Synthesis of the dimeric, N substituted μ2-O aminoalkoxy complexes of rhenium [(CO)3Re(μ2-O∩NHR)]2

Article abstract of DOI:10.1016/S1387-7003(03)00119-9

The allyl rhenium complex Re(CO)₄ (η³-C₃H₅) (1) reacts with the N substituted amino alcohols 2a-f to give the N substituted dimeric μ₂-O-bridged tricyclic aminoalkoxy complexes of rhenium of the type

Full text of DOI:10.1016/S1387-7003(03)00119-9

Inorganic Chemistry Communications 6 (2003) 845–851
www.elsevier.com/locate/inoche
Synthesis of the dimeric, N substituted l2-O aminoalkoxy
complexes of rhenium ½ðCOÞ Reðl2-O\NHRފ
3
2
*
R. Wilberger, H. Piotrowski, P. Mayer, M. Vogt, I.-P. Lorenz
Department of Chemistry, Ludwig-Maximilians University Munich, Butenandtstraße 5-13, D-81377 Munich, Germany
Received 17 February 2003; accepted 8 March 2003
Abstract
The allyl rhenium complex ReðCOÞ4ðg3-C3H5Þ (1) reacts with the N substituted amino alcohols 2a–f to give the N substituted
dimeric l2-O-bridged tricyclic aminoalkoxy complexes of rhenium of the type ½ðCOÞ3Reðl2-O\NHRފ (3a–f). The compounds have
2
been characterized by spectroscopic (IR, NMR, MS), analytical (C, H, N) and X-ray diffraction techniques (3a–f).
Ó 2003 Elsevier Science B.V. All rights reserved.
Keywords: Rhenium complexes; Tricyclic complexes; b-Amino alcohol; X-ray
1. Introduction
In this paper, the formation of differently N-
substituted, binuclear, rhenium complexes containing
two l2-O bridges is reported, where the oxygen is
Recently we reported on the synthesis of the dimeric
l2-O aminoalkoxy complexes of rhenium ½ðCOÞ Re
part of
a
chelating 1,2-aminooxyethane ligand,
ðl2-O\NH2ފ which are obtained\ from ðCOÞ43Re
forming five-membered ring systems with the rhenium
centers.
2
ðg3-C3H5Þ and amino alcohols HO NH2. They can
be transformed with acetone into their condensation reac-
tion products of the type ½ðCOÞ3Reðl2-O\N@CMe2ފ
2
[1]. Our complexes can be added to the few examples of
polynuclear oxygen bridged rhenium complexes which
have been hitherto reported. The binuclear rhenium
complexes ½NEt4Š½fðCOÞ3Reg2ðl-OMeÞ3Š [2] and
½fReðCOÞ3g2ðl-OMeÞ2ðl-DPPMފ [3], with three l2-
bridging ligands have been described in the literature.
Beck and co-workers [4] also reported a bi- and tetra-
nuclear methoxy bridged rhenium complex, and
Struchkov and co-workers [5] obtained a binuclear
rhenium complex by the reaction of potassium o-
phenylazophenolate with ReðCOÞ5Br, and determined
its molecular structure. In all cases the l2-O bridge is
derived from alkoxy or aryloxy ligands.
2. Experimental
To exclude oxygen, all operations were carried out
under an argon atmosphere in dry and argon-satu-
rated solvents [6]. ReðCOÞ4ðg3-C3H5Þ (1) was prepared
according to the literature procedures [7]. 2-Amino
ethanol, 1-amino-propane-2-ol, 2-amino phenol and 2-
amino benzyl alcohol were used as purchased. NMR
spectra were recorded on Jeol Eclipse 270 (1H: 270.17
MHz and 13C: 67.94 MHz) and Jeol EX 400 (1H: 399.78
MHz and 13C: 100.54 MHz) in [D6]-acetone and CD2Cl2
solvents. Mass spectra were obtained on a Jeol MSta-
tion JMS 700. IR spectra were measured on Nicolet 520
FT-IR-Spectrometer and Perkin–Elmer Spectrum One
FT-IR. Raman spectra were recorded using a Perkin–
Elmer Spectrum 2000 NIR FT-Raman. Elemental
analyses were performed on a Heraeus Elementar Vario
EL.
* Corresponding author. Tel.: +49-89-2180-77486; fax: +49-89-2180-
77867.
E-mail address: ipl@cup.uni-muenchen.de (I.-P. Lorenz).
1387-7003/03/$ - see front matter Ó 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S1387-7003(03)00119-9

846
R. Wilberger et al. / Inorganic Chemistry Communications 6 (2003) 845–851
3. Synthesis
3.86%. Calc. for C14H20N2O8Re2 (716.74 g/mol): C,
23.46%; H, 2.81%; N, 3.91%. MS (DEI) m=z (%):
716.2 (83) [Mþ], 688.2 (100) [Mþ–CO], 660.2 (42) [Mþ–2
CO], 632.2 (36) [Mþ–3 CO], 604.3 (70) [Mþ–4 CO],
576.3 (24) [Mþ–5 CO], 548.2 (8) [Mþ–6 CO], 516.2 (12),
473.2 (12), 359.2 (21) [Mþ/2+H], 329.2 (44), 301.2 (11),
272.2 (10).
3.1. General procedure for 3a–f
Complex 1 and one equivalent of the amino alcohol
2a–f were dissolved in 10 cm3 octane and refluxed for 2
h. The solvent was then evaporated and the colorless
residue was washed with pentane (10 cm3) and dried in
vacuum.
3.1.3. trans-Bis½5-tert-butyl-1,1,1-tricarbonyl-azað5Þ-l-
oxað2Þ-rhenað1Þ-cyclopentaneŠ ð3cÞ
3.1.1. trans-Bis½1,1,1-tricarbonyl-5-methyl-azað5Þ-l-oxa
ð2Þ-rhenað1Þ-cyclopentaneŠ ð3aÞ
159.0 mg (0.469 mmol) 1 and 46.5 ll (0.397 mmol) N
tert-butylamino ethanol (2c). Yield: 178 mg (0.230
1
90.9 mg (0.268 mmol) 1 and 21.4 ll (0.268 mmol) 2-
methylamino ethanol (2a). Yield: 90 mg (0.131 mmol,
mmol, 98%), colourless solid, m.p. >270 °C (dec.). H
NMR (399.79 MHz, CD2Cl2): d 1.50 (s, 18 H, CH3),
2.80–2.89 (m, 2 H, N–HCH), 3.54–3.62 (m, 2 H, N–
HCH), 3.71 (br, 2 H, N–H), 4.24–4.31 (m, 2 H, O–
1
98%), colourless solid, m.p. >220 °C (dec.). H NMR
(270.17 MHz, [D6]-acetone): d 2.65–2.74 (m, 2 H, N–
CH2), 3.28 (s, 6 H, N–CH3), 3.87–3.98 (m, 2 H, N–
1
HCH), 4.35–4.41 (m, 2 H, O–HCH). 13Cf Hg NMR
CH2), 4.18–4.38 (m, 4 H, O–CH2). 13Cf Hg NMR
(100.64 MHz, CD2Cl2): d 28.75 (C–ðCH3Þ3), 45.67 (N–
CH2), 57.39 ðC–ðCH3Þ3Þ, 76.82 (O–CH2), 196.16,
198.29, 206.34 (CO). IR (KBr) [cmÀ1]: 3238.3 s (m N–H),
3018.5 w, 2981.9 s (m CH2), 2930.7 m (m CH2), 2886.7 s (m
CH2), 2007.4 vs (m CO, a1), 1877.6 vs (m CO, e), 1631.2 m
(d NH), 1477.8 vs (d CH2), 1466.3 s (d CH2), 1397.1 vs (d
C(CH3Þ3), 1379.0 s (d C(CH3Þ3), 1194.3 s, 1137.6 s,
1086.0 vs, 1041.5 s, 1015.0 m, 916.6 m, 879.9 m, 666.0 m,
652.6 m, 590.9 m, 562.4 m, 535.6 vs, 507.9 s, 478.9 s,
437.8 m, 396.3 m, 343.0 m. IR (CH2Cl2) [cmÀ1]: 2010.4
vs (m CO, a1), 1895.3 vs (m CO, e). Anal. found: C,
27.74%; H, 3.39%; N, 3.59%. Calc. for C18H28N2O8Re2
(772.85 g/mol): C, 27.97%; H, 3.65%; N, 3.63%. MS
(DEI) m=z (%): 772 (46) [Mþ], 744 (80) [Mþ–CO], 716
(14) [Mþ–2 CO], 688 (7) [Mþ–3 CO], 660 (21) [Mþ–4
CO], 632 (8) [Mþ–5 CO], 604 (10) [Mþ–6 CO].
1
(67.94 MHz, [D6]-acetone): d 44.89 (N–CH3), 53.17 (N–
CH2), 78.73 (O–CH2), 196.63, 196.99, 198.80 (CO). IR
(KBr) [cmÀ1]: 3266.2 s (m N–H), 2985.3 w (mCH2), 2947.1
m (m CH2), 2923.5 m (mCH2), 2876.5 s (m CH2), 2817.7 w
(m N–CH3), 2361.7 m, 2332.3 m, 2011.9 vs (m CO, a1),
1885.3 vs (m CO, e), 1475.3 s (dCH2), 1463.4 m (d CH2),
1422.8 m, 1404.5 m, 1355.1 w, 1288.5 w, 1188.1 m,
1083.0 s, 1068.0 m, 1039.3 s (m C–O), 982.8 m, 884.1 s,
667.2 m, 644.2 m, 551.4 s, 514.7 s, 491.2 s, 358.5 w. IR
(CH2Cl2) [cmÀ1]: 2011.0 vs (m CO, a1), 1898.2 vs (m CO,
e). Anal. found: C, 21.21%; H, 2.37%; N, 3.85%. Calc.
for C12H16N2O8Re2 (688.69 g/mol): C, 20.93%; H,
2.34%; N, 4.07%. MS (DEI) m=z (%): 688.5 (64) [Mþ],
660.6 (72) [Mþ–CO], 632.6 (24) [Mþ–2 CO], 604.5 (30)
[Mþ–3 CO], 576.5 (61) [Mþ–4 CO], 548.5 (22) [Mþ–5
CO], 345.4 (15) [Mþ/2+H].
3.1.4. trans-Bis½1,1,1-tricarbonyl-5-phenyl-azað5Þ-l-oxað2Þ-
rhenað1Þ-cyclopentaneŠ ð3dÞ
3.1.2. trans-Bis½1,1,1-tricarbonyl-5-ethyl-azað5Þ-l-oxað2Þ-
rhenað1Þ-cyclopentaneŠ ð3bÞ
114.5 mg (0.337 mmol) 1 and 42.1 ll (0.337 mmol) 2-
anilino ethanol (2d). Yield: 132 mg (0.162 mmol, 96%),
109.9 mg (0.324 mmol) 1 and 29.3 ll (0.300 mmol) 2-
ethylamino ethanol (2b). Yield: 100 mg (0.140 mmol,
1
colourless solid, m.p. >230 °C. H NMR (270.17 MHz,
1
86%), colourless solid, m.p. >250 °C (dec.). H NMR
CD2Cl2): d 3.35–3.52 (m, 2 H, N–HCH), 4.02–4.15 (m, 2
H, N–HCH), 4.41–4.65 (m, 4 H, O–CH2), 7.43–7.55 (m,
3
(400.18 MHz, CD2Cl2): d 1.44 (t, 6 H, J ¼ 7:12 Hz,
1
NH–CH2–CH3), 2.66–2.75 (m, 2 H, NH–HCH–CH2–
O), 3.28–3.38 (m, 2 H, NH–HCH–CH3), 3.46 (br, 2 H,
NH), 3.52–3.62 (m, 2 H, NH–HCH–CH3), 3.79–3.87
(m, 2 H, NH–HCH–CH2–O), 4.25–4.31 (m, 2 H, NH–
CH2–HCH–O), 4.34–4.40 (m, 2 H, NH–CH2–HCH–O).
10 H, Ar–H). 13Cf Hg NMR (67.93 MHz, CD2Cl2): d
53.80 (N–CH2), 78.44 (O–CH2), 121.27 (o–Ar–C),
126.71 (p–Ar–C), 130.11 (m–Ar–C), 147.35 (Ar–Cq). IR
1
13Cf Hg NMR (100.64 MHz, CD2Cl2): d 15.03 (NH–
CH2–CH3), 50.89 (NH–CH2–CH2–O), 52.07 (NH–
CH2–CH3), 77.82 (NH–CH2–CH2-O), 196.29 (CO),
197.45 (CO), 198.33 (CO). IR (KBr) [cmÀ1]: 3248 m
(m NH), 2965 w (m CH2), 2894 m (m CH2), 2006 vs (m CO,
a1), 1889 vs (m CO, e), 1870 vs (m CO, e), 1622 w, 1473 m
(d CH2), 1455 w, 1411 m, 1249 w, 1182 w, 1125 w, 1090
m, 1051 s, 898 m, 810 w, 664 w, 549 m, 536 w, 510 m,
489 m, 385 w. IR (CH2Cl2) [cmÀ1]: 2010 vs (m CO, a1),
1896 vs (m CO, e). Anal. found: C, 23.47%; H, 2.78%; N,
Scheme 1. Synthesis of 3a–f.

R. Wilberger et al. / Inorganic Chemistry Communications 6 (2003) 845–851
847
(KBr) [cmÀ1]: 3237.6 s (m N–H), 3089.6 w (m Ar–H),
3049.7 w (m Ar–H), 3024.1 w (m Ar–H), 2955.8 w (mCH2),
2927.3 m (m CH2), 2878.9 s (mCH2), 2013.0 vs (m CO, a1),
1909.8 vs, 1884.9 vs (m CO, e), 1598.5 s, 1494.7 m (m
C@C), 1477.3 s (d CH2), 1405.6 m, 1240.3 m, 1212.6 m,
1142.0 m, 1076.7 m, 1050.5 s (m C–O), 1008.9 m, 918.7 s,
893.6 w, 759.5 s (c Ar), 695.0 (c Ar), 665.0 w, 641.1 w,
574.4 w, 554.3 m, 521.2 m, 509.9 s, 454.8 m, 349.6 w. IR
(CH2Cl2) [cmÀ1]: 2015.0 vs (m CO, a1), 1907.9 vs, 1892.9
vs (m CO, e). Anal. found: C, 32.43%; H, 2.50%; N,
3.43%. Calc. for C22H20N2O8Re2 (812.83 g/mol): C,
32.51%; H, 2.48%; N, 3.45%. MS (DEI) m=z (%): 813
(32) [Mþ], 785 (36) [Mþ–CO], 757 (1) [Mþ–2 CO], 729
(38) [Mþ–3 CO], 701 (19) [Mþ–4 CO], 673 (17) [Mþ–5
CO].
3.53 (m, 2 H, N–HCH), 4.02 (br, 2 H, N–H), 4.21–4.40
3
(m, 6 H, O–CH2, Ph–HCH), 4.80 (dd, J ¼ 13:80 Hz,
2J ¼ 3:93 Hz, 2 H, Ph–HCH), 7.38–7.50 (m, 10 H,
1
Ar–H). 13Cf Hg NMR (67.93 MHz, CD2Cl2): d 50.95
(N–CH2), 61.48 (Ph–CH2), 77.77 (O–CH2), 128.54
(o–Ar–C), 128.63 (p–Ar–C), 129.11 (m–Ar–C), 136.29
(Ar–Cq). IR (KBr) [cmÀ1]: 3252.9 s (m N–H), 3091.8 w
(m Ar–H), 3062.5 w (m Ar–H), 3040.5 w (m Ar–H), 3003.9
w (m Ar–H), 2974.6 w (m CH2), 2952.6 m (m CH2), 2923.3
m (m CH2), 2879.4 s (m CH2), 2009.6 vs (m CO, a1), 1905.1
vs, 1881.6 vs (m CO, e), 1497.0 m (m C@C), 1472.7 s
(d CH2), 1460.8 s (d CH2), 1410.5 vs, 1206.1 m, 1143.7 s,
1069.6 vs, 1045.0 s, 985.8 vs, 964.9 m, 916.7 w,
873.6 m, 758.5 s (c Ar), 702.9 (c Ar), 663.8 w, 639.4 m,
608.3 m, 544.7 vs, 524.7 s, 511.0 vs, 497.3 s, 478.0 s,
441.7 m, 406.1 w, 360.0 w, 337.5 m. IR (CH2Cl2) [cmÀ1]:
2011.1 vs (m CO, a1), 1898.5 vs (m CO, e). RAMAN
[cmÀ1]: 3249 (m N–H), 3076 (m Ar–H), 3041 (m Ar–H),
2976 (m CH2), 2958 (m CH2), 2925 (m CH2), 2877 (m CH2),
2021 (m CO, a1), 1898, 1866 (m CO, e), 1604 (m C@C),
1587 (m C@C), 1462 (d CH2), 1451, 1411, 1297, 1206,
1184, 1074, 1030, 1004, 876, 817, 761 (c Ar), 652, 621,
3.1.5. trans-Bis½5-benzyl-1,1,1-tricarbonyl-azað5Þ-l-oxað2Þ-
rhenað1Þ-cyclopentaneŠ ð3eÞ
92.2 mg (0.272 mmol) 1 and 39.1 ll (0.272 mmol) 2-
benzylamino ethanol. Yield: 113 mg (0.134 mmol, 99%),
1
colourless solid, m.p. >170 °C (dec.). H NMR (270.17
MHz, CD2Cl2): d 2.60–2.73 (m, 2 H, N–HCH), 3.40–
Table 1
X-ray structure analyses of 3a–c [8]
3a
3b
3c
Empirical formula
C12H16N2O8Re2
C14H20N2O8Re2
C18H28N2O8Re2
Formula weight (g/mol)
Crystal size (mm)
Crystal colour, habit
Crystal system
688.67
716.72
772.82
0:22 ꢀ 0:20 ꢀ 0:10
Colourless prismatic
Monoclinic
P21=n
7.91690(10)
12.10470(10)
8.87520(10)
90
0:20 ꢀ 0:12 ꢀ 0:07
Colourless block
Monoclinic
C2/c
0:41 ꢀ 0:29 ꢀ 0:17
Colourless prismatic
Monoclinic
P21=n
8.3633(9)
11.0490(8)
12.7436(14)
90
Space group
ꢀ
a (A)
ꢀ
19.0324(16)
7.1218(4)
13.7330(12)
90
b (A)
ꢀ
c (A)
a (°)
b (°)
c (°)
93.5172(5)
90
93.994(10)
90
104.529 (13)
90
ꢀ3
Volume (A )
848.923(16)
2
2.694
1856.9(2)
4
2.564
1139.93(2)
2
2.252
Z
Density calc. (g cmÀ3
)
Absorption coefficient (mmÀ1
)
14.288
632
13.070
1328
10.654
728
F ð000Þ
Index ranges
À9 6 h 6 10
À15 6 k 6 15
À11 6 l 6 11
2.85–27.47
16715
À24 6 h 6 24
À9 6 k 6 8
À18 6 l 6 18
2.15–27.97
7724
À11 6 h 6 11
À12 6 k 6 14
À16 6 l 6 16
2.47–27.92
8718
h-Range (°)
Reflections collected
Independent reflections
Observed reflections
Parameter/restrains
R1=wR2 (all data)
R1=wR2 (final)
1942
1798
2219
1920
2708
2294
110/0
158/0
139/0
0.0310/0.0713
0.0287/0.0698
1.271
0.0236/0.0377
0.0179/0.0370
1.016
0.0383/0.0794
0.0317/0.0774
1.061
Goodness of fit
Min./max. qe (e A )
ꢀ3
)2.952/0.911
200(2)
)1.260/0.518
200(2)
)3.253/0.949
298(2)
Temperature (K)
Diffractometer used
Scan type
Nonius Kappa CCD
Area detection
SIR97
Stoe IPDS
Area detection
SHELXS-97
SHELXL-97
Stoe IPDS
Area detection
SHELXS-97
SHELXL-97
Solution
Refinement
SHELXL-97

848
R. Wilberger et al. / Inorganic Chemistry Communications 6 (2003) 845–851
522, 515, 486, 441, 290, 244, 140, 113. Anal. found: C,
34.53%; H, 2.99%; N, 3.46%. Calc. for C24H24N2O8Re2
(840.88 g/mol): C, 34.28%; H, 2.88%; N, 3.33%. MS
(DEI) m=z (%): 840.7 (53) [Mþ], 812.7 (85) [Mþ–CO],
784.7 (6) [Mþ–2 CO], 756.7 (35) [Mþ–3 CO], 728.7 (20)
[Mþ–4 CO], 700.6 (10) [Mþ–5 CO].
1056.3 vs (m C–O), 1004.1 m, 930.9 vs (d Ring), 883.4 s (d
Ring), 835.6 m, 768.2 s, 666.0 s, 642.7 s, 550.1 vs, 514.4
vs, 500.4 s, 484.4 vs IR (CH2Cl2) [cmÀ1]: 2008.0 vs (m
CO, a1), 1891.9 vs (m CO, e). RAMAN [cmÀ1]: 3085 (m
Az–H), 3010 (m Az–H), 2957 (m CH2), 2930 (m CH2),
2878 (m CH2), 2011 (m CO, a1), 1898, 1877, 1865, 1849 (m
CO, e), 1464 (d CH2), 1456, 1250, 1190, 1166, 1132,
1099, 1063, 929, 887, 833, 792, 768, 647, 588, 534, 522,
513, 497, 449, 395, 288, 242, 216, 145, 130, 103. Anal.
found: C, 23.87%; H, 2.28%; N, 4.08%. Calc. for
C14H16N2O8Re2 (712.71 g/mol): C, 23.59%; H, 2.26%;
N, 3.93%. MS (DEI) m=z (%): 712.5 (83) [Mþ], 684.5
(66) [Mþ–CO], 656.5 (6) [Mþ–2 CO], 628.5 (57) [Mþ–3
CO], 600.5 (30) [Mþ–4 CO], 572.4 (100) [Mþ–5 CO],
544.5 (26) [Mþ–6 CO], 357.4 (17) [Mþ/2+H].
3.1.6. trans-Bis½{l2-Oðg2-N,OÞ-2-aziridinylethoxy}tricar-
bonyl-rheniumðIÞ Š ð3fÞ
181.5 mg (0.535 mmol) 1 and 42.8 ll (0.535 mmol) N-
hydroxyethyl aziridine. Yield: 176 mg (0.247 mmol,
1
92%), colourless solid, m.p. >275 °C (dec.). H NMR
(400.18 MHz, [D6]-acetone): d 2.59-2.64 (m, 2 H, Az–
HCH), 2.85–2.89 (m, 2 H, Az–HCH), 2.90–2.95 (m, 4 H,
Az–HCH), 3.20–3.35 (m, 4 H, N–CH2), 4.26–4.36 (m,
1
4 H, O–CH2). 13Cf Hg NMR (100.64 MHz, [D6]-
acetone): d38.71 (Az–CH2), 38.94 (Az–CH2), 62.83 (N–
CH2), 79.50 (O–CH2). IR (KBr) [cmÀ1]: 3003.9 w
(m Az–H), 2960.0 w (m CH2), 2930.7 s (m CH2), 2879.4 s
(m CH2), 2520.5 w, 2396.0 w, 2004.5 vs (m CO, a1), 1869.7
vs (m CO, e), 1463.7 s (d CH2), 1454.7 m (d CH2), 1371.3
w, 1347.7 w, 1251.2 vs, 1166.7 m, 1129.3 s, 1099.7 m,
4. Results and discussion
The reaction of the p-allyl complex ReðCOÞ4ðg3-
C3H5Þ (1) with a series of N substituted b-amino alco-
hols RHNCH2CH2OH (2a–f) in boiling octane results
Table 2
X-ray structure analyses of 3d–f [8]
3d
3e
3f
Empirical formula
C22H20N2O8Re2
C24H24N2O8Re2
C14H16N2O8Re2
Formula weight (g/mol)
Crystal size (mm)
Crystal colour, habit
Crystal system
812.80
840.87
712.69
0:25 ꢀ 0:20 ꢀ 0:15
Colourless prismatic
Trigonal
R3
0:31 ꢀ 0:055 ꢀ 0:05
Colourless prismatic
Monoclinic
P21=c
11.01170(20)
6.42940(10)
18.43990(29)
90
0:15 ꢀ 0:10 ꢀ 0:06
Colourless prismatic
Monoclinic
P21=n
6.88180(10)
9.52910(10)
13.76730(10)
90
Space group
ꢀ
a (A)
ꢀ
24.3994(2)
24.3994(2)
10.0548(2)
90
b (A)
ꢀ
c (A)
a (°)
b (°)
c (°)
90
120
100.3726(7)
90
99.4670(10)
90
ꢀ3
Volume (A )
5183.97(12)
9
2.343
1284.184(37)
2
890.527(17)
2
2.658
Z
Density calc. (g cmÀ3
)
2.17464(6)
9.468
792
Absorption coefficient (mmÀ1
)
10.549
3420
13.626
656
F ð000Þ
Index ranges
À27 6 h 6 34
À34 6 k 6 34
À14 6 l 6 14
1.67–30.03
28163
À14 6 h 6 14
À8 6 k 6 8
À23 6 l 6 23
2.66–27.48
20653
À7 6 h 6 7
À10 6 k 6 10
À15 6 l 6 15
2.61–24.00
12686
h-Range (°)
Reflections collected
Independent reflections
Observed reflections
Parameter/restrains
R1=wR2 (all data)
R1=wR2 (final)
3341
3221
2938
2783
1402
1297
154/0
211/0
118/0
0.0255/0.0840
0.0206/0.0643
1.421
0.0282/0.0566
0.0244/0.0557
1.263
0.0226/0.0412
0.0177/0.0392
1.123
Goodness of fit
Min./max. qe (e A )
ꢀ3
)2.755/0.976
200(2)
)1.592/0.917
200
)1.529/1.003
200(2)
Temperature (K)
Diffractometer used
Scan type
Nonius Kappa CCD
Area detection
SIR97
Nonius Kappa CCD
Area detection
SHELXS-97
SHELXL-97
Nonius Kappa CCD
Area detection
SIR97
Solution
Refinement
SHELXL-97
SHELXL-97

R. Wilberger et al. / Inorganic Chemistry Communications 6 (2003) 845–851
849
ꢀ
Fig. 1. Molecular structure of 3a: Selected bond lengths (A) and angles
(°): Re(1)–C(1) 1.907(5), Re(1)–C(3) 1.912(5), Re(1)–C(2) 1.913(6),
Re(1)–O(4) 2.136(3), Re(1)–O(4A) 2.150(4), Re(1)–N(6) 2.225(4),
C(1)–O(1) 1.155(6), C(2)–O(2) 1.151(8), C(3)–O(3) 1.150(7), N(6)–C(6)
1.492(7); O(4)–Re(1)–O(4A) 72.56(14), Re(1)–O(4)–Re(1A) 107.44(14).
ꢀ
Fig. 3. Molecular structure of 3c: Selected bond lengths (A) and angles
(°): Re(1)–C(5) 1.896(6), Re(1)–C(4) 1.901(5), Re(1)–C(6) 1.909(6),
Re(1)–O(1) 2.143(4), Re(1)–O(1A) 2.148(3), Re(1)–N(1) 2.255(4),
O(4)–C(4) 1.142(7), O(6)–C(6) 1.143(8), O(5)–C(5) 1.152(7), N(1)–C(3)
1.513(7); O(1)–Re(1)–O(1A) 72.97(14), Re(1)–O(1)–Re(1A) 107.03(14).
ꢀ
Fig. 2. Molecular structure of 3b: Selected bond lengths (A) and angles
(°): Re(1)–C(1) 1.904(4), Re(1)–C(2) 1.908(4), Re(1)–C(3) 1.909(3),
Re(1)–O(4) 2.144(3), Re(1)–O(4A) 2.147(2), Re(1)–N 2.218(3), O(1)–
C(1) 1.152(5), O(2)–C(2) 1.152(5), O(3)–C(3) 1.152(5), N–C(6)
1.494(5); O(4)–Re(1)–O(4A) 73.08(11), Re(1)–O(4)–Re(1A) 106.92(11).
ꢀ
Fig. 4. Molecular structure of 3d: Selected bond lengths (A) and angles
(°): Re(1)–C(2) 1.909(5), Re(1)–C(1) 1.916(5), Re(1)–C(3) 1.919(4),
Re(1)–O(11A) 2.154(3), Re(1)–O(11) 2.161(3), Re(1)–N(41A) 2.231(4),
C(1)–O(1) 1.154(6), C(2)–O(2) 1.151(6), C(3)–O(3) 1.145(6), N(41)–
C(111) 1.453(5); O(11A)–Re(1)–O(11) 73.67(13), Re(1A)–O(11)–Re(1)
106.33(13).
in the formation of binuclear rhenium complexes of the
type ½ðCOÞ3Reðl2-O\NHRފ (3a–f) (Scheme 1). Even
2
N-hydroxyethyl aziridine (2f) is suitable for this reac-
tion, which, as in all cases, combines a nucleophilic ni-
trogen donor with an additional acidic OH group in the
b-position.
Initially, a CO group is eliminated by thermolysis
and is substituted by the nitrogen atom of the amino
alcohol. The hydroxy group of the amino alcohol then

850
R. Wilberger et al. / Inorganic Chemistry Communications 6 (2003) 845–851
ꢀ
Fig. 6. Molecular structure of 3f: Selected bond lengths (A) and angles
(°): Re(1)–C(12) 1.898(5), Re(1)–C(11) 1.904(5), Re(1)–C(13) 1.906(5),
Re(1)–O(1) 2.136(3), Re(1)–O(1A) 2.158(3), Re(1)–N(3) 2.208(4),
C(11)–O(11) 1.164(6), C(12)–O(12) 1.157(6), C(13)–O(13) 1.165(6),
N(3)–C(4) 1.485(6), N(3)–C(5) 1.487(6), C(4)–C(5) 1.472(8); O(1)–
Re(1)–O(1A) 74.05(12), Re(1)–O(1)–Re(1A) 105.95(12), C(4)–N(3)–
C(5) 59.4(3), C(5)–C(4)–N(3) 60.4(3), C(4)–C(5)–N(3) 60.2(3).
perature stable (ꢁ200 °C). They are moderately soluble
in ketones and CH2Cl2 and are insoluble in pentane.
Only the ethyl substituted complex 3b shows moderate
solubility in boiling octane.
The IR spectra of 3a–f show two m(CO) absorptions
(A1 þ E, C3v local symmetry) at about 2010 and
1895 cmÀ1. No great substituent effects are observed,
although the wave numbers for the m(CO) mode E
slightly decrease with larger substituents at the nitrogen.
In the mass spectra of compounds 3a–f, the parent
peaks as well as peaks corresponding to compounds
resulting from the loss of up to six carbonyl groups are
observed. The hydrogen atoms in the ethylene bridge are
diastereotopic. Therefore, in the 1H NMR spectra of
3a–f, a multiplet for each hydrogen atom is observed.
The NMR shifts for the CH2 group vicinal to N are
about 2.7 and 3.8 ppm. Only the chemical shifts for the
phenyl substituted compound 3d and the aziridine
substituted compound 3f lie slightly down-field. The
ꢀ
Fig. 5. Molecular structure of 3e: Selected bond lengths (A) and angles
(°): Re(1)–C(3) 1.901(5), Re(1)–C(1) 1.907(5), Re(1)–C(2) 1.913(5),
Re(1)–O(4) 2.148(3), Re(1)–O(4A) 2.157(3), Re(1)–N 2.213(4), C(1)–
O(1) 1.157(6), C(2)–O(2) 1.151(6), C(3)–O(3) 1.163(6), N–C(6)
1.478(7); O(4)–Re(1)–O(4A) 73.04(12), Re(1)–O(4)–Re(1A) 106.96(12).
protonates the allyl group, which is subsequently elim-
inated as propene, and the free coordination site at
rhenium is occupied by the oxygen. The resulting 16
valence electron fragment is not stable and is therefore
stabilized by dimerization, forming the relatively stable
binuclear l2-alkoxy bridged rhenium complexes 3a–f.
Complexes 3a–f were obtained as colorless solids,
which are quite stable towards air and reasonably tem-
Table 3
Comparison of the most important bond lengths of 3a–f
ꢀ
Bond length (A)
3a
3b
3c
3d
3e
3f
R ¼ Me
R ¼ Et
R ¼ tBu
R ¼ Ph
R ¼ Bz
R ¼ Az
Re–N
N–R
2.225
1.492
2.136
2.150
2.218
1.494
2.144
2.147
2.255
1.513
2.143
2.148
2.231
1.453
2.154
2.161
2.213
1.478
2.148
2.157
2.208
1.485
2.136
2.158
1.487
Re–O (5-ring)
Re–O

R. Wilberger et al. / Inorganic Chemistry Communications 6 (2003) 845–851
851
NMR shifts for the CH2 group vicinal to O are all about
4.3 and 4.4 ppm.
the steric effect of the different substituents at the
nitrogen atom: Whereby the larger the R substituent is,
the longer the N–R bond length is. On the other hand,
the geometry of the planar ðRe–OÞ2 four-membered ring
remains virtually unaltered.
A comparison of the 13C NMR data of 3a–f also shows
the influence of the different substituents at the nitrogen.
As the size of the substituents increases (3a–c), the signal
of the CH2 group next to the nitrogen atom shifts to
higher field. The influence of a phenyl group (3d) is
comparable to a methyl group (3a) and a benzyl group
(3e) is comparable to an ethyl group (3b). On the other
hand, the signal for the N-hydroxyethyl derivative 3f lies
down-field. The NMR shifts for the CH2 group next to the
oxygen atom may be correlated with the N–CH2 group,
but the effect of the substituent is significantly smaller,
because of the larger distance to the nitrogen.
References
[1] R. Wilberger, H. Piotrowski, P. Mayer, I.-P. Lorenz, Inorg. Chem.
Commun. 5 (2002) 897–902.
[2] V.G. Albano, G. Ciani, M. Freni, P. Romiti, J. Organomet. Chem.
96 (1975) 259–264.
[3] P.M.N. Low, Y.L. Yong, Y.K. Yan, T.S.A. Hor, S.-L. Lam, K.K.
Chan, C. Wu, S.C.F. Au-Yeung, Y.-S. Wen, L.-K. Liu, Organo-
metallics 15 (1996) 1369–1375.
The compositions and structures of the binuclear rhe-
nium complexes obtained (3a–f) were confirmed by X-ray
structure analyses. The collection data are summarized in
Tables 1 and 2; the molecular structures and the most
important bond lengths and angles are given in Figs. 1–6.
The central ðRe–OÞ2 four-membered ring is almost
planar, and the two rhenium centers are surrounded in a
distorted octahedral arrangement with three CO ligands,
two oxygen and one nitrogen atom. Because of the sp3
hybridization of the nitrogen and carbon atoms, a
slightly distorted envelope conformation in the five-
membered ring is observed, similar to cyclopentane, and
the rhenium atom lies above the ring plane.
[4] B. Aechter, K. Polborn, W. Beck, Z. Anorg. Allg. Chem. 627
(2001) 43–54.
[5] G.G. Aleksandrov, V.V. Derunov, A.A. Johansson, Y.T. Struch-
kov, J. Organomet. Chem. 188 (1980) 367–371.
[6] Trocknen im Labor, brochure from the series, Reagenzien, Merck,
Darmstadt.
€
[7] R. Kramer, E. Lippmann, K. Noisternig, M. Steimann, U. Nagel,
W. Beck, Chem. Ber. 126 (1993) 927–932.
[8] Crystallographic data for structures 3a–f reported in this paper
have been deposited with the Cambridge Crystallographic Data
Centre as supplementary publications no. CCDC 206543 (3a),
CCDC 206538 (3b), CCDC 206540 (3c), CCDC 506541 (3d),
CCDC 506539 (3e), and CCDC 206542 (3f). Copies of the data can
be obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB2 1 EZ, UK (fax: int. code +44 (1223)
336-033, e-mail: deposit@ccdc.cam.ac.uk).
A comparison of the most important bond lengths of
the molecular structures of 3a–f (Table 3) clearly shows