 (5.18) %.
IR (KBr): 3018 s, 2963 s, 2933 m, 2876 m, 2757 w, 2718 m, 1455 m, 1402 w,
1384 m, 1316 w, 1277 w, 1231 w, 1216 w, 1154 w, 1129 w, 1099 w, 1080 m,
1036 m, 1002 w, 949 w, 912 m, 852 m, 806 w, 768 w, 621 w, 582 w, 461 w,
431 w cmϪ1. MS (FAB-pos): m/z ϭ 506 (Mϩ, 19 %), 435 (Mϩ ϪAz, 100 %),
363 (Mϩ Ϫ2 Az, 44 %). 1H NMR (CD2Cl2) δ ϭ 1.01-1.08 (m, 6 H, EtϪCH3),
1.64-1.72 (m, 15 H, Cp*ϪCH3), 2.05-2.16 (m, 4 H, EtϪCH2), 2.24-2.31 (m,
2 H, AzϪHCH), 2.45-2.55 (m, 2 H, AzϪHCH), 2.73-2.83 (m, 2 H, AzϪCH),
4.80, 5.06 (br, 2 H, NH). 13C NMR (CD2Cl2) δ ϭ 8.48, 8.65, 8.82, (Cp*
ϪCH3), 10.74, 10.79, 11.16, 11.40 (EtϪCH3), 24.74, 24.79, 26.34 (EtϪCH2),
25.33, 25.44, 30.36, 30.69 (AzϪCH2), 34.06, 34.30, 39.40, 39.79 (AzϪCH),
85.93, 85.95 (Cp*ϪCq).
Z. Anorg. Allg. Chem. 2007, 1985Ϫ1994
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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1994
www.zaac.wiley-vch.de
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 1985Ϫ1994