Chloro-N,N’-bis{1-[1-(n-hexyl)-3-methyl-5-oxo-2-pyrazolin-
(CQN), 1043 (MnRN), 606 (Mn–N), 473 (Mn–O). Anal.
.
28 46 7 2
calcd for C H N O Mn: C, 59.25; H, 8.17; N, 17.27; Mn,
4
-yl]}ethyliden-1-yl}-1,2-diaminopropanemanganese(III) H
2
O (2b).
Yield 91%; mp 55 1C. IR (KBr) n/cm : 3300 (OH), 1572
CQN), 602 (Mn–N), 470 (Mn–O), 323 (Mn–Cl). Anal. calcd
for C H N O MnCl: C, 54.68; H, 7.82; N, 14.20; Cl, 5.98; Mn,
ꢁ
1
9.68; found: C, 59.60; H, 8.20; N, 17.30; Mn, 9.72.
(
2
7
46
6
3
Nitrogen transfer reactions
9
.26. Found: C, 54.90; H, 7.90; N, 13.80; Cl, 5.60; Mn, 8.98.
Styrene (0.04 mmol, 0.05 ml) and trifluoroacetic anhydride
(0.36 mmol, 0.05 ml) were dissolved in methylene chloride (15
ml) and then 3 (0.36 mmol) was added at once. The solution
was stirred for 1 h and then neutralized by adding a mixture of
Chloro–N,N’-bis{1-[1-(n-hexyl)-3-methyl-5-oxo-2-pyrazolin-
.
-yl]propyliden-1-yl}ethylenediaminomanganese(III) 2H O (2c).
2
4
ꢁ
1
Yield 80%; mp 87 1C. IR (KBr) n/cm : 3250 (OH), 1575
CQN), 604 (Mn–N), 478 (Mn–O), 323 (Mn–Cl). Anal. calcd
for C28 MnCl: C, 53.80; H, 8.10; N, 13.40; Cl, 5.70;
Mn, 8.80; found: C, 54.00; H, 8.10; N, 13.30; Cl, 5.70; Mn,
.60.
3
aqueous saturated NaHCO (5 ml) and THF (5 ml). The
(
organic phase was analyzed by GC-MS (Hewlett Packard
HP-5890 series 2 gas chromatograph and HP 5972 mass
spectrometer). Yields of N-(2-hydroxy-2-phenylethyl)-2,2,2-
trifluoroacetamide were 91, 75 and 77% when 3a, 3b and 3c
were used, respectively.
50 6 4
H N O
8
Synthesis of nitridomanganese(V) complexes (3). General
procedure
X-Ray crystallography
To a solution of complex 2 (0.50 mmol) in a CH Cl –CH OH
2
2
3
mixture (4 : 1, 50 ml) aqueous ammonia was added in one
portion (1.0 ml 25%, 7.0 mmol). The mixture was stirred
vigorously for 10 min and then bleach (3.3 ml 5.5% NaClO,
A blue-violet single crystal with dimensions of 0.25 ꢂ 0.24 ꢂ
3
0.13 mm was mounted on a Bruker SMART CCD area-
detector diffractometer with graphite monochromated Mo-
˚
2
.3 mmol) was added dropwise. The resulting biphasic mixture
Ka radiation (l = 0.710 73 A). A total of 9221 reflections
was stirred at room temperature until its color changed to blue-
violet. The product was extracted with methylene chloride,
then washed with water to neutral pH. The solution was then
concentrated in a rotary evaporator and the remaining materi-
al was crystallized from a 90 : 10 ethanol–water mixture.
were collected in the range 1.781 r y r 27.991 at 297 K, 6483
of which were independent (Rint = 0.062) and 3338 observed
with [I 4 2s(I)]. The structure was solved by direct methods
(SHELXS97) and successive difference Fourier syntheses, and
refined by full-matrix least-squares techniques with anisotropic
thermal parameters for all non-hydrogen atoms. Hydrogen
atoms were located theoretically and refined with a riding
model, both in position as well as in isotropic thermal para-
meters (SHELXL97). Crystal data for 3c: C H MnN O ,
Nitrido-N,N’-bis{1-[1-(n-hexyl)-3-methyl-5-oxo-2-pyrazolin-
-yl]ethyliden-1-yl}ethylenediaminomanganese(V) (3a). Yield
4
7
2
1
1
2
8
48
7
2
2%; mp 126 1C. H NMR d: 0.88 (t, 6 H, J = 6.3 Hz,
0
0
0
0
2
-5 ),
MW 569.67, triclinic, space group P-1, a = 9.2780(11),
˚
CH
.76 (m, 4 H, 2 CH
3
-6 ), 1.32 (m, 12 H, 2 CH
0
2
-3 , 2 CH
2
-4 and 2 CH
-2 ), 2.34, 2.39 (both s, 12 H, 4 CH ), 3.31
b = 13.5310(16), c = 13.9489(17) A, a = 113.953(3)1,
2
3
3
˚
b = 90.227(2)1, g = 102.320(2)1, U = 1555.4(3) A , Z = 2,
(
m, 2 H, CH
2
), 3.71 (m, 2 H, CH
13
2
), 3.82 (t, 4 H, J = 7.4 Hz,
0
ꢁ
3
D = 1.216 g cm , final R = 0.0672 and wR = 0.1961
0
c
1
2
2
2
3
1
CH -1 ). C NMR d: 13.90 (2 C-6 ), 17.26, 17.65 (2 C-7,
2
0
0
0
[I 4 2s(I)].
C-8), 22.50, 26.30, 29.20, 31.30 (2 C-5 , 2 C-4 , 2 C-2 , 2 C-
0
0
), 45.02 (2 C-1 ), 54.92 (2 C-9), 103.50 (2 C-4), 144.82 (2 C-3),
ꢁ
1
62.04 (2 C-5), 169.17 (2 CQN C-6). IR (KBr) n/cm : 1583
Acknowledgements
(
CQN), 1043 (MnRN), 607 (Mn–N), 474 (Mn–O). Anal.
calcd for C26 Mn: C, 57.87; H, 7.85; N, 18.17; Mn,
0.18; found: C, 58.10; H, 7.80; N, 18.20; Mn, 10.20.
42 7 2
H N O
This research was supported by the Universidad de Concep-
cion through a grant from Direccion de Investigacion (PDI
03.023.032-1.0) and FONDECYT 1040461. The graduate
scholarship for Mr. Fredy Perez was provided by the MECES-
UP Programme of the Chilean Government. The authors are
very grateful to Dr Marıa Teresa Garland from the Universi-
1
´
´
´
2
Nitrido-N,N’-bis{1-[1-(n-hexyl)-3-methyl-5-oxo-2-pyrazolin-
-yl]ethyliden-1-yl}-1,2-diaminopropanemanganese(V) (3b). Yield
´
4
6
1
1
0
9%; mp 40 1C. H NMR d: 0.81 (t, 6 H, J = 6.0 Hz, 2 CH -6 ),
´
3
0
0
0
.31 (m, 12H, 2 CH
=
2
-3 , 2 CH -4 and 2 CH
2
2
-5 ), 1.37 (d, 3 H, J
6.5 Hz, CH ), 1.65 (m, 4 H, 2 CH -2 ), 2.21, 2.29 (both s,
3
dad de Chile for the X-ray measurements.
0
2
1
4
1
3
2H, 4 CH
3
), 3.50 (m, 1 H, CH ), 3.67 (m, 1 H, CH
2
2
), 3.73 (m,
0
0
13
H, 2 CH -1 ), 3.96 (m, 1 H, CH). C NMR d: 13.97 (2C-6 ),
References
2
5.42 (2C-8), 17.26 (2C-7), 19.40 (C-10), 22.50, 26.32, 29.00,
0
1
(a) R. A. Sheldon and J. K. Kochi, Metal-Catalyzed Oxidation of
Organic Compounds, Academic Press, New York, 1981; (b) E. N.
Jacobsen, in Comprehensive Organometallic Chemistry II, eds. E.
W. Abel, F. G. A. Stone and G. Wilkinson, Pergamon Press,
Oxford, UK, 1995, vol. 12, p. 1097; (c) S.-I. Murahashi and
T. Naota, in Comprehensive Organometallic Chemistry II, eds. E.
W. Abel, F. G. A. Stone and G. Wilkinson, Pergamon Press,
Oxford, UK, 1995, vol. 12, p. 1177.
0
0
0
0
1.31 (2C-5 , 2 C-4 , 2 C-2 , 2 C-3 ), 45.04 (2C-1 ), 49.50, 49.80
(
1
2C-9), 104.00 (2C-4), 145.00 (2C-3), 164.30 (2C-5); 168.4,
ꢁ
1
69.10 (2CQN C-6). IR (KBr) n/cm : 1583 (CQN), 1048
(MnRN), 601 (Mn–N), 485 (Mn–O). Anal. calcd for
C H N O Mn: C, 58.58; H, 8.01; N, 17.71; Mn, 9.92; found:
C, 58.98; H, 8.10; N, 17.50; Mn, 9.60.
2
7
44
7
2
2
3
(a) E. N. Jacobsen, in Catalytic Asymmetric Synthesis, ed.
I. Ojima, VCH, New York, 1993, p. 159; (b) K. A. Jørgensen,
Chem. Rev., 1989, 89, 431; (c) R. A. Johnson and K. B. Sharpless,
in Catalytic Asymmetric Synthesis, ed. I. Ojima, VCH, New York,
Nitrido-N,N’-bis{1-[1-(n-hexyl)-3-methyl-5-oxo-2-pyrazolin-
-yl]propyliden-1-yl}ethylenediaminomanganese(V) (3c). Yield
7%; mp 105 1C. H NMR d: 0.80 (t, 6 H, J = 6.2 Hz,
4
6
2
2
1
1
993, p. 103; (d) E. J. Corey and M. C. Noe, J. Am. Chem. Soc.,
0
0
CH
CH
3
-6 ), 1.12 (t, 6 H, J = 7.6 Hz, 2 CH
0
3
), 1.25 (m, 12 H,
0
1996, 118, 11038; (e) H. C. Kolb, M. S. VanNieuwenhze and
K. B. Sharpless, Chem. Rev., 1994, 94, 2483.
0
2
-3 , 2 CH
2
-4 and 2 CH
2
-5 ), 1.69 (m, 4 H, 2 CH
), 2.72 (q, 4 H, J = 7.6 Hz, 2 CH ), 3.34 (m, 2 H,
2
-2 ), 2.28
(a) G. Li, H. H. Angert and K. B. Sharpless, Angew. Chem., Int.
Ed., 1997, 36, 2813; (b) J. Rudolph, P. C. Sennhenn, C. P. Vlaar
and K. B. Sharpless, Angew. Chem., Int. Ed., 1997, 36, 2810; (c) D.
Mansuy and J.-P. Mahy, in Metalloporphyrin Catalyzed Oxida-
tions, eds. F. Montanari and L. Casella, Kluwer Academic Pub-
lishers, Dordrecht, The Netherlands, 1994, p. 175; (d) D. A. Evans,
M. M. Faul and M. T. Bilodeau, J. Am. Chem. Soc., 1994, 116,
(s, 6 H, 2 CH
CH ), 3.61 (m, 2 H, CH
3
2
0
2
2
), 3.74 (t, 4 H, J = 7.4 Hz, 2 CH
0
2
-1 ).
1
3
C NMR d: 11.81 (2 C-9), 13.94 (2 C-6 ), 16.62 (2 C-7), 22.46
2 C-5 ), 23.34 (2 C-8), 26.31, 28.88, 31.28 (2 C-4 , 2 C-2 , 2 C-
0
0
0
(
0
0
), 45.07 (2 C-1 ), 54.24 (2 C-10), 102.18 (2 C-4), 144.38 (2 C-3),
3
1
ꢁ
1
62.49 (2 C-5), 173.83 (2 CQN C-6). IR (KBr) n/cm : 1585
2
86
N e w J . C h e m . , 2 0 0 5 , 2 9 , 2 8 3 – 2 8 7